REFINERY-WIDE OPTIMIZATION

by

XUAN LI, B.E. A DISSERTATION IN CHEMICAL ENGINEERING Submitted to the Graduate Faculty of Texas Tech University in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Approved

May, 2000

COPYRIGHT 2000, XUAN LI

ACKNOWLEDGEMENTS

Refinery-wide optimization would become "Mission Impossible" without innumerable help from other people. Many people have given help in many different ways. It is imperative for me to give them my appreciation. I want to express my sincere appreciation to Dr. James B. Riggs for providing me with the opportunity to study at Texas Tech University, for guiding me and encouraging me throughout the whole project, and for supporting me financially during the course of this work. His style of clarifying every statement and developing insight of every problem and his determination to get things done will influence me in my whole career. I also want to extend my sincere thanks to Dr. Theodore F. Wiesner for his guidance in my qualifying project. His fighting spirit and positive attitude show me the correct way to deal with obstacles. I would also like to thank my other committee members. Dr. Richard W. Tock and Dr. W. J. Bryan Oldham for their assistance in my Ph.D. research. Appreciation is extended to the industrial members of the Texas Tech Process Control Consortium for their financial support and invaluable inputs to my research. A special thanks go to Scott Boyden of Aspen Technology Incorporation and Dr. Charlie Cutler, for their input on my research. This work would not have much industrial relevance without the plant data obtained from the refinery considered in this work. I wish to express my appreciation to all the engineers and technicians who helped me during their busy schedule. I also wish to extend my thanks to Dr. Taskar and Robert Ellis for leading me through the modeling and optimization of reformer and FCCU and for introducing the NFL to me. Go Cowboys! I would also like to thank Joe, Marshall, and Matt, for their technical support on all computer issues. Special thanks go to Govindhakannan for reviewing my dissertation draft and for innumerous discussion on research and life, which is invaluable during the last one and a half years.

Finally, I would like to thank my parents for their love and support through the years. Lastly, I would like to dedicate this work to my dear wife, Jenny. Let us be together and start a more exciting life!

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TABLE OF CONTENTS

ACKNOWLEDGEMENTS ABSTRACT LIST OF TABLES LIST OF FIGURES CHAPTER 1. INTRODUCTION 2. LITERATURE REVIEW 2.1 Single-Unit Modeling and Feed Characterization 2.2 Refinery-Wide Optimization 3. CRUDE UNIT MODELING 3.1 Introduction 3.2 Atmospheric Tower Modeling 3.2.1 Feed Characterization 3.2.2 Side-Draw Product Calculation 3.2.3 Atmospheric Tower Furnace Calculation 3.2.4 Flash Zone Calculation 3.2.5 Side Stripper Calculation 3.2.6 Draw Tray Locations 3.2.7 Draw Tray Temperature Calculation 3.2.8 Side-Draw product temperatvire calculation 3.3 Vacuum Tower Modeling 3.3.1 Vacuum Tower Furnace Calculation 3.3.2 Side-Draw Product Calculation 3.3.3 Flash Zone Calculation 3.4 Separation Section Calculation 3.5 Comparison between the Developed Model and Tray-to-Tray ChemCad Model 3.6 Auxiliary Processes in the Crude Unit 3.6.1 Rerun Unit

ii vii ix xiv

1 8 8 14 16 16 20 22 28 36 36 42 43 45 48 50 51 52 52 54 55 63 64

IV

3.6.2 Residue Oil Solvent Extraction (ROSE) Unit 3.6.3 Debutanizer 3.6.4 Naphtha Splitter 4. FCC FEED CHARACTERIZATION AND MODEL BENCHMARKING 4.1 Process Overview 4.2 Model IV FCC Unit Modeling 4.3 FCC Feed Characterization 4.3.1 Volume and Weight of FCC Feed 4.3.2 FCC feed Characterization 4.3.3 Weight Fractions ofLumps in the FCC Feed 4.4 Model Benchmarking 4.5 FCC Gasoline Octane Model Modification 5. REFORMER FEED CHARACTERIZATION AND MODEL BENCHMARKING 5.1 Process Overview 5.2 Reformer Modeling 5.3 Reformer Feed Characterization 5.3.1 Naphtha Desulfurizer 5.3.2 Paraffins-Naphthenes-Aromatics (PNA) in the Reformer Feed 5.3.3 Molar Flow Rates of the Pseudo-Components in the Reformer Feed 5.4 Reformer Model Benchmarking 5.5 Average Reformer Operation 5.5.1 Operation Time Fraction of Low Severity 5.5.2 On-Stream Factor 5.5.3 Regeneration Cost 6. MODELING OF GAS PLANT, ALKYLATION UNIT AND DIESEL HYDROTREATER 6.1 Gas Plant 6.1.1 Sources of Light Gas 6.1.2 Fuel Gas Production 6.1.3 Depropanizer

65 66 66 68 68 71 73 73 74 82 87 92 94 94 96 100 100 103 108 110 114 114 115 118 120 120 121 123 124

6.2 Alkylation Unit 6.3 Diesel Hydrotreater 7. GASOLINE BLENDING MODELING 7.1 Process Overview 7.2 Properties of the Gasoline Blending Stocks 7.2.1 Light Straight-Run (LSR) Gasoline 7.2.2 Other Gasoline Blending Stocks 7.3 Gasoline Blending Model 7.3.1 Octane Model 7.3.2 RVP Blending Model 7.3.3 Percent Distilled Model 8. REFINERY-WIDE OPTIMIZATION 8.1 Formulation of the Optimization Problem 8.1.1 Formulation of the Obj ecti ve Function 8.1.2 Obj ective Function Evaluation 8.1.3 Price Structure 8.1.4 Decision Variables 8.1.5 Constraints 8.1.6 Optimization Algorithm 8.2 Optimization Case Studies 8.2.1 Base Case 8.2.2 Summer Mode 8.2.3 Winter Mode 8.2.4 Optimal Solution Analysis 8.2.5 Profitability Improvement 8.3 Single-Unit Optimization 9. CONCLUSIONS AND RECOMMENDATIONS 9.1 Conclusions 9.2 Recommendations BIBLIOGRAPHY APPENDIX
VI

126 134 136 136 141 141 145 148 148 152 155 156 156 15 6 15 9 160 162 166 171 171 171 172 181 187 189 190 196 196 200 203 208

ABSTRACT

A fuel-oriented refinery converts crude oil into various fuel products which are used for transportation and heating. It also provides feedstock for petrochemical plant. Based on a real refinery in the Gulf coast, a first-principle, nonlinear, plant-wide model was developed by integrating several single-unit models into an overall model. Detailed models were developed for two major units, crude unit and gasoline blending. The crude unit model is a non-stage-by-stage, steady-state model based on material balance and energy balance. The model calculates the yields and properties of the products based on the feed information and product specifications. The gasoline blending model calculates the complete set of gasoline specifications of three grades of gasoline from the information of gasoline blending stocks. Existing detailed models of fluidized catalytic cracking (FCC) unit and catalytic reformer were used in this work after minor modification. Simplified first-principle models were developed for other units in the refinery. Each single-unit model was benchmarked against the industrial data obtained from the refinery. In the refinery-wide model, the outputs of models of upstream units are used as the inputs to the models of downstream units. The intermediate streams are characterized in the overall model to provide necessary information for the models of downstream units. Detailed composition information of feeds to FCC unit and catalytic reformer is calculated. General properties, volume, weight, and specific gravity are calculated for other intermediate streams. A constrained nonlinear optimization was carried out using the developed refinery-wide model. The objective of the optimization is to maximize the daily revenue of the whole refinery. The decision variables are the collection of the process variables of each unit that has significant influence on the economy of whole refinery operation. The nonlinear and linear constraints in the optimization are the summation of constraints of each unit. Two operation modes. Summer Mode and Winter Mode, were studied. The optimal solutions obtained from refinery-wide optimation show that the revenue increase

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over the normal operating conditions is 4.5% for Summer Mode and 3.6%) for Winter Mode. The revenue from refinery-wide optimization is about 1.6% over single-unit optimization.

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LIST OF TABLES

3.1 Feedstock Makeups. 3.2 Gap (5-95) ASTM Temperature between Adjacent Side-Draw Products in the Atmospheric Tower. 3.3 A and B Variables for Equation 3.10. 3.4 Pressure in the Atmospheric Tower. 3.5 Tray Numbers of Separation Sections in Atmospheric Tower. 3.6 Draw Tray Location. 3.7 Separation Specifications of Side-Draw Products. 3.8 Comparison of the Gains Obtained from the Simplified Model with ChemCad model, ASTM 95% Point, Furnace Outlet Temperatiire, and VGO TBP End Point versus Product Flow Rate, Summer Mode. 3.9 Comparison between the Gains Obtained from the Simplified Model and ChemCad Model, Pumparound Heat Duty versus Product Flow Rate, Atmospheric Tower, Summer Mode. 3.10 Comparison between the Gains Obtained from the Simplified Model and ChemCad Model, Pumparound Return Temperature versus Product Flow Rate, Vacuum Tower, Summer Mode. 4.1 Boiling Range ofLumps in Ten-Lump FCC Reaction Network. 4.2 Industrial Data of FCC Feed. 4.3 Comparison between the Industrial Data and Feed Characterization of the FCC Feed. 4.4 Weight Fractions of Eight Lumps in an FCC Feed of API=23. 4.5 Weight Fractions of the Eight Lumps in the FCC feed across the Operating Range. 4.6 FCC Model Benchmarking: Industrial Data and Model Prediction. 4.7 Adjustable Variables in FCC Model Benchmarking. 4.8 Process Constraints of FCC Unit. 4.9 FCC Octane Model. 5.1 Octane Ratings of the Typical Gasoline Blending Stocks. 5.2 Chemical Components ofthe Reformer Feed. 5.3 Ratios in the Calculation of the Naphtha Hydrotreater.

22 29 33 37 44 44 57

60

61

62 73 75 82 84 86 88 89 91 93 94 98 101

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5.4 Industrial Data of Crude A. 5.5 Industrial Data of Crude B. 5.6 Industrial Data of Crude C. 5.7 Industrial Data of Crude D. 5.8 Comparison of Volume Percentages of PNA from Feed Characterization and the Industrial Data. 5.9 Catalyst Weight in Each Reactor Bed. 5.10 Comparison ofthe Industrial Data and Model Prediction after Benchmarking. 5.11 Adjustable Prameters in the Reformer Model Benchmarking. 5.12 Reformer Operation Limit. 5.13 Coke Contents in Dfferent Regions. 5.14 Ratios between Average Coking Rate and Coking Rate at the Begiiming of a Cycle. 6.1 Light Gas Production Rates in the Crude Unit. 6.2 Compositions of Light Gas from FCC Unit. 6.3 Losses of Heavy Hydrocarbons in the Fuel Gas. 6.4 Portion ofthe Propylene in the C3 Product. 6.5 Weight Percentage ofthe Propylene that Reacts in the Second Reaction Path in the Alkylation Unit. 6.6 Octane Number ofthe Butylene Alkylate and Propylene Alkylate. 6.7 Weight Percentage ofthe Unreacted Isobutane in the Alkylation Unit. 6.8 Weight Ratios ofthe Hydrogen and the Products in the Diesel Hydrotreater. 6.9 Volumetric Ratios ofthe Hydrogen and the Products in the Diesel Hydrotreater. 7.1 Volumes and Sources ofthe Gasoline Blending Stocks in Typical Summer Mode Operation. 7.2 Specification of Three Grades of Gasoline Produced in the Refinery Considered in This Work. 7.3 Industrial Data ofCrude A and Crude B. 7.4 Industrial Data of Crude C and Crude D. 7.5 Properties ofGasoline Blending Stocks. 7.6 Universal Set ofthe Binary Interaction Parameter between Components. 8.1 Chemicals Purchased by the Refinery Considered in This Work.

104 104 105 105 108 110 111 112 116 116 117 122 123 124 124 129 130 132 134 135 137 138 142 143 147 150 157

8.2 Price Structure ofthe Refinery-Wide Optimization. 8.3 Decision Variables of Refinery-Wide Optimization. 8.4 Nonlinear Constraints of Refinery-wide Optimization. 8.5 Comparison of Model Prediction ofthe Base Case with the LP report. Summer Mode. 8.6 Comparison of Model Prediction ofthe Base Case with the LP Report, Winter Mode. 8.7 Optimum Values ofthe Decision Variables of Refinery-wide Optimization, Summer Mode. 8.8 Active Constraints in Refinery-wide Optimization, Summer Mode. 8.9 Comparison ofthe Decision Variables of Refinery-wide Optimization with Base Case, Summer Mode. 8.10 Comparison ofthe Decision Variables of Refinery-wide Optimization with Base Case, Winter Mode. 8.11 Active Constraints in Refinery-wide Optimization, Winter Mode. 8.12 Comparison ofthe Product Slates ofthe Optimum Solution with the Base Case, Winter Mode. 8.13 The Mean and Variance of the Feasible Solutions. 8.14 Change of the Objective Function Value around Optimal Solutions. 8.15 Profitability Improvement of the Refinery-wide Optimization. 8.16 Prices of the Side-draw Products from the Crude Unit, Summer Mode. 8.17 Prices of the Side-draw Products from the Crude Unit, Summer Mode. 8.18 Comparison of Single-unit Optimization with Refinery-wide Optimization, Summer Mode. A.l Constants of Polynomial Expression for the TBP Curve ofthe Mixed Crude in Summer Mode, Calculating the Vol.%) Given the Temperature in F. A.2 Constants of Polynomial Expression for the TBP Curve ofthe Mixed Crude in Summer Mode, Calculating the Temperature in F Given the Vol.%. A.3 Constants of Polynomial Expression for the TBP Curve ofthe Crude in Winter Mode, Calculating the Vol.% Given the Temperature in F. A.4 Constants of Polynomial Expression for the TBP Curve ofthe Crude in Winter Mode, Calculating the Temperature in F Given the Vol.%. A.5 Constants of Polynomial Expression for the API Gravity Curve ofthe Mixed Crude in Summer Mode, Calculating the API Gravity Given the Vol.%.

158 164 167 173 174 177 178 179 183 184 185 187 189 190 191 192 193 208 208 209 209 210

XI

A.6 Constants of Polynomial Expression for the API Gravity Curve ofthe Mixed Crude in Winter Mode, Calculating the API Gravity Given the Vol.%. A.7 Constants of Polynomial Expression for the Sulfur Curve ofthe Mixed Crude in Summer Mode, Calculating the Sulfur Given the Vol.%o. A. 8 Constants of Polynomial Expression for the Sulfur Curve ofthe Mixed Crude in Winter Mode, Calculating the Sulftir Given the Vol.%. A.9 Constants of Polynomial Expression for Converting ASTM End Point to TBP End Point. A. 10 Constants of Polynomial Expression for Converting Gap (5-95) ASTM to Gap (0-100) TBP. A. 11 Constants of Polynomial Expression for Calculating the Molecular Weight of a Crude Cut Given the Mean Average Boiling Point and API gravity. Characteristic Factor from 12.1 to 12.6. A. 12 Constants of Polynomial Expression for calculating the molecular weight of a Crude Cut Given the Mean Average Boiling Point and API gravity. Characteristic Factor from 11.7 to 12.0. A. 13 Constants of Polynomial Expression for Calculating the Molecular Weight of a Crude Cut Given the Mean Average Boiling Point and API gravity. Characteristic Factor from 11.3 to 11.6. A. 14 Constants of Polynomial Expression for Calculating the Enthalpy of a Crude Cut from Its API Gravity, Temperature and Phase. A. 15 Constants of Polynomial Expression for Calculating the Enthalpy of a Crude Cut in Saturated Vapor Phase from Its API Gravity and Temperature. A. 16 Constants of Polynomial Expression for Calculating the Steam-free Delta T Given the Value of the Percent Stripout of Crude Cuts. A. 17 Constants of Polynomial Expression for Calculating Stripout from Steam Rate. A. 18 Constants of Polynomial Expression for Calculating the Steam-free DT Minus Actual DT(F) from the Temperature (F) Difference between Feed and Stripping Steam and Percent Stripout. A. 19 Constants of Polynomial Expression for Calculating the Enthalpy of Steam from Temperature. A.20 Constants of Polynomial Expression for Calculating the Enthalpy of Air from Temperature. A.21 Constants of Polynomial Expression for Calculating the Enthalpy of Water from Temperature.

210 211 211 212 212

213

213

214 214 219 221 222

223 223 224 224

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A.22 Constants of Polynomial Expression for Calculating the Slope of Flash Reference Line from Corresponding Distillation Reference Line. A.23 Constants of Polynomial Expression for Calculating the Ratio of DT(flash)/DT(TBP) from Volumetric Percent Distillated. A.24 Constants of Polynomial Expression for Calculating the Temperature Difference between the Distillation and Flash Reference Curves from the Slope of Distillation Reference Curve. A.25 Constants of Polynomial Expression for Calculating the T50 of Flash Curve under Vacuum from the Pressure and T50 ofthe Flash Curve under Atmospheric Pressure.

225 225

226

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LIST OF FIGURES

3.1 Block Flow Diagram of a Fuel-Oriented Refinery. 3.2 Schematic of a Fuel Type Crude Unit. 3.3 Schematic of the Model of the Atmospheric Tower of the Crude Unit. 3.4 Crude Cuts on a TBP-Volumetric Curve. 3.5 TBP Curve of the Crude Used in Summer Mode. 3.6 API Curve of the Crude Feed Used in Summer Mode. 3.7 Sulfur Curve ofthe Crude Feed Used in Summer Mode. 3.8 Flash Zone of the Atmospheric Tower. 3.9 Flowchart for the Calculation of Flash Zone Pressure and Temperature. 3.10 Energy and Material Balance Quantities at a Side-Draw Tray. 3.11 Flowchart ofthe Side-Draw Tray Temperature Calculation. 3.12 Schematic of a ChemCad Crude Unit Model. 3.13 Comparison of Simplified Model and ChemCad Rigorous Model, Summer Mode. 3.14 Comparison of Simplified Model and ChemCad Rigorous Model, Winter Mode. 3.15 Comparison of Temperature Profile in the Atmospheric Tower. 4.1 Schematic of a Model IV Fluidized Catalytic Cracking (FCC) Unit. 4.2 Ten-Lump Reaction Network. 5.1 Process Flow Scheme of a Semi-Regenerative Catalytic Naphtha Reformer. 6.1 Schematic of the Gas Plant in the Fuel-Oriented Refinery. 6.2 Schematicof a Hydrofluoric Acid Alkylation Unit. 7.1 Flowchart for the Calculation ofthe Tio%, TSQO/O,
T9OO/

17 18 21 23 25 27 27 39 40 46 49 56 58 58 63 70 72 97 121 127 ofGasoline Blends. 154 161 180 186 195

8.1 Flowchart of the Execution of the Refinery-Wide Model. 8.2 Comparison of Product Slates of Refinery-Wide Optimization with Base Case, Summer Mode. 8.3 Comparison of Product Slates of Refinery-Wide Optimization with Base Case, Winter Mode. 8.4 Comparison of Product Slates of Single-Unit Optimization (Crude Unit) with Refinery-Wide Optimization, Summer Mode.

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CHAPTER 1 INTRODUCTION

Crude oil is the dominant fuel resource in the world today. Products from crude oil are extensively used in industry and normal life. The products directly coming from crude oil include fuel gas, liquidified petroleum gas (LPG), gasoline, jet fuel, diesel, heating oils, lubricated oil, fuel oils, solvents, asphalt, etc. Crude oil is also the raw material for the petrochemical and chemical industries. To use crude oil efficiently and to make its usage environmental safe, it is necessary to refine crude oil into various products that have different specifications that satisfy the usage requirement and environmental regulations. The process of refining the crude oil into various products is normally carried out in refineries. Although there is a long history of using crude oil as burning material, it is not until 1860 that the first real petroleum refinery was built at Titusivlle, PA, at a cost of about $15,000 (Nelson, 1958). Since then, petroleum refining has developed into a major industry in almost every country. In 1998, the total worldwide crude oil production was about 73 million barrels per day. The worldwide refining capacity is about 67 million barrels per day (Beck, 1999). Population growth and continued world economic expansion produce an everincreasing demand for fuel. This indicates that worldwide refining capacity will keep increasing in the future. Although conventional fuel from petroleum faces challenges from fuels obtained from renewable resources, it is expected to remain a dominant player at the beginning of the 21st century (Bensabat, 1999). The worldwide oil reserves in 1999 are about I trillion barrels. If the oil production is maintained at the level of 1998, the current oil reserve can sustain about 39 years. With technical advancement and further exploration, the oil reserve keeps increasing. The reasonable forecast is that crude oil will stay as the largest fuel resource in the first half of 21st century. Petroleum refining has developed from simple separation in the early stage to a very complex process today. The early development of petroleum refining technology

includes applying continuous distillation, vacuum distillation, and thermal cracking, etc. The refining industry has undergone tremendous expansion and change since World War II. Many new processes with high efficiency have been invented. These new processes include Fluidized Catalytic Cracking (FCC), Catalytic reforming, Alkylation, catalytic desulfurization, delayed coking, etc. Enormous increases in the size of process units, new catalytic processes, shifting product demands, and new sources of petroleum from tar sands and oil shales have made present-day technology and economics of petroleum refining a very complex and sophisticated science (Gary and Handwerk, 1984). For decades, the large and mature U.S. transportation fiiel market has been dominating the global petroleum supply (Bensabat, 1999). Consequently, transportation fuels including gasoline, jet fuel and diesel, has the largest quantity among all the products made from crude oil. By far, passenger vehicles make up the largest sector with respect to number of vehicle and fuel consumption. Most of U. S. passenger vehicles are fueled by gasoline in conventional combustion engines. They consume about 8.5 million barrel per day of gasoline, or 12% of global petroleum demand (Bensabat, 1999). Most of transportation fuel consumed in U. S. is produced domestically. Due to such massive production, many refineries in U. S. are fuel-oriented refineries whose main fiinction is to produce transportation fiiel. There are other types of refineries. For example, some refineries provide aromatics and olefin for petrochemical pleints. Some refineries also produce lubricants and asphalt while producing transportation fuel. In the past thirty years, innovation in new products and new processing approaches has slowed dowoi. Even the capacity expansion has slowed down in the United States. No grass-root refinery has been buih after 1980. The emphasis ofthe refining industry has shifted to improving economic performance ofthe existing plants. Increasing competition in the refining business and stricter environmental and safety pressures have forced refiners to invest more money and time on process monitoring, process control and optimization. Recent crude oil price decrease resulted in a sharp decline in the refining margin, and consequently, decline in revenues and profits for North American oil and gas companies (Beck, 1999). In order to survive in such

changing market, companies needs to lower the operating cost and increase the revenue to remain competitive. Recent industrial practices showed that advanced process control and optimization are the way to accomplish this. The common goal of all refiners is to provide safe, profitable, quality product manufacturing (Pelham and Pharris, 1996). Process control and optimization have become indispensable tools to realize this goal. Significant advancement in instrumentation and computers has made the implementations of process control and optimization cheaper and more reliable. Before we go into the discussion of optimization which is the main topic of this dissertation, we need to introduce process control first since the benefits of optimization can not be realized without implementation of process control. Chemical Process Control (CPC) is concerned with operating a plant such that the product quality and production rate specifications are met in a safe and reliable manner (Riggs, 1999). Process Control is also necessary to reach other operation objectives such as environmental protection, equipment protection, and profit return, etc. (Marlin, 1995). The controllers in a refinery were mostly PID Controllers 20 years ago. Two key technical developments occurred during the late 1970s that led to dramatic acceptance and growth in the number of advanced control systems. The two key developments were the Distributed Control System (DCSs) and Model Predictive Control (MPC) Technology (Pelham 1993). The DCS combines the hardware and software needed for data acquisition and basic control fiinctions. It is based on using a number of local control units which have their owoi microprocessors and are connected by shared communication lines as well as connected to operator/engineer consoles, a date acquisition system, and a general purpose computer (Riggs, 1999). The industrial standard for MPC is dynamic matrix control (DMC) technology, which was implemented in late 1960s. Since then, model-based process control has become a common industrial practice in refining industry. It has been estimated about 3 o incremental profit can be realized through % implementing model-based process control (Ellis, 1998).

The basic task for a controller is to maintain a process variable at a given setpoint. Since every refining company needs to make profit, these setpoints must be as economically favorable as possible. This economic target can be expressed in different form: largest production, the greatest profit, the minimum cost, and the least energy usage (Edgar and Himmelblau, 1988). Now the question is raised: how to choose those setpoints which make the process most profitable while observing process constraints and meeting all product specifications? This is an optimization problem. In some refineries, the values of those setpoints are set by operators and process engineers based on their experience and intuitions. Such decision making approach can not be consistent due to different backgrounds of people making the decisions. In a modem refinery, a more systematic approach is followed. Usually, there is one experienced individual known as a planner/scheduler. The responsibility of this individual is to develop an operating plan for the next several days, given current levels of crude stocks, operating capacities, offtakes and inventory constraints (Pelham and Pharris, 1996). He may use linear programming as a pragmatic guideline. Today, largescale linear programming (LP) technology is well established with respect to planing and scheduling and no major change in that status is anticipated (Pelham, 1993). After the solution is found using an LP, the planning engineer sends the values in the solution as setpoints to engineers in unit operation. Usually, the planer/scheduler gives a range for the setpoints to a process variable instead of a single value in order to enable some flexibility. In plant operation, the engineers in a specific unit then use the information to choose the setpoints for each respective control loop. They also need to decide the setpoints that are not provided by the LP. There are several obstacles in using LP for operation scheduling in a refinery: (1) If the refinery is operated at constant conditions and LP model well represents the refining processes at the fixed operating conditions, LP is the answer to scheduling problem in a refinery. However, this is rarely the case. Due to continuous change ofthe crude quality, and fluctuating market demands and prices, the operation of a refinery is

always changing to adapt to such changes. Since refining processes are inherently nonlinear, especially those processes with reaction systems, linear models will not be able to precisely represent those processes with linear relationship, and (2) the linear models used by the planner/scheduler are simplified models that do not include all the details (Jones, 1999). This simplification is done to speed up LP solution finding. The linear models are developed by linearizing a nonlinear process at certain operating conditions. When the operating conditions changes, the linear models become invalid. Hence, the optimization results based on such linear models are susceptible to error, and (3) the LP does not consider the elements of time and storage. It assumes that all activities occur simultaneously (Hartmann, 1997), which is not the case in reality, and (4) the LP is only suited to find an optimum at the intersections of constraints. However, it is quite possible that the optimal solution of refinery-wide operation lies inside constraints due to the nonlinearity ofthe optimization problems. A possible remedy to linear programming is to update the linear models continuously based on plant data (Cutler, 1999). However, with the increasing complexity of refineries, it is very difficult to maintain the required data consistency (Hartmann, 1997). In addition, the continuous updating will add tremendous workload. On the other hand, nonlinear models have been built and single-unit optimization has been implemented for several important refining processes, such as crude unit, FCC unit, and gasoline blending, etc. Some software vendors have provided simulation software packages for modeling, such as AspenPlus from Aspen Technology, PR02 from Simulation Sciences, and HYSYS from Hyprotech, etc. Some vendors even supply optimization packages, such as real-time optimziation (RT-Opt) from Aspen Technology, and Romeo process optimization from Simulation Sciences. It has been estimated about 3% incremental profit can be realized through implementing real-time on-line optimization on single unit (Ellis, 1998). However, a single-unit optimizer covers only a subset of a large problem (Friedman, 1995). It is hard to make the optimal solutions from single-unit optimization to be consistent with the plant-wide operation strategy. The reason is that single-unit

optimization needs correct price information ofthe intermediate streams. However, such price information is not always available from the market since some intermediate streams are not sold on the market. Intermediate product price is a function of quality and product rate. It also depends on tankage consideration, lifting schedule, the current content of intermediate tanks and finally on future crude runs (Friedman, 1995). To solve this problem, some engineers used the shadow prices ofthe refinery LP to evaluate the prices of intermediate products. A shadow price is the change in the optimal value ofthe objective fimction per unit change in an active constraint. However, the shadow prices of LP are not valid when the operation shift to different product qualities or a different schedule. The single-unit optimization based on imprecise price information can results in conflict with plant-wide operation strategy. In order to overcome the inherent disadvantages of LP and single-unit nonlinear optimization, a new approach is applied to tackle the optimization problem in the refinery. In this work, several nonlinear single-unit models are integrated into a refinerywide model and this model is used in nonlinear optimization to find the optimal operating conditions for the entire refinery. The main advantage of such an approach is that it uses detailed nonlinear models to represent nonlinear refining processes and it does not need prices of intermediate streams. The primary objectives of this work are to: 1. Develop nonlinear single-unit models for important processes in a fuel-oriented refinery. 2. Integrate developed single-unit models into a overall refinery-wide model. 3. Carry out nonlinear optimization using the developed models to find the optimal operating conditions for the whole refinery. 4. Evaluate the incremental profit of using such optimization approach by comparing with results from normal operating conditions. 5. Compare refinery-wide nonlinear optimization with single-unit nonlinear, optimization.

Modeling every unit in detail is formidable task if not impossible. However, a detailed plant-wide model is not necessary for optimization to capture the major part of the benefit obtained from nonlinear optimization just like LP does not need to use detailed models to be helpfiil in guiding the planer/scheduler. To keep this work manageable, the following approach is applied. Detailed models for four major units were developed. Those units include crude unit, FCC unit, catalytic reformer, gasoline blending. Simplified models are used to represent other units in the refinery. The previous research on refinery modeling and optimization is reviewed in Chapter 2. The single-unit model development and benchmarking are described from Chapter 3 to Chapter 7. Those units including crude unit, FCC unit, catalytic reformer, gasoline blending, gas plant and alkylation unit, etc. Most ofthe models were benchmarked against the industrial data obtained from a fuel-oriented refinery. Chapter 3 discusses the development of a simplified first principle model of a crude unit and the model benchmarking. In Chapter 4, the rigorous steady-state model of a Model IV FCC unit is briefly discussed. The emphasis is on the modification ofthe existing model to fit the FCC unit in the ftael-oriented refinery. Again, the model benchmarking is discussed. In Chapter 5, the rigorous steady-state model of a catalytic reformer unit is briefly discussed. The emphasis is on the modification of the existing model to fit the reformer unit in the fuel-oriented refinery. Again, the model benchmarking is discussed. Chapter 6 discusses the modeling of gas plant, alkylation unit and other auxiliary units in the refinery. Chapter 7 discusses the development a detailed model ofthe gasoline blending process. Chapter 8 discusses the optimization results obtained from applying successive quadratic programming (SQP) technique to the refinery-wide model. The comparisons among nonlinear refinery-wide optimization, normal operating conditions and nonlinear single-unit optimization are also given. The results of this work and recommendations for future studies are presented in Chapter 9.

CHAPTER 2 LITERATURE REVIEW This research is divided into two parts: (1) Single-unit modeling and feed characterization; (2) Steady-state optimization. The literature review is also divided into the same two parts.

2.1 Single-Unit Modeling and Feed Characterization The focus ofthe present work is the modeling and optimization of a fiiel-oriented refinery. A typical fiael-oriented refinery includes the following major units: crude unit, FCC unit, catalytic reformer, gasoline blending, gas plant, and alkylation unit. For a large-scale refinery processing heavy crude, a hydrocracker or a delayed coker is often included to process the heavy end ofthe crude. The refinery that the model was benchmarked against is a small-scale refinery processing light crude. Hence, a hydrocracker or delayed coker was not installed. Beside these major units, there are some auxiliary and pretreating units in the refinery: naphtha desulfurizer, diesel hydrotreater, Debutanizer, naphtha splitter, Claus and Scott units, Merox and Amine treater, fuel gas mix drum, and gas turbines, etc. They are also important in the refinery-wide optimization because their capacity may become active constraints in searching the optimal operating conditions. Refining process modeling is a hot topic in both industry and academia. The industry has an edge in this area because it has large amount of operation data which accurate and detailed models can be built on. However, refining companies rarely publish their models. Models are built in academia for control and optimization studies. The models in the public domain usually are based on a specific set of industrial data. Hence, they can not be used directly in this work without further benchmarking. In U.S., 40-50 percent of gasoline comes from FCC gasoline. Therefore, FCC unit is a critical unit when studying the economy of a fuel-oriented refinery. Ellis (1996) developed a steady-state model of FCC unit on the basis of a Model IV FCCU Dynamic Simulator (McFarlane et al., 1993) while using the Mobil ten-lump yield model (Jacob et

al., 1976) to predict product yields. The ten-lump model includes eight lumps for gas oil components, one lump for FCC gasoline and another lump for coke and light gas. The detailed composition modeling for FCC gasoline and light gas is not available from the ten-lump model. Empirical correlations were used in the FCC model to calculate octane number of FCC gasoline and the light gas composition. A detailed literature survey on FCC modeling and optimization is included in the thesis of Ellis (1996). Catalytic reformer produces about 20-35 percent gasoline ofthe gasoline pool. Reformate, the gasoline blending stock produced in reformers, is the major gasoline booster in the gasoline pool. A rigorous steady-state model of catalytic reformer was developed by Taskar (1996). The model uses 35 components, including real chemical species and pseudo-components, and 36 reactions to model the reaction system of a reformer. The model provides detailed information of reformate. A detailed literature survey on reformer modeling and optimization is included in the dissertation of Taskar (1996). The literature review here focuses on crude unit modeling and gasoline blending modeling. A crude unit includes pretreating facilities, preheat train, fiimace, atmospheric tower, vacuum tower and separation train. A detailed model, which includes all the units, has not been presented in literature. Instead, most ofthe publishing research focused on the tray-to-tray rigorous modeling ofthe atmospheric and vacuum towers. Edmister (1955) proposed an integral method for making petroleum distillation calculations. Taylor and Edmister (1971) applied the method to a gasoline rerun column. However, this method requires a curve of K versus mole fraction, which is not easily obtained. In addition, it uses a trial and error in root searching, which causes slow convergence in the digital computation. Cechhetti et al. (1963) studied a 62-stage Exxon crude tower and built a steady-state model which uses 6-method of convergence. Hess et al. (1977) and Holland and Liapis (1983) used 2N Newton-Raphson method to solve this steady-state model. In the above studies, the pseudo-component approach is used in vapor liquid equilibrium (VLE) calculations. The crude is divided into 35 pseudo-components in order to represent the true-boiling-point (TBP) curve. Cechetti et al. (1963) first

presented the physical properties ofthe pseudo-components. Hess (1977) curve-fitted those physical properties into formulas to correlate the equilibrium K values and enthalpies as a function of temperature only. Since the conventional bubble-point algorithm in temperature calculation is inherently unstable in the face of enthalpy inversion caused by the extremely wideboiling nature ofthe crude feed, Chung and Riggs (1995) proposed a dynamic stagewise adiabatic flash (DSAF) algorithm which efficiently provides stable solutions for an extensive operating range. A dynamic model was constructed based on DSAF algorithm and was used for control studies. All the above studies used sequential modular approach in modeling. Mizoguchi et al. (1995) constructed a dynamic model using open-equation approach for control study. The model is based on a crude unit in the Petro-Canada Ontario Refinery. It uses 34 pseudo-components to represent the crude feed. The complete model has 2297 differential/algebraic equations, 263 fixed external variables, 9 external manipulated variables, and 2297 dependent variables. The present work concentrates on the economic optimization ofthe whole refinery instead of a single unit. Hence, it is not strictly necessary to build a tray-to-tray rigorous model for atmospheric tower and vacuum tower. The most important characteristic that a crude unit model must have is that it should be able to predict the volumetric flow rate and properties ofthe products accurately. Watkins (1979) presented a design method which can be used to build a first-principle steady-state model. This approach uses material and energy balance to calculate the sfreams in and out of each fractional section between adjacent side-draw trays. Empirical correlations are used to evaluate the properties of feed and products. Since this approach serves the main purpose of this work, the crude unit has been modeled using the approach outlined by Watkins (1979). Gasoline cuts coming from various upstream process units are blended into various grades of gasoline in the gasoline blending unit. The purpose ofthe gasoline blending model is to predict the property specifications for various grades of gasoline

10

from the properties of incoming gasoline cuts. Some specifications ofthe final product can simply be calculated as the summation of corresponding properties ofthe blending agents. Such specification include oxygen content, sulfur content, benzene content, etc. Other specifications need a more complex, usually nonlinear, model in order to make accurate predictions. Such specifications include octane number, Reid Vapor Pressure (RVP), and volatility. The refinery considered in this work mainly produces regular grades of gasoline. Reformulated gasoline which is used in some areas of U.S. has more specifications. The calculations of extra specifications of reformulated gasoline are not included in the gasoline blending model. There are two approaches used in octane number calculation ofthe gasoline blending model. The first approach is to convert the octane numbers of gasoline cuts into blending octane values and calculate the octane of final gasoline on a volumetric average basis. This approach is widely used in industry. Gary and Handwerk (1984) and Unzelman (1996) gave the blending octane values of some gasoline cuts. However, blending octane numbers are usually derived from regression analysis of a small data set, e.g., those derived from gasoline of a single refinery. Muller (1992) used the concept of "excess octane number" and formulated the equations to calculate the deviation of blending octane number from ideal blending. The excess octane numbers are derived directly from original refinery blending data. This approach is very similar to the blending value approach. Zahed et al. (1993) presented ein empirical correlation of calculating gasoline octane number using constants regressed from a specific refinery. The disadvantage ofthe blending value approach is that blending values can only be to calculate the blends where the blending values are derived from. The blending value of one gasoline cut may change dramatically when blending is changed. The advantage of the approach is that if the blending values are derived from a complete gasoline blending study in a refinery, the blending value approach is more accurate for that specific refinery than general methods introduced below. A more theoretical approach is the interaction method. It is well known that the octane numbers do not blend linearly due to nonlinear interactions among gasoline cuts.

II

If the interaction coefficients among various gasoline cuts can be calculated, the octane number of blended gasoline can be predicted accurately. Schoen and Mrstik (1955) first presented a graphical correlation for predicting octane numbers of binary blends from the octane numbers and olefin content ofthe two base blending stocks. Stewart (1959) used the same approach but made the method more self-sustained and expanded it to multi-cut blends. The interaction method is first proposed by Morris (1986). The key to the accuracy ofthe interaction method is having accurate interaction coefficients. Interaction coefficients can be derived from an octane blending study wherein accurate octane data are obtained on all components and all 50:50 blends (Morris, 1986). Morris et al. (1994) then expanded the interaction method to multi-agents blending. The disadvantage of Morris's approach is that interaction coefficients can only be used for the blending ofthe specific set of gasoline cuts where the interaction coefficients were derived from. The interaction parameters not only depend on types ofthe gasoline cuts, but also depend on the octane levels and octane difference ofthe gasoline cuts in the blending. The value of interaction coefficient between two gasoline cuts can vary from large negative to large positive in different blending situations (Twu and Coon, 1996). The ideal solution is to have an accurate generalized method to predict interaction coefficients without the need for a blending study. Such a method is commercially available but is not available in open literature (Morris, 1985). The interaction method proposed by Morris only considers the interaction coefficients among blending cuts. It does not use the information ofthe composition of gasoline cuts. Twu and Coon (1996) proposed a component-oriented interaction approach that is general and can be used in any gasoline blending without blending studies. This approach only needs the octane numbers of gasoline agents and the information ofthe concentrations of olefins, aromatics, and saturates in the gasoline cuts. A universal set of the binary interaction parameters is given. Twu and Coon (1997) further extend this method to be more consistent in methodology by applying the same binary interaction parameters to components in each gasoline cut and their blends. Due to the lack of a

12

complete blending study ofthe refinery considered in this work, Twu and Coon's approach was used in the octane number calculation in this work. Reid vapor pressure (RVP) is widely used as a criterion to measure the volatility of gasoline. Thus, the accurate prediction of RVP is critical in product blending and refinery-wide optimization. A similar blending value approach is widely used in industry. Chevron Research Company developed an empirical method which uses vapor pressure blending indices (VPBI), which is a fiinction ofthe RVP ofthe individual blending cuts. The table of VPBI versus RVP is given in Gary and Handwerk (1984). Stewart (1959) formulated the first theoretical method to predict RVPs of ftiel blends. It is based on the standard RVP test defined by the American Society for Testing and Materials (ASTM) under the designation ASTM D323-56. It makes a VLE calculation with respect to the Reid test conditions with the assumption of ideal gas phase and uses the Sounders' state of equation to calculate the vapor-liquid equilibrium K values. However, this method ignores the presence of air and water vapor in the Reid test. It also assumes that the volatile components have the molar density of butanes and the nonvolatile components have the thermal expansion characteristics of n-octane. Vazquez-Esparragoza et al. (1992) followed the same approach but used the more accurate Soave-Redlich-Kwong equation of state in VLE calculation. Stewart's approach represents gasoline blending cuts in pseudo-components and requires the physical properties of those pseudo-components, which can only be obtained through empirical correlations. This adds to the inaccuracy of this approach. Since Chevron's VPBI method is accurate enough (Gary and Handwerk, 1984) and widely used in the refining industry, the VPBI method is used in the RVP calculation in the present work. Empirical correlations are used in the feed characterization for the FCC unit and the reformer unit. The most important feed information is the compositions of paraffins, olefins, naphthenes, and aromatics (PONA). The PONA information in FCC feed can be calculated by TOTAL method (Dhulesia, 1986) and n-d-M method (ASTM, 1985). The reformer feed characterization uses the crude assays obtained from the refinery considered in this work.

13

After a refinery-wide model had been developed, optimization studies were carried out to find the optimal operating conditions for the whole refinery. 2.2 Refinery-Wide Optimization Refinery-wide optimization involves many decision variables and constraints. Linear Programming (LP) is the most widely used technique in refinery operation optimization, which is called planning and scheduling in industry. The linear programming was first proposed by Dantzig in 1947 to refer to the optimization problems in which both the objective function and the constraints are linear (Dantzig, 1963). LP problems exhibit the special characteristic that the optimal solution ofthe problem must lie on some constraints or at the intersection of several constraints. Dantzig first proposed the most popular algorithm in LP called the Simplex algorithm in 1947. Symonds (1956) used an LP to solve a simplified gasoline refining and blending problem. The advantage of LP is its quick convergence and ease to implement. However, it is suitable only for linear and nearly linear process. One method to solve a nonlinear problem by using LP is to repeatedly linearize the objective function and constraints at some estimate ofthe solution (Edgar and Himmelblau, 1988). This procedure is the basis of a method called successive linear programming (SLP). According to Edgar and Himmelblau (1988), SLP has been demonstrated to be successful on problems with a moderate degree of nonlinearity. The disadvantage of SLP is that it may converge very slowly when the optimum lies in the interior ofthe feasible region and when there are a large number of nonlinear variables. Generalized Reduced Gradient (GRG) algorithm is a popular nonlinear optimization method used in industry. Basically, GRG uses a reduced form of gradient to find the search direction. It defines new variables that are normal to the constraints and expresses the gradient in terms of this normal basis. GRG may sometimes have difficult to return from an infeasible point to the feasible region during the search. Generally, the performance ofthe GRG algorithm is comparable to that of Successive Quadratic Programming discussed below.

14

Successive Quadratic Programming (SQP) is widely used to solve large-scale nonlinear problems. Edgar and Himmelblau (1988) made the statement that SQP might be the best in solving nonlinear programming problems. Riggs (1994) suggested using SQP for large-scale problems. SQP is the method used in the leading on-line optimization software package, RT-OPT, developed by Aspen Technology, Inc. SQP approximates the objective function locally by a quadratic function and linearized constraints. The search direction is decided by solving the quadratic programming subproblem. After that, a minimization algorithm is used to calculate a step size in the search direction. Several tries of line search are employed in deciding the appropriate step size. SQP repeatedly applies the procedure until it successfully finds a point that satisfies the first-order KuhnTucker condition or fails after certain number of tries. Detailed mathematical proof on SQP can be found in Gill et al. (1981). SQP usually requires less iterations and converges much faster to interior optimum points than Successive Linear Programming. It should be noted that SQP may go through an infeasible path while searching for the optimum. The bounds and linear constraints are always satisfied along the search while the nonlinear constraints will not generally be satisfied until an optimal point is reached (Gill et al., 1986). The NPSOL 4.0 (Gill et al., 1986) software package is used as the optimization engine in this work.

15

CHAPTER 3 CRUDE UNIT MODELING 3.1 Introduction The crude unit separates the crude into various product cuts with different boiling ranges. The downstream units, such as FCC unit, reformer, further process these cuts to make final products. A block diagram of a fuel-oriented refinery is shown in Figure 3.1. It can be seen that downstream units receive their feed from the crude unit. The crude unit is the first major processing unit in almost all the refineries. The products from crude oil are usually characterized by their boiling range. Many properties of crude cuts are related to the boiling range. For example, molecular weight and sulfur content increase with boiling range. The aromatics content also increases with boiling range while the pEiraffin content decreases with boiling range. Distillation is the cheapest and the easiest method to separate crude into different cuts. Higher efficiencies and lower costs are achieved if the crude oil separation is accomplished in two steps: first, by fractionating the total crude oil at a atmospheric pressure; then, by feeding the high-boiling bottoms fraction from the atmospheric still (atmospheric tower) to a second fractionator (vacuum tower) operated at a high vacuum (Gary and Handwerk, 1984). The flow diagram ofthe atmospheric tower and the vacuum tower is shown in Figure 3.2. From the point of view of plant-wide economy, the cut points between adjacent cuts in the distillation columns ofthe crude unit are among the most important operating decision points. If the crude cuts are not specified properly, the downstream processing units may have trouble in processing the cuts to make products within the specifications. The quality of crude cuts may also affect the normal operation of downstream units, such as catalyst poisoning, equipment corrosion, etc. Therefore, operating atmospheric tower and vacuum tower properly is crucial for the entire refinery operation.

16

u
0)

-o c

17

Vapor Distillate

f
29

Water Liquid * Light Naphtha

U^

^
Atmospheric Tower

Steam

~:*~fieavy
Naphtha Steam

Kerosene

Steam

-:0^

Diesel

Steam *^^

Atmospheric Gas Oil

To jets

>

Light Vac. Gas Oil

Heavy Vac. Gas Oil Overflash

Vac. Bottoms

Figure 3.2 Schematic of a Fuel Type Crude Unit.

18

The crude unit modeling in this work focuses on the atmospheric tower and the vacuum tower, the core ofthe crude unit. The modeling procedure as described in Watkins (1979) and Lin (1988) has been followed in most ofthe work. In the crude unit, the crude from crude storage tanks first goes through dewatering, desalting and then exchanges heat with the side-stream products and pimiparounds from the atmospheric tower and the vacuum tower. The crude is further heated in a furnace before entering the bottom ofthe atmospheric tower called flash zone. The crude then partially vaporizes in the flash zone due to the pressure drop at the injection point. The atmospheric tower has only a rectifying section. The vapor formed in the flash zone flows upward and is separated into overhead gas, light naphtha (LN), and several side-draw products: heavy naphtha (HN), light distillate (LD), heavy distillate (HD), and atmospheric gas oil (AGO). These side-draw products are drawn out ofthe tower from the side-draw trays ofthe atmospheric tower. The light naphtha is further separated into liquidified petroleum gas (LPG) and light straight-run gasoline (LSR). The heavy naphtha is fed to the reformer to make reformate, a gasoline blending stock. The light distillate is further treated to make jet fuel. The heavy distillate goes through the hydrodesulfurization unit to make diesel. The AGO goes through the rerun unit to recover some diesel components and the rest ofthe AGO is fed to the FCC unit to produce FCC gasoline. The nonvolatile part ofthe crude, which is called the reduced crude, exits from the bottom ofthe atmospheric tower and is fed to the vacuum tower for ftirther separation. The function of vacuum tower is to maximize the extraction of distillate liquids from the raw crude feed. The reduced crude is first heated up in a vacuum tower furnace and then enters the flash zone ofthe vacuum tower at the bottom. The reduced crude vaporizes in the flash zone due to pressure drop. The vapor flows upward and is separated into light vacuum gas oil (LVGO) and heavy vacuum gas oil (HVGO) and product cuts are drawn from the tower on side-draw trays. The nonvolatile part ofthe vacuum tower feed leaves the bottom ofthe vacuum tower and goes for further treatment.

19

The LVGO and the HVGO are combined and fed to FCC unit. The vacuum residue goes through the residue oil solvent extraction (ROSE) unit to recover the gas oil in the vacuum residue. The rest of residue is further treated to make No. 6 fuel oil. The crude unit model in this work includes an atmospheric tower, a vacuum tower, a debutanizer, a rerun unit, a ROSE unit and a naphtha splitter. The inputs to the crude unit model are crude assays and crude feed rate, the ASTM 95% points ofthe light naphtha, the heavy naphtha, the light distillate and the heavy distillate, the true boiling point (TBP) cut point ofthe heavy vacuum gas oil, atmospheric tower fiamace outlet temperature, and vacuum tower furnace outlet temperature. The model calculates the volume and the properties of those side-draw products and the vacuum bottom stream. It also calculates the temperature profile in the towers. Two standard tests are defined here since they will be often referred to in the follow text. The ASTM 95%) point is the temperature corresponding to the 95 vol.%) on the distillation curve measured by the distillation test defined by the American Society for Testing and Materials (ASTM) under the designation of ASTM D86. The ASTM method D86 is an easy test that is run in an Engler-flask at atmospheric pressure with no trays or reflux between the stillpot and the condenser. TBP curve is measured by the ASTM D2892 test, which uses a distillation column with 14 or more theoretical stages and reflux ratio of 5 or more. Temperature at any point on the TBP-volumetric yield curve represents the actual boiling point ofthe hydrocarbon material present at the volume percentage corresponding to that point. ASTM D2892 test is more expensive than ASTM D86 test. 3. 2 Atmospheric Tower Modeling The schematic ofthe atmospheric tower model is shown in Figure 3.3. The text box with gray background has internal iterations inside. The text box with white background does not have internal iterations. The indices ofthe text boxes with gray background are referred to when discussing some calculations with iterations in the following text.

20

Start

Side-draw Product Specifications, ASTM 95% point TBP 100% point

Calculate the mixed crude's curves of TBP, API gravity, and sulfur content

Crude Assays, Crude Makeup

Operating pressure, Crude Temperature, steam rate

Calculate the properties of side-draw prodcuts

Steam rate, side stripper type

Calculate flash zone temperature, Calculate the extra energy left in the tower after flash zone (1)

Calculate the properties of unstripped product witlidrawn from the draw trays (2)

Draw tray location

Calculate the temperature of the draw trays (3)

Calculate the temperature of the condenser

Calculate the temperature of side-draw products (4)

End

Figure 3.3 Schematic ofthe Model ofthe Atmospheric Tower ofthe Crude Unit.

21

3. 2.1 Feed Characterization The refinery that the model was benchmarked against processes four different crude oils: Crude A, Crdue B, Crdue C, Crdue D. They are from different resources with slight different properties. The refinery uses a Linear Programming (LP) technique for scheduling and planning. In the present work, nonlinear optimization methodology is used and results are compared with LP report. The normal crude unit feedstock makeups are given in Table 3.1. Table 3.1 Feedstock Makeups. Crude Type API Gravity Sulftir, Wt. Summer Mode Vol.% 17 8 48 27 Winter Mode Vol.% 0 0 0 100

Crude A CrudeB CrudeC CrudeD

37.4 34.2 33.7 36.1

0.08 0.54 1.04 0.32

All four crudes processed in the refinery can be characterized as light crude type. The specific gravity of these crudes range from 33.7 to 37.4. Among these crudes, only crude C is a sour crude and has a sulfur content of 1.04 wt.%. Other crudes have very low sulfur content, less than 0.54wt.%.. The refinery was designed to process light crude with low sulfur content. It can not process heavy crudes or crudes with high sulfur content. The volumetric flow rate of a side-draw product is equal to the volumetric flow rate ofthe total crude feed multiplied by the volumetric percentage ofthe side-draw product in the crude feed. Once the initial boiling point (IBP) and end boiling point (EBP) ofthe side-draw product are known, the volume percentage ofthe side-draw product can be found from the true boiling point (TBP)-volumetric yield curve ofthe whole crude as shown in Figure 3.4.

22

1000

AGOLVGO
^ 800

H V G p / Resid.

3
5 600
(U Q.

HD LD HN LN

jfl) 4 0 0

200

10

20

30

40

50 60 volume%

70

80

90

100

Figure 3.4 Crude Cuts on a TBP-Volumetric Curve. The volume percentage of a side-draw product is calculated using the formula given below:

%V,=%V,,,,-%V^j,

(3.1)

where i - side-draw product; light naphtha (LN), heavy naphtha (HN), light distillate (LD), heavy distillate (HD), atmospheric gas oil (AGO), light vacuum gas oil (LVGO), heavy vacuum gas oil (HVGO), %)Vi- volume percentage ofthe side-draw product i in the crude, %oVijBp, %iVi,EBP- volume percentage corresponding to the IBP ofthe side-product i on the TBP-volumetric yield curve ofthe crude, respectively. Hence, the TBP-volumetric yield curve ofthe crude feed is essential to calculate the volumetric flow rates ofthe side-draw products. The crude assays of these four types of crude oils were obtained from the refinery. The TBP-volumetric yield curve ofthe crude oil entering the crude unit is calculated

23

The crude assays of these four types of crude oils were obtained from the refinery. The TBP-volumetric yield curve ofthe crude oil entering the crude unit is calculated based on the TBP curves of each crude and its volumetric fractions in the feed. Ideal mixing is assumed here because these crude oils themselves are complex mixtures where deviations from the ideal mixing are assumed to be cancelled out. In addition, they are all low sulfur, light crudes with similar properties. The equation to calculate the TBP curve of mixed crude oil is given below:

v(T) = Y^v,(T)xvol,,

(3.2)

where i - crude type: A, B, C, and D, v(T)- volumetric percent ofthe mixed crude with boiling temperature lower than T, vol.%, Vi(T)- volxmietric percent of crude i with boiling temperature lower than T , vol.%, vol,- volume fraction ofthe crude i in the mixed crude. The TBP curve ofthe mixed crude oil used in Summer Mode operation is shown in Figure 3.5. For the convenience of digital computations, the TBP curve ofthe mixed crude is regressed using a polynomial expression. The regression was carried out in MathCad Plus 6.0 from Mathsoft Incorporation. The order of a polynomial expression is selected by looking at the mean square errors ofthe predictions. In this work, a polynomial expression usually has the order in the range of 5 to 7. For this polynomial expression and any polynomial expression mentioned in the following text, the order and the constants ofthe polynomial expression are listed in Appendix A. It should be noted that different TBP curves are used in the Summer Mode and the Winter Mode due to the fact that different crudes are used for different operation Mode.

24

"

600

10

20

30

40

50

60

70

80

90

100

volume% Figure 3.5 TBP Curve ofthe Crude Used in Summer Mode. Another curve required by the crude unit model is the API-volumetric yield curve. The relation between API Gravity and specific gravity is given below:

API =

141 5 ^^!^-131.5, SPG

(3.3)

where API- API gravity, SPG- specific gravity. The API-volumetric yield curve ofthe mixed crude is calculated from the APIvolumetric yield curves ofthe crude sources. The procedure of calculating the APIvolumetric yield curve ofthe mixed crude is given below: a. Approximate the API-volumetric yield curve of a particular crude by a polynomial expression.

25

b. Use a certain number of intermediate temperature points to represent the boiling range ofthe crude. For each temperature, calculate the corresponding volume percentage from the TBP-volumetric yield curve ofthe crude. c. For each volume value, find the corresponding API value using the API-volumetric yield curve ofthe crude. d. Convert API to specific gravity using equation 3.3. e. Repeat step a to step b for all four types of crudes. f. The API ofthe mixed crude is calculated using the following equation:

SPG(v) = Y, SPG^ (v) X vo/. ,

(3.4)

where SPG(v)- specific gravity of mixed crude, SPGi(v)- specific gravity of crude i, voli- volume percentage of crude i. g. Convert specific gravity to API gravity. h. Construct API-volumetric yield curve using the calculated API and approximate it by a polynomial expression. The API-volumetric yield curve ofthe mixed crude oil used in Summer Mode operation is shown in Figure 3.6. The sulfur-volumetric yield curve ofthe mixed crude is also calculated using similar procedure. It should be noted that the sulfur concentration is expressed as weight percentage instead of volume percentage. The sulfur-volumetric yield curve ofthe mixed crude oil used in the Summer Mode is shown in Figure 3.7. The sulfur-volumetric yield curve was also regressed using a polynomial expression. The polynomial expressions developed above are then used repeatedly in the atmospheric tower model and vacuum tower model. The crude processed in Winter mode operation has one crude type and no mixing calculation is required. 26

10

20

30

40

50

60

70

80

90

100

volume% Figure 3.6 API Curve of the Crude Feed Used in Summer Mode.
2.5 T

Figure 3.7 Sulfur Curve ofthe Crude Feed Used in Summer Mode.

27

3.2.2 Side-Draw Product Calculation The boiling range specification for a side-draw product is usually defined by ASTM 95% point. Since TBP test is more expensive, TBP test is only run on crude oils but not on product fractions. Hence, the side-draw product specification is defined using ASTM data instead TBP data. Conversion from ASTM 95% points to TBP cut points in the model is required in order to use the TBP-volumetric curve ofthe crude feed. It is assumed that the atmospheric tower and the vacuum tower are able to separate the side-draw products according to the ASTM 95%) specifications. This assumption is made based on the fact that the values ofthe ASTM 95% points are limited in a narrow range in the optimization studies and the crude unit has enough separation capacity to satisfy the separation requirements in this range. This assumption is confirmed by the operating personel in the refinery considered in this work. The properties ofthe side-draw products can then be calculated using the ASTM 95% point specifications without considering whether these specifications can be reached or not. Since the volume percentages ofthe side-draw products in the crude feed can only be obtained from the TBP ciuve ofthe crude feed, it is necessary to convert the specifications in the form of ASTM 95% points to TBP end points using the relation curve given by Watkins (1979). The curve has been regressed into a polynomial expression given below:

TBP end po int = X ^' ' i^^^TM 95% po int) ,

i=0

(3.5)

where Ci- constants ofthe polynomial expression. In order to decide the volume percentage of a side-draw product in the crude feed, the initial boiling point (IBP) is also required. It should be noted that the overlap ofthe TBP curves of two adjacent side-draw products can not be avoided since two side-draw streams can not be completely separated in the atmospheric tower and the vacuum tower.

28

In other words, there are always some components in the boiling range ofthe lighter stream entering the heavy streams and vice versa. Therefore, the IBP ofthe heavier product is always lower than the end boiling point (EBP) ofthe adjacent lighter product. The extent ofthe overlap represents the separation efficiency in the atmospheric tower. The smaller the overlap, the better the separation. The separation is defined by Gap (595) ASTM, which is the temperature difference between the ASTM 5% point ofthe heavier product and the ASTM 95% point ofthe adjacent lighter product. The values of Gap (5-95) ASTM in normal industrial practice (Watkins, 1979) are used here for all pairs of adjacent side-products except the pair ofthe heavy distillate and the atmospheric gas oil. The value from the Lin (1988) is used for the Gap (5-95) ASTM between the heavy distillate and the atmospheric gas oil uses. The Gap (5-95) ASTM for each pair of adjacent side-draw products is listed in Table 3.2.

Table 3.2 Gap (5-95) ASTM Temperature between Adjacent Side-Draw Products in the Atmospheric Tower. Stream Light NaphthaHeavy Naphtha Heavy NaphthaLight Distillate Light DistillateHeavy Distillate Heavy distillateAtmospheric gas oil 5 10 35 Gap Spec, (5-95) ASTM, F 25

The Gap (0-100) TBP, which is the temperature difference between the 0% TBP point ofthe heavier product and the 100%) TBP point ofthe adjacent lighter product, can be calculated from corresponding Gap (5-95) ASTM temperature using the conversion curves given by Watkins (1979). The curve has been regressed into a polynomial expression shown below: 29

Gap {O -1 GO) TBP = X ^z [Gap (5 - 95) ASTM]

;=

(3.6)

where Cj- constant ofthe polynomial expression. Once the values ofthe Gap (0-100) TBP are knowoi, the IBP of each side-draw product is calculated from the EBP ofthe adjacent lighter product using the following formula:

IBP of heavier product = EBP of adjacent light product - Gap (0-100) TBP, (3.7)

The IBPs of all side-draw products are calculated using equation 3.7 except the light naphtha, the lightest stream. The IBP ofthe light naphtha is the IBP ofthe whole crude oil. The TBP cut point of a side-draw product is then calculated using following equation:

TBP cut point = -(t,, +to), where tiooL- TBP 100% point ofthe lighter stream, ""F, toH- TBP 0% point ofthe heavy stream, ""F.

(3.8)

This methodology has been established by analysis of operating data which has shown that, for well stripped sidestreams, the volume interchange between two streams around the TBP cut point are equal (Watkins, 1979). The TBP cut points can then be applied to determine the volume percentage of each side-draw product in the crude feed from the whole crude TBP-volumetric curve.

30

The volumetric flow rates of all side-draw products except the AGO can be calculated by multiplying the volume percentage of the side-draw product by the volumetric flow rate ofthe crude feed. For the AGO, the ASTM 95% point, which determines the total volume of products from the atmospheric tower, is not an independent variable once the atmospheric furnace outlet temperature is defined. This is because that the total volume ofthe top product and the side-draw products is approximately equal to the volume ofthe feed vaporized in the flash zone, which is determined by the temperature and pressure in the flash zone. The total volume ofthe product can then decide the ASTM 95% ofthe AGO. Hence, the ASTM 95% point ofthe AGO is not an independent variable in the atmospheric tower model. Instead, it is calculated in the crude unit model according to the conditions in the flash zone ofthe atmospheric tower. At the beginning ofthe crude unit model calculation, an initial value ofthe ASTM 95%) point ofthe AGO is set and the final value is calculated in the model. The mass flow rate ofthe side-draw products can be obtained from the corresponding volumetric flow rates and API gravity values. The API gravity for a crude cut with narrow boiling range is calculated by applying the middle-point temperature to the API-volumetric curve. Since the API-volumetric curve ofthe whole crude is very close to a slight line over a narrow temperature interval, this approximation gives almost the same value as the more accurate approach in which numerical integration is used leading to a high computational load. However, for a wide cut, the API-volumetric curve is not a straight line over the boiling range ofthe cut. Hence, the weight ofthe cut is first calculated by integration along the volumetric-API curve over its boiling range. The TBP boiling range ofthe side-draw product is divided into 10 intervals. The API gravity value of each interval is obtained from the API-volumetric curve and is converted to specific gravity. Simpson's rule is then used to calculate the weight ofthe side-draw product by integrating along volumetric-API curve over its boiling range. The API gravity ofthe cut is then determined by the volume and the weight ofthe cut. The weights of all side-draw products are obtained from the API-volumetric curve using either ofthe two methods introduced above.

31

The TBP curve of each side-draw product is the same as the portion ofthe whole crude TBP curve between the IBP and EBP ofthe side-draw product. For example, the TBP curve ofthe heavy naphtha is the same as the portion ofthe whole crude TBP curve between the IBP and EBP ofthe heavy naphtha. The ASTM curve of a side-draw product is an important property. The ASTM curve can be used to calculate other properties ofthe side-draw product. The ASTM curve of each crude cut is converted from the TBP curve using the correlation given by Daubert (1994). Daubert gave the procedure to convert an ASTM curve to a TBP curve explicitly. Converting a TBP curve to an ASTM curve is done by reversing the procedure. The conversion from a TBP curve to an ASTM curve follows the steps above: a. Calculate the TBP 50% point from ASTM 50% point using the following formula:

ASTM(50) = 0.87180 where

(TBP( 50 ))""'',

(3.9)

TBP(50)- TBP distillation temperature at 50 vol.% distilled, F, ASTM(50)- ASTM distillation temperature at 50 vol.% distilled, F. It is claimed that equation 3.9 best correlates data with ASTM 50% point temperatures below 480 F. b. Calculate the temperature difference among the points on the ASTM curve from the temperature difference among the points on the TBP curve using the formula given below:

(AASTM)^

= -(ATBP)i B, A

(3.10)

where (A TBP)i- difference in TBP distillation temperatures between two cut points, F,

32

(A ASTM)i- difference in ASTM D86 distillation temperatures between two cut points, F, The values of A and B are given in Table 3.3 for various cut point ranges with the maximum values of (A ASTM)i that can be applied in the correlation.

Table 3.3 A and B Variables for Equation 3.10. Number Cut-point range 100% to 90% 90% to 70% 70% to 50% 50% to 30% 30% to 10% 10%toO% A B Maximum applicable (A ASTM)i, F
-

1 2 3 4 5 6

0.11798 3.0419 2.5282 3.0305 4.9004 7.4012

1.6606 0.75497 0.82002 0.80076 0.71644 0.60244

100 150 250 250 100

c. The TBP temperatures are calculated using equations from 3.11 a to 3.11 f. ASTM(O) = ASTM(50)-(AASTM), ASTM(10) = ASTM(50)-(AASTM), ASTM(30) = ASTM(50)-(MSTM),, ASTM{1Q) = ASTM {SO) + (AASTM)^, ASTM(90) = ASTM (50) + (AASTM), + (MSTM),, ASTM(IOO) = ASTM(50) + (AASTM), + (AASTM)^ + (AASTM),. -(AASTM), -(AASTM),, -(AASTM),, (3.11a) (3.11b) (3.11c) (3.1 Id) (3.1 le) (3.1 If)

It is claimed that this method is more accurate than other methods (Daubert, 1994). The volume average boiling point (VABP) and mean average boiling point (MeABP) are calculated from the ASTM curve using the correlation given by Lin (1988). The VABP is calculated from the following formula:

33

-., ASTM(IO) + ASTM(30) + ASTM(50) + ASTM(70) + ASTM(90) VABP = (3.12)

MeABP can not be calculated by its definition. It is calculated from VABP using the following formula:

MeABP = VABP-AT,

(3.13)

where AT- temperature difference between VABP and MeABP, "^C. AT is a function ofthe VABP and the slope ofthe ASTM curve S. The slope ofthe ASTM curve S is calculated using the following formula:

^_ASTM(90)-ASTM(10) 90-10 Where S- Slope of ASTM cruve, C/%. AT is calculated using following formula:

lnAT = -1.53181-0.0128-(VABP)"''"'

+3.6474-S""'\

(3.15)

The units of VABP, MeABP, and AT are all C. The molecular weight of each side-draw product is calculated from the MeABP and the API gravity ofthe side-draw product using the correlation given by Riazi and Daubert (1980) using the following formula:

34

Molecular Weight = 4.5673E - 5 (MeABP)'""

SPG-""'',

(3.16)

where SPG- specific gravity of the crude cut. However, it is found that this formula predicts molecular weights of heavy cuts lower than the industrial data obtained from the refinery considered in this work. Hence, the molecular weights of crude cuts heavy than light naphtha are calculated from the curves given by Maxwell (1950) which correlate the molecular weight of crude cut to its MeABP and characterization factor. The characterization factor is calculated using the formula given below:

Characterization Factor = SPG

(3.17)

where MeABP has units of R. Maxwell (1950) gave three molecular weight curves of crude cuts corresponding to three regions ofthe characterization factors, 12.1-12.6, 11.7-12.0, and 11.3-11.6. The three curves were regressed using polynomial expressions in this work. The polynomial expression has the following formula:

Molecular Weight = J ] ^/" {MeABP) ,

(3.18)

where MeABP has units of F. The molecular weight ofthe crude cut whose characteristic factor falls in one ofthe three regions is calculated from equation 3.18 using the polynomial constants corresponding to it. For example, the characteristic factor of a crude cut is 11.8, which is in the region of 11.7-12.0. The molecular weight of this crude cut is calculated using the polynomial constants corresponding to the region of

35

11.7-12.0. For all the crude cuts in this work, the characteristic factors are between 11.3 and 12.6. Hence, Maxwell method can be applied to any crude cut in this work. 3.2.3 Atmospheric Tower Furnace Calculation The temperature ofthe crude before entering the atmospheric furnace is set at 481 F according to the operation data obtained from the refinery considered in this work. The heat duty ofthe fiimace is calculated as the enthalpy difference between the crude entering and exiting the furnace. The enthalpy ofthe crude cut is calculated from the graph of enthalpy of petroleum fractions in Watkins (1979). The enthalpy is a function of API gravity, temperature and phase. For a particular API gravity and phase, an enthalpytemperature curve is given. For the convenience of digital computation, polynomial expressions were used to represent the curves in the graph. The vaporization enthalpy of a crude cut is calculated by evaluating the difference between enthalpies ofthe crude cut in liquid phase and in vapor phase.
3.2.4 Flash Zone Calculation The temperature and the pressure in the flash zone are required to calculate the volume of total distillate products. The flash zone pressure is often set at the minimum possible level in order to maximize the crude vaporization at a certain temperature. The pressure in the condenser ofthe atmospheric tower and pressure drops across the condenser and associated piping, trays, and transfer line between the atmospheric furnace and flash zone in the atmospheric tower considered here are listed in Table 3.4. The pressure in the flash zone is then calculated as below:

P
flashzom

- P
condenser

+ AP
piping

+ AP
lower'

Ci 1Q"*
\-' ^ ^)

36

Table 3.4 Pressure in the Atmospheric Tower. Pressure value Condenser Pressure Pressure drop across the condenser and associating line Pressure drop between the column top and the flash zone Pressure drop across the transfer line 5 psi 1.9 psi 14.5 1.9 Pressure unit Pisa psi

It is assumed that in the overflash, the extra vaporization which provides reflux in the section between the flash zone and the first side-stream product draw tray, is 2 vol.% ofthe crude feed based on common industrial practice (Watkins, 1979). Further, it is assumed that the bottom stream is steam stripped at a rate of 10 pound steam per barrel of the reduced crude according to common industry practice. The overflash and steam rate used in the refinery varies in the operation. The assumed values are in the normal operation range ofthe refinery. The flash zone ofthe atmospheric tower is shown in Figure 3.8. The steps involved in the heat and material balance calculations are listed below: a. Calculate the volume, weight and API gravity of each side-draw product except AGO using the given ASTM 95% points and whole crude TBP-volumetric curve and APIvolumetric curve. b. Assume an initial value for ASTM 95% cut point of AGO. 1. Calculate the volume, weight and API gravity of AGO. 2. Calculate the volume and weight of total distillate product ofthe atmospheric tower. 3. Calculate the volume and weight ofthe reduced crude. c. Assume an initial value for the flash zone temperature. Calculate the feed flash and bottom stripping required to yield the required volume of vapor. The curves given by Watkins (1979) are used to calculate the volume percentage of nonvaporized crude which

37

is stripped out. The curves in Watkins (1979) were regressed using polynomial expressions. 1. Calculate the volume percentage of crude distilled in the flash zone. Equilibrium flash vaporization (EFV) curves are constructed from the flash data calculated in ChemCad 4.0 software package from Chemstations, Incorporation. The constants of the EFV curves are listed in Appendix A. Flash curves between 26 psia and 48 psia are constructed in this work. The pressure in the flash zone is then calculated by interpolating among these EFV curves according to the volume percentage distilled. Calculate the total enthalpy in the flash zone. 2. Calculate the total enthalpy at the furnace outlet using the given fiimace outlet temperature. d. Compare the total enthalpy in the flash zone and the ftimace outlet. If they do not match, calculate the flash zone inlet temperature using secant method (Riggs, 1994). Return to step c. e. Compare the flash zone pressure obtained above and the flash zone pressure calculated from equation 3.19. If they do not match, calculate new value of ASTM 95% point of AGO using secant method. Return to step b. The flowchart ofthe calculation ofthe flash zone pressure and temperature is shown in Figure 3.9. The above iterative procedure is inside the gray block no.I in the schematic ofthe atmospheric tower model shown in Figure 3.3.

38

Tray 5

fo

Vapor Liquid Tray 4

Crude
"fo

v.

Furnace Stripout Tray 1 Stripping Steam

Figure 3.8 Flash Zone ofthe Atmospheric Tower.

39

Start

Crude Assay Property Calculation of Side-draw Products except AGO Initial Guess of ASTM 95% Point of AGO AGO Calculation Total Product Calculation Reduced Crude Calculation Initial Guess of Flash Zone Temperature Flash Calculation at Furnace Outlet and Flash Zone Yes Calculate New Flash Zone Temperature ASTM 95% Points of Side-draw Products

Yes

Calculate New ASTM 95% of AGO

No

End

Figure 3.9 Flowchart for the Calculation of Flash Zone Pressure and Temperature.

40

In step c, the curves in Watkins (1979) to calculate the amount of stripout from the steam rate are regressed using polynomial expressions given by the following formula:
n

Stripout = ^ c, {steam rate)

i=0

(3.20)

where stripout has the unit vol.% and steam rate has the units of pounds of steam/barrels of stripped liquid. The heat balance ofthe flash zone is then calculated using the flash zone temperature obtained above. The vapor in the flash zone is the summation ofthe feed vaporized in the flash zone and the steam stripout ofthe nonvaporized feed dropping from the flash zone to the tower bottom. Thus, the enthalpy of vapor in the flash zone is the summation ofthe enthalpies of these two streams which have been calculated above. The temperature ofthe flash zone vapor is calculated from the enthalpy ofthe flash zone vapor. There are usually four trays between the flash zone and the tower bottom. The temperature ofthe reduced crude is calculated on the basis ofthe energy balance for the tower bottoms. The calculation is carried out using following steps: a. Assume the temperature ofthe tower bottom is about 30F cooler than the tower inlet temperature. Calculate the temperature of tray 4 assuming linear temperature distribution in the four trays between the flash zone and the tower bottom. It should be noted that the temperature of tray 4 is different from the inlet temperature ofthe crude feed. b. Calculate the enthalpy ofthe stripout ofthe liquid dropping from the flash zone. The amount ofthe stripout is calculated using equation 3.20. c. Calculate the enthalpy ofthe overflash liquid. It is assumed that the overflash falls to the flash zone at a temperature of 20'^F cooler than the tower inlet temperature. d. Calculate the enthalpy ofthe reduced crude by making an energy balance around the tower bottom.

41

e. Calculate the temperature drop across the four trays between the flash zone and the tower bottom using the enthalpy ofthe reduced crude and the specific heat ofthe reduced crude. Calculate the tower bottom temperature. f. Compare the calculated tower bottom temperature with the initial guess. If they do not match, return to step a with the new value ofthe tower bottom temperature equal to the calculated tower bottom temperature. The above iterative procedure is inside the gray block no.2 in the schematic ofthe atmospheric tower model shown in Figure 3.3. It is assumed that the temperature ofthe reduced crude is equal to the tower bottom temperature. The external energy left in the tower above the flash zone is then calculated using the equation below:

External energy = enthalpy of crude and steam - enthalpy of the reduced crude . (3.21)

The enthalpy of steam is obtained from Moran and Shapiro (1996). The data were regressed into polynomial expression for the convenience of digital computations. The external energy calculated here will be used in the following side-draw temperature calculation. 3.2.5 Side Stripper Calculation When the side-draw product liquid is withdrawn from the tower, there are some light components in the stream which belong to lighter side-draw products. To recover these light components, side strippers are used to strip the light components from the unstripped product stream. There is a side stripper for each side-draw product. Although the strippers with reboiler are sometimes used in industry, only the side strippers with steam are used in the refinery considered in this work. Hence, only steam side strippers were considered in the present work. The side stripper models are used to calculate the properties of unstripped products for later use in side-draw temperature calculation. It

42

should be noted that the volume and properties ofthe stripped product have already been calculated in the procedure presented in section 3.2.2. After an unstripped side-draw product stream is withdrawn from the draw tray, it enters the side stripper at the top. The steam enters the side stripper at the bottom. Since the partial pressure of crude components in the gas phase is low in the side-stripper, some light components are vaporized and flow with the steam back to the column. The stripped product exits from the bottom ofthe stripper. The volume percentage of the unstripped side-draw products vaporized in the side strippers is calculated using equation 3.20. For the unstripped product, its EBP is the EBP ofthe stripped product while its IBP is obtained from the whole crude TBP-volumetric curve using the temperature corresponding to the volume pecentage equal to the summation ofthe volumetric flow rate ofthe stripout and the stripped product. Volumetric Flow Rates of Unstripped Pr oduct = Stripout + Volumetric Flow Rates of Unstripped Pr oduct

After the corresponding IBP and EBP ofthe unstripped side-draw product are obtained, the API gravity ofthe unstripped side-draw product can then be obtained from the whole crude API-volumetric curve. The mass flow rates ofthe unstripped side-draw product are calculated using its volumetric flow rates and the API gravity. 3.2.6 Draw Tray Locations The atmospheric tower model here represents the preflash tower and the atmospheric tower ofthe refinery considered in this work together. Thus, the draw tray locations ofthe atmospheric tower in the refinery are not applied here. In addition, since the crude unit is not a common distillation column, normal shortcut methods to calculate the number of theoretical trays are not applicable here. Actually, accurate draw tray location is not vital in the present modeling work because material balances and energy balances are carried out around separation sections instead of single trays.

43

The number of trays for a separation section between a particular pair of adjacent side-draw products is almost the same for every atmospheric tower. The numbers suggested by Lin (1988) are used here. The number of trays of each separation section is listed in Table 3.5. The total number of trays in the atmospheric tower is 38.

Table 3.5 Tray Numbers of Separation Sections in Atmospheric Tower. Separation section Light naphtha-heavy naphtha Heavy naphtha-light distillate Light distillate-heavy distillate Heavy distillate-atmospheric gas oil Feed-atmospheric gas oil Bottom-Feed Tray number 7 8 7 9 3 4

The draw tray location can then be calculated from Table 3.5. It should be noted that the numbering is from the bottom to the top. In the crude unit ofthe refinery considered in the work, a packing section is used between AGO side-draw tray and the flash zone. The separation capability ofthe packing section is equal to 3-4 trays. In this study, 3 trays are assumed. The important tray locations are listed in Table 3.6. Table 3.6 Draw Tray Location. Separation section Reduced Crude Feed tray AGO draw tray Diesel draw tray Kerosene draw tray Heavy naphtha draw tray Light naphtha draw tray Tray number Bottom 4 7 16 23 31 Top

44

There are two pumparounds with this crude column. One pumparound is located in the separation section between the heavy naphtha side-draw tray and the kerosene sidedraw tray and the other pumparound is located in the separation section between the diesel side-draw tray and the atmospheric gas oil side-draw tray. The locations ofthe pumparound are set according to normal industrial practice (Watkins, 1979). Usually, the pumparound withdraws liquid from a tray above the lower draw tray, exchanges heat with crude feed and returns the liquid to a tray ftirther up in the tower but below the upper draw tray. In the model, the upper pumparound returns the liquid to the tray below the corresponding upper draw tray. The lower pumparound returns the liquid to the third tray below the corresponding draw tray. The fimction of pumparounds is to reduce the liquid and vapor traffic at the upper section ofthe atmospheric tower and reduce the heat load ofthe overhead condenser. The disadvantage of using pumparounds is that several trays between the pumparound withdrawing tray and returning tray can only be considered as only one actual tray for fractionation purposes (Watkins, 1979). The benefit of having two pumparounds is that two different temperature levels of heat sources are provided for crude preheating. 3.2.7 Draw Tray Temperature Calculation The calculation procedure for draw temperature is similar for all draw trays. Only the general methodology is described here. The sequence of draw tray calculation is from the bottom to the top. The envelops used in the energy balance and material balance include all the lower part ofthe tower to the bottom ofthe tray above the draw tray. A draw tray and its envelop for energy balance and material balance are shown in Figure 3.10. The draw tray calculation follows the procedure in Watkins (1979). The draw tray temperature is calculated using energy balance. For each energy balance around the envelop corresponding to the draw fray, the difference between the enthalpy ofthe vapor going up and the enthalpy ofthe liquid coming down is calculated. This enthalpy difference is regarded as the external energy left in the tower which will be absorbed by pumparounds above the draw tray and by overhead condenser. The external

45

energy calculated in the lower draw tray can be used directly in energy balance of the upper draw tray. This approach eliminates the need to calculate the all the inlet streams and outlet streams below the draw tray. The energy balance for a draw tray only requires that the inlet and outlet streams around the draw tray are calculated. Usually, the outlet stream in the energy balance is the side-draw product stream. The inlet stream is the steam used in the side-stripper which then enters the tower. If a pumparound exists between the draw tray and adjacent lower draw tray, the external energy left in the tower is subtracted by the amount ofthe heat load ofthe pumparound. The pumparound heat loads are fixed according to common industrial practice (Watkins, 1979).

stripout

tray

unstriped ^ product steam

Envelop containing all the lower part o f t h e tower

side-draw product

Envelope for the energy balance of a side-draw tray

Envelope containing all the lower part o f t h e tower

Figure 3.10 Energy and Material Balance Quantities at a Side-Draw Tray.

46

The draw temperature calculation follows the steps below: a. Make an initial guess for the draw tray temperature. Calculate the enthalpies ofthe liquid and vapor leaving the draw tray. The volume ofthe vapor is the summation of volumes of all the lighter products withdrawn above the separation section. The liquid is the unstripped side-draw product that has already been calculated in side stripper calculation. b. Calculate the heat absorbed in passing across the draw tray by the liquid that is vaporized in the side-draw product stripper. The temperature of tray above the draw tray is set at I5F higher than the draw tray temperature. c. Calculate the reflux heat on the basis ofthe energy balance ofthe envelope corresponding to the draw tray. d. Calculate the volumetric flow rate ofthe reflux falling from the tray above the draw tray according to reflux heat and the specific heat ofthe refiux. The specific heat of the reflux is assumed to be the same as the specific heat capacity ofthe side-draw product. e. Calculate the molar flow rate ofthe reflux and all the lighter products. Calculate the pressure ofthe draw tray according to the known flash zone pressure and assumed constant pressure drop for each tray. f. Calculate the hydrocarbon partial pressure according to the mole fraction ofthe reflux, which has the same composition as the side-draw product, in the total vapor leaving the draw tray. This approach is suggested by Lin (1988). g. Calculate the TBP curve ofthe stripped product. Convert the TBP curve to the Equilibrium Flash Vaporization curve (EFV) wdth the partial pressure using the method given by Maxwell (1950). The initial point ofthe EFV curve is the bubble point ofthe stripped side-draw product. h. Compare the calculated bubble point with the draw tray temperature. If they do not match, use the calculated bubble point as the draw tray temperature and return to step a.

47

The flowchart for the calculation ofthe draw tray temperature is shown in Figure 3.11. The above iterations are inside the gray block no.3 in the schematic ofthe atmospheric tower model shown in Figure 3.3. The temperature ofthe condenser is calculated as the bubble point ofthe overhead product, light naphtha, under the condenser pressure. Only the temperature calculation in step g above is required for condenser temperature calculation.

3.2.8 Side-Draw product temperature calculation In order to calculate the enthalpy ofthe side-draw product which is used in the calculation ofthe external heat left in the tower, the temperature ofthe stripped side-draw product is required. The temperatwe ofthe side-draw product can be calculated through applying an energy balance arovmd the side stripper. It is assumed that each side stripper has four trays (Watkins, 1979). The vmstripped product enters the first tray from the top and the steam enters the fourth tray. The stripped side-draw product leaves the side stripper at the bottom. The stripout and steam exit from the top ofthe side-stripper and flow back to the atmospheric tower. The calculation follows the steps below: a. Estimate the steam-free At across the side-stripper using the graph in Watkins (1979). Polynomial expressions are used to represent the curves in the graph. b. Estimate the temperature correction for the steam-free At using the correlation in Watkins (1979). Calculate real At across the side-stripper. This value becomes the initial guess for At. c. Assume equal temperature differences across each ofthe four stripping trays (Watkins, 1979). Calculate the temperature ofthe top tray and the bottom tray according to the side-draw tray temperature. d. Make an energy balance around the side-stripper using the temperature calculated above. The enthalpy of exiting water comes from Moran and Shapiro (1996). The enthalpy ofthe stripped side-draw product is calculated using this enthalpy balance. The temperature ofthe stripped side-draw product is obtained from the enthalpy value.

48

Start Initial Guess ofthe Temperature ofthe Side-draw Tray Enthalpy Calculation of Vapor and Liquid Leaving the Side-draw Tray

Reflux Heat Calculation Reflux Rate Calculation

Calculation ofthe Molar Fraction ofthe Reflux

Hydrocarbon Partial Pressure CaVs^ation

Side-draw Product Bubble Point Calculation

No

End

Figure 3.11 Flowchart ofthe Side-Draw Tray Temperature Calculation.

49

e. Compare this temperature with the bottom temperature calculated before. If they do not match, return to step c with the new calculated bottom temperature. The above iterations are inside the gray block no.4 in the schematic ofthe atmospheric tower model shown in Figure 3.3. After the temperature ofthe side-draw product is calculated, the external heat left in the tower is then calculated by subtracting the heat output ofthe side-draw product and adding the heat input of steam to previously calculated external heat. This value is then used in temperature calculation of upper draw trays. In Calculating the temperature profile in the atmospheric tower, it is assumed that temperature distribution between adjacent draw trays is linear. Temperature profile along the trays can then be obtained on the basis ofthe temperature and pressure of draw trays. 3.3 Vacuum Tower Modeling Under normal pressure and temperature in the flash zone of an atmospheric tower, the maximum amount of oils which will vaporize is described by the whole crude TBP cut points between 700F and 800F. Further increasing the temperature in the flash zone will result in thermocracking and coking in the flash zone. The reduced crude usually still contains a large volume of distillable oil which can be recovered by vacuum process. The distillable oil is lighter, cleaner, thus, has higher market value than the reduced crude. The fimction ofthe vacuum tower is to recover this part of distillable oil. The vacuum tower modeled here is a fuel-oriented type. That is, the vacuum tower produces feed to FCC unit for gasoline production and produces vacuum residue for the No.6 fuel oil. Since No. 6 fuel oil has a low market price, the amount of vacuum residuum should be minimized. This is called pitch operation. If the vacuum residue is used for asphalt, some gas oil must be left in the residuum in order to provide the proper degree of plasticity (Watkins, 1979). Pitch operation is used in the refinery considered in this work. Hence, the same operation mode is considered for the vacuum tower modeling. A fliel-oriented vacuum tower normally does not require any particular degree of fractionation between cuts. The HVGO and LVGO side-draw streams produced in a 50

vacuum tower will be combined together after the vacuum tower and become the feed to FCC unit. Using two side-draw streams is to decrease the liquid and vapor traffic in the upper section ofthe vacuum tower, which is a common constraint of vacuum tower operation. A fiael-oriented vacuum tower usually uses pumpback reflux, grid type contacting sections and chimney draw trays (Watkins, 1979). The pumpback withdraws liquid on the product side-draw tray, cools the liquid, and return the liquid to the top of corresponding grid type contacting section. It can be seen from the schematic ofthe vacuum tower shown in Figure 3.2 that pumpback is used for both separation sections. There is also an overflash stream in the vacuum tower to provide enough wetting liquid for the section between overflash liquid draw tray and the flash zone. The overflash can also be used to control the quality ofthe HVGO, preventing high viscosity material from entering HVGO. The overflash is set at 2 vol.% ofthe reduced crude according to normal industrial practice (Watkins, 1979). The overflash stream withdrawn from the vacuum tower on the overflash draw tray returns to the vacuum crude as the feed to the vacuum tower. The light crude processed in the refinery considered in this work does not have a large volume of heavy ends. Hence, the capacity ofthe vacuum tower is not an active constraint in operation. In fact, the capacity of downstream units limits the product rates from the vacuum tower. Therefore, for the range ofthe TBP end point ofthe HVGO, enough separation capacity is assumed for the vacuum tower. The modeling of a ftiel-oriented vacuum tower follows the procedure in Watkins (1979). The basic approach is similar to that used in atmospheric tower modeling. Therefore, only the steps which are different from the atmospheric tower model are described here. 3.3.1 Vacuum Tower Furnace Calculation The outlet temperature ofthe furnace ofthe vacuum tower is set at 763 F according to the design documents for the refinery. The reduced crude exiting the atmospheric tower bottom first exchanges heat with the fresh crude feed and then flows to the furnace. The inlet temperature is set at 558F according to the process flow 51

diagram (PFD) ofthe vacuum operation. The heat duty ofthe furnace is calculated as the enthalpy difference between the reduced crude entering and exiting the furnace. 3.3.2 Side-Draw Product Calculation The total volume of side-draw products is calculated using the TBP-volumetric curve ofthe whole crude using the given TBP end point ofthe HVGO. According to industrial data, the volumetric percent ofthe LVGO in the total VGO is 61.22 vol.% in the winter and 49.78 vol.%o in the summer. Hence, the volumes of LVGO and HVGO can be calculated using these values. The volume ofthe overflash is also calculated according to 2 vol.%) ofthe reduced crude.

3.3.3 Flash Zone Calculation The flash zone temperature is assumed to be the same as the fiimace outlet temperature, 780 F. The flash zone hydrocarbon pressure is calculated based on the equilibrium flash vaporization. An initial value ofthe flash zone hydrocarbon pressure is assumed and an equilibrium flash vaporization is performed. The calculated total vaporization is compared with the total volume ofthe side-draw products plus the overflash. If two values are different, new value is set for the flash zone pressure. The secant method (Riggs, 1994) is used in the flash zone pressure solving. The equilibrium flash vaporization (EFV) curve for the flash zone pressure is needed to calculate the volume percent ofthe reduced crude flashed. The EFV curve for atmospheric pressure is obtained from the TBP curve ofthe reduced crude using the method given by Maxwell (1950). The steps ofthe method are as follows: a. Construct a distillation reference line using the formulas given below:

c/ fr^i?r Slope of DRL =

TBP{70)-TBP{\0) ^f^Z^ '

(^-23) (3.24)

DRL{50) = TBP{\ 0) + Slope of DRL -(50-10),

where

52

DRL- the distillation reference line, DRL(50)- the 50% ofthe distillation reference line. b. Construct a flash reference line. The slope and 50%) point ofthe flash reference line are obtained from those ofthe distillation reference line based on the graph in Maxwell (1950). The curves in Maxwell (1950) were regressed using polynomial expression. c. Use intermediate points to represent TBP curve ofthe reduced crude and corresponding distillation reference curve. The ATdri, the temperature difference between the corresponding intermediate points on TBP curve and distillation reference curve, is calculated using the following equation:

AT^^, = TBP(i) - DRL(i).

(3.25)

d. Obtain the ratios between

ATDRL

and ATFRL, the temperature difference between the

corresponding intermediate points on the EFV curve and the flash reference curve from the curves given Maxwell (1950). The curves in Maxwell (1950) were regressed using polynomial expression.
ATFRL

is then calculated using the following equation:

^Tp^j = AT^^j Ratio^^.

(3.26)

e. Use intermediate points to represent the EFV curve ofthe reduced crude. These intermediate points are calculated using the following equation:

EFV(i) = FRL(i) + ATp^,.

(3.27)

The difference between EFV curves under atmospheric pressure and flash zone pressure is calculated using the method given by Lin (1988). The steps ofthe method are given below:

53

a. Find the EFV(50) under the low pressure from the EFV(50) of atmospheric pressure based on the curves given by Lin (1988). The curves in Lin (1988) were regressed using polynomial expressions. b. Use intermediate points to represent the EFV curve under atmospheric pressure. Usually 11, 9, 7, and 5 intermediate points are used to represent the EFV curve depending on the requirement ofthe empirical correlations. Calculate temperature difference among these intermediate points. c. Assume that the temperature difference among these intermediate points do not change with pressure. Construct the EFV curve by calculating the intermediate points ofthe EFV curve under the flash zone pressure using the EFV(50) and temperature difference obtained in step a and b. It is claimed that the error of above method is no greater thein 14C (Lin, 1988). A constant air leak is assumed for the vacuum tower. The weight of air leak is set at 44 pounds per hour according to Watkins (1979). The air is considered as an inert in the calculation. The total pressure ofthe flash zone is then calculated assuming ideal mixture. The temperature ofthe vacuum residue is assumed to be the flash zone temperature. An energy balance is carried out around the flash zone. The enthalpy of air is obtained from Moran and Shapiro (1996). The external heat left in the tower, which is enthalpy ofthe vapor going upward, is calculated. The flash zone calculation of vacuum tower is similar to that of atmospheric tower. 3.4 Separation Section Calculation The vacuum tower has three separation sections: Overflash section, HVGO section and LVGO section. There is no overhead condenser. The cooling is provided totally by the pumpbacks. It is assumed that 3.81 millimeter Hg pressure drop for each chimney tray and each grid separation section according to plant data. The pressure distribution is then calculated from the assumed pressure drop and the flash zone pressure calculated above.

54

The energy and material balances calculation ofthe separation sections in the vacuum tower are similar to those in the atmospheric tower model.

3.5 Comparison between the Developed Model and Tray-to-Tray ChemCad Model Since the crude unit model is a simplified model, it is necessary to compare it with a more rigorous model to find out if the developed model can satisfy the requirement ofthe refinery-wide optimization. For this purpose, a ChemCad model was constructed for comparison. The ChemCad model is a rigorous tray-to-tray model constructed using software package CHEMCAD 4.0. In the ChemCad model, 45 pseudocomponents are used to represent the crude feed. The atmospheric tower and vacuum tower in ChemCad model have exactly the same design as the developed model. Same crude is used in the ChemCad model in the Summer Mode and the Winter Mode. The values ofthe overhead pressure, pressure drop and steam usage used in the developed model are also used in the ChemCad model. The side-draw tray locations and the sidestripper type are also the same. In addition, the heat duties ofthe pumparounds and condenser for both models are the same. The fiowsheet of ChemCad model is shown in Figure 3.12. The most important fimction ofthe crude unit is predicting the volumetric flow rates ofthe side-draw products. The volumefric flow rates ofthe side-draw products are decided by the given ASTM 95%) point or TBP 100%. The separation specifications of side-draw products are shown in Table 3.7. The same specifications are used in the ChemCad model except that the ASTM 90%) point is used for Heavy Vacuum Gas Oil. The discrepancy may be due to the fact that the Crude Assays obtained from the refinery do not have detailed information at the high boiling range which results in the inaccurate information ofthe pseudo-components at the heavy ends ofthe distillation curve.

55

0) 0

o
2 C D

0) 0 3 H U

a u

e
tt)

u
14-1

o
0
H 4-> IB

e
o

0)

u
H
[I4

Table 3.7 Separation Specifications of Side-Draw Products. Side-draw Product Light Naphtha Heavy Naphtha Light Distillate (Kerosene) Heavy Distillate (Diesel) Heavy Vacuum Gas Oil Specification, F 257 430 530 650 1050 SpecificationType ASTM 95% ASTM 95% ASTM 95% ASTM 95% TBP 100%

The comparisons between the side-draw product flow rates ofthe developed model and ChemCad model in the Summer Mode and the Winter Mode are shown in Figure 3.13 and Figure 3.14. The flow rates match well for most ofthe side-draw products. The small mismatch will only affect the refinery-wide optimization if the separation specifications, ASTM 95%) or TBP 100%) point, are at the specification limits, which is rarely the case in the optimization studies. The side-draw product rates are usually constrained by the capacities of downstream units instead ofthe specification limits. Another important test is the gain comparison, that is, the comparison between the changes of product flow rate versus the changes ofthe separation specifications obtained from two models. Having correct gain is critical in optimization studies. The optimization routine needs the gain information between the decision variables and the optimization objective fianction to decide the optimization search direction. The gains between the separation specifications and the product rates significantly affect the gain between the separation specifications and the objective function. Hence, the developed model must have correct gains so that it can be used in the following optimization studies. The normal operating values for the base case are listed in Table 3.7. The furnace ouflet temperature is set at 653F in the base case. Each ofthe ASTM 95% point, TBP 100% point, and furnace outiet temperature is perturbed by plus 5F and minus 5F sequentially in the test.

57

16000 14000 12000 ^

(3

D Simplified Model ChemCad Model

10000 8000 6000 4000 2000 0 light naphtha heavy naphtha kerosene diesel AGO VGO

2 oa

m
vacuum residue

Figure 3.13 Comparison of Simplified model and ChemCad Rigorous Model, Summer Mode. 18000 16000 14000 12000 I" 10000 m 8000
CQ

D Simplified Model ChemCad Model

6000 4000 2000 0

M
light naphtha

heavy naphtha

kerosene

diesel , ,

AGO

VGO

vacuum residue

volume%) Figure 3.14 Comparison of Simplified Model and ChemCad Rigorous Model, Winter Mode.

58

The product rates after the perturbation were compared to those ofthe base case and the gains were estimated by the formula given below.

^-^>..

(3.28)

^^y

Ti-Tj,^,,

The average gains were calculated as the arithmetic average of gains ofthe positive and negative perturbation. The comparison between the Gains obtained from the developed model and the ChemCad model are shown in Table 3.8. It is observed that only diagonal elements have significant values. It means that the ASTM 95% or TBP 100% for one product mainly influences the volumetric flow rates of this product and adjacent heavier product while having little effect on the volumetric flow rates of other products. It is also observed that although there is some mismatch between the gains ofthe developed model and the ChemCad model, the corresponding gains are in the same order and have the same sign. The mismatch is expected because the developed model uses simplified approaches and empirical correlations. However, the mismatch is not expected to distort the searching direction in optimization. Since the volumetric fiow rates ofthe side-draw product are the most important in the refinery wide optimization, it is also necessary to find if other operating variables have significant influence on the product rates. Another process variable which may have significant influence is the pumparound heat duty. The pumparound heat duties are defined explicitly in the atmospheric tower modeling. In the vacuum tower, the pumparound duties are defined by the returning temperature.

59

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60

The results ofthe corresponding sensitivity tests on pumparounds are shown in Table 3.9 and Table 3.10. It is found that the pumparound heat duties have little effect on the product flow rates as long as the pumparounds satisfy the cooling requirements of each tower and provide enough reflux in each separation section. Pumparounds may affect the energy usage in the crude unit. Nevertheless, energy consumption is a secondary factor in the refinery-wide optimization. Hence, the pumparound heat duties are fixed when refinery-wide optimization is conducted and they are not used as decision variables. The same approach of selecting decision variables was used in other units introduced in the following text. Those process variables only affecting energy consumption are not selected to be decision variables ofthe refinery-wide optimization.

Table 3.9 Comparison between the Gains Obtained from the Simplified Model and ChemCad Model, Pumparound Heat Duty versus Product Flow Rate, Atmospheric Tower, Summer Mode. AF Units AFin, ChemCad model AFjn, Approximated model AFhn > ChemCad model AFhn, Approximated model AFid. ChemCad model AFjd, Approximated model AFhd: ChemCad model -^Fhd' Approximated model AFago, ChemCad model AFago, Approximated model BBL/hr/MMBtu BBL/hr/MMBtti BBL/hr/MMBtu BBL/hr/MMBtu BBL/hr/MMBtu BBL/hr/MMBtti BBL/hr/MMBtu BBL/hr/MMBtti BBL/hr/MMBtu BBL/hr/MMBtti
l^Qpa^

AF
^Qpal

-0.195 0 0.3749 0 -0.0993 0 0.1097 0 -0.0035 0

0.0335 0 -0.4677 0 -0.4229 0 0.8632 0 -0.0008 0

61

Table 3.10 Comparison between the Gains Obtained from the Simplified Model and ChemCad Model, Pumparound Rettim Temperature versus Product Flow Rate, Vacuum Tower, Summer Mode. APV Units AFhvgo, ChemCad model AFhvgo, Approximated model AFresid, ChemCad model AFresid, Approximated model BBL/hr/F BBL/hr/F BBL/hr/T BBL/hr/F ^Tpal -0.0009 0 0.0008 0 APV ^Tpa2 -0.1765 0 0.0327 0

On the other hand, pumparounds may become the decision variables of single-unit optimization ofthe crude unit. This is because energy usage is a major factor in singleunit optimization. The pumparounds are used to preheat the crude. While satisfying separation requirement and heat requirement in the atmospheric tower and vacuum tower, maximizing pumparounds may be beneficial since it provides maximal heat to preheat the crude, which may decrease the fuel usage in the preheat furnace. Another comparison is done on the temperature profile ofthe atmospheric tower ofthe developed model and ofthe ChemCad Model. The comparison is on the basis of using the same separation specifications, condenser pressure, pressure drop in the tower and the fiimace outlet temperature. The comparison ofthe temperature distribution in the crude tower between the developed model and the Chemcad model is shown in Figure 3.15.

62

800 700 600 500 Simplified Model - ChemCad Rigorous Model

2 400
PQ OD

300 200 100 0 10 15 20 tray number 25 30 35 40

Figure 3.15 Comparison of Temperature Profile in the Atmospheric Tower. It is observed that although the crude unit model in this work is a simplified model and linear temperature distribution is assumed in each separation section, temperature profiles in two models are similar in shape. The biggest temperature difference appears on tray 29 to 35, where the temperatures predicted by the simplified model are about 20%) higher than those of ChemCad model. There are only small differences from tray 1 to tray 28, where the average relative difference is 2.9%. The average relative temperature difference for all trays is 5.8%. Tray temperature difference only affect the estimation of utility cost in the atmospheric tower, which only has an insignificant effect on plant-wide economics.

3.6 Auxiliary Processes in the Crude Unit There are some auxiliary processes in the crude unit which prepare the side-draw products exiting the atmospheric tower and vacuum tower for ftirther processing in the refinery. These processes includes Rerun unit. Residue Oil Solvent Extraction (ROSE) unit, debutanizer, Naphtha Splitter, etc. These units are not critical from plant-wide

63

operation point of view. However, they must be included in the refinery-wide model in order to run the refinery-wide model. The models of these units are required when calculating the amount ofthe feeds to downstream units or products for sale. In addition, the capacities of these processes may become active constraints in refinery-wide optimization. Simplified models were developed for these processes. Since the operations of these processes in the Summer Mode are quite different from the operations in the Winter Mode, different parameters were used to account for the difference in operation. 3.6.1 Rerun Unit The fianction ofthe Rerun Unit is to recover the diesel components from the AGO and the LVGO. Due to incomplete separation between the diesel, the AGO and the LVGO, the AGO stream and the LVGO stream may contain some components whose boiling points are in the diesel boiling range. Since diesel itself has high market value, it is more profitable to recover this part of diesel component and sell it directly instead of using it as the feed to FCC unit to make FCC gasoline. The core ofthe rerun unit is a distillation column. Using the AGO stream and part ofthe LVGO stream as feed, the diesel components come out from the column overhead. The overhead stream combines with the diesel directly produced from the atmospheric tower and flows to hydrodesulftirizer (HDS) unit. The bottom stream is combined with the rest ofthe LVGO stream and the HVGO stream as the feed to the FCC unit. All AGO side-draw product from the atmospheric tower is sent to Rerun unit. Only part ofthe LVGO stream from the vacuum tower is sent to the rerun unit. The typical percent of LVGO used as Rerun feed is 13 vol.%) in the Summer Mode and 11 vol.% in the Winter Mode. The volumetric flow rate ofthe overhead product ofthe rerun distillation column is about 25 vol.%) ofthe total rerun feed in the summer and 23 vol.%) ofthe total rerun feed in the winter. These values are used directly in the model to calculate the amount ofthe LVGO stream sent to the rerun unit and the amount ofthe diesel component produced in the Rerun unit.

64

3.6.2 Residue Oil Solvent Extraction (ROSE) Unit The function ofthe ROSE unit is to recover FCC cracking feed from the vacuum residue. The vacuum residue is rich in metals, tar, and asphalt. Metals are poisonous to the FCC catalyst. Tar and asphalt can deposit large amount of carbon on the FCC catalyst which could severely decrease the catalyst activity and could lower the FCC unit processing capability. Hence, the vacuum residue can not be used directly as FCC feed. Without treatment, vacuum residue can only be sold as low-value No. 6 fuel oil. However, the vacuum residue still contains a large amount of hydrocarbons that is suitable for catalytic cracking. If this portion of hydrocarbons in the vacuum residue can be recovered, it can be used to produce high-value FCC gasoline. Thus, recovering FCC feed from residue is economically favorable. Since the vacuum residue has very high boiling range, distillation can not be used to separate the vacuum residue. The most efficient way to separate the vacuum residue is solvent extraction. The solvents normally used in a refinery are propane and butane. Paraffinic and naphthenic hydrocarbons have a large solubility in the above mentioned solvents while metals and asphalt material have very low solubility. The extraction operation consists of a series of countercurrent contacts between oil and solvent (Nelson, 1958). The separation between the solvent and the hydrocarbon is easily done by flash because the solvent is much lighter than the hydrocarbon. The recovered hydrocarbon is called deasphalted oil (DAO). According to the refinery considered in this work, the entire vacuum residue is sent to the ROSE unit. The typical percent of DAO product is about 60 vol.%) ofthe vacuum residue in both the Summer Mode and the Winter Mode. This value is directly used to calculate the DAO rate from the vacuum residue. DAO is then considered as a crude cut and its properties are calculated as the same as those of any other crude cut. DAO is combined with the HVGO produced directly from the vacuum tower and rerun column bottom stream as the feed to FCC unit. The insolvable part of vacuum residue is sold as No. 6 fuel oil.

65

3.6.3 Debutanizer The function ofthe debutanizer in the crude unit is to separate the light components from the light naphtha in order to stabilize the light straight-run gasoline (LSR). Most ofthe overhead products from the debutanizer are propane and butane. This stream becomes liquefied petroleum gas (LPG) and flows to the gas plant ofthe refinery. The bottom product from the debutanizer flows to the naphtha splitter to make LSR and reformer feed. The Debutanizer adds flexibility to refinery operation. When the Reid Vapor Pressure (RVP) specification for gasoline is high in the winter, more butane is left in the LSR. When the RVP specification is lower in the summer, most ofthe butane enters LPG and is used as alkylation feed to produce alkylate, a lower RVP gasoline blending stock. In the atmospheric tower model, the vapor stream and liquid stream coming out the overhead condenser are combined as the light naphtha stream. Before the calculation ofthe debutanizer, the amount of light gas in the light naphtha is calculated according to industrial data and is subtracted from the light naphtha The LPG production rate from the debutanizer depends on the quality ofthe crude. Since the crude slates are different in different seasons, the LPG product rates are different. Using industrial data, the weight and volume of LPG are calculated from the weight and volume ofthe debutanizer feed. The weight ofthe debutanizer bottom steam is then estimated according to material balance. According to industrial data, the total volume loss is negligible in the debutanizer, less than \%. In other words, the summation ofthe volumetric flow rates of LPG and debutanizer bottom product is almost equal to the volumetric flow rate ofthe debutanizer feed. Assuming that there is no volume loss, the volumetric flow rate ofthe debutanizer bottom stream is then calculated.

3.6.4 Naphtha Splitter The function ofthe naphtha splitter is to split the debutanizer bottom stream into light straight-run (LSR) gasoline and heavy naphtha. The naphtha splitter also adds flexibility in refinery operation. The operation ofthe naphtha splitter can be adjusted 66

according to downstream gasoline blending. If the octane number ofthe gasoline pool is low, more light naphtha is used as the reformer feed to produce high-octane reformate. When RVP specification of gasoline is low in the summer, the amount of high RVP light straight-run gasoline (LSR) is reduced. More naphtha is used as reformer feed to produce medium-RVP reformate. Using industrial data, the volumetric flow rates ofthe LSR are calculated from the volumetric flow rate ofthe feed to naphtha splitter. The LSR is then considered as a crude cut and its properties, including weight, are calculated as any other crude cut. The weight ofthe splitter bottom is estimated based on material balance. According to industrial data, the total volume loss is negligible in the naphtha splitter and is less than 1%). Hence, assuming that there is no volume loss, the volumetric flow rate ofthe debutanizer bottom stream is calculated from the volumefric flow rates ofthe feed and the LSR.

67

CHAPTER 4 FCC FEED CHARACTERIZATION AND MODEL BENCHMARKING

4.1 Process Overview Fluidized Catalytic Cracking, better known as FCC, is one ofthe most important and complicated processes in petroleum refining. For many refiners, FCC is the key to profitability in that the successful operation ofthe unit can determine whether or not a refiner can stay in business and remain competitive in today's market (Sadeghbeigi, 1995). In 1989, 40 vol.% of gasoline blending stocks in the U.S. were produced from the FCCU (Lin, 1993). In the refinery considered in this work, FCC provides about 45 vol.% blending stock ofthe gasoline pool. Since gasoline is the largest volume product from a fuel-oriented refinery, an economic study on the refinery-wide operation must consider the operation ofthe FCC unit. The FCC unit converts large quantities of heavy feed into more valuable product, called FCC gasoline. The FCC unit also produces light cycle oil (LCO), heavy cycle oil (HCO) or slurry oil, and light gas. LCO has the same boiling range as of diesel. It is blended with the diesel stream directly from the crude unit to produce the diesel product. HCO from FCC is either recycled to the FCC feed or combined with the vacuum residue from the crude unit to make No. 6 fuel oil. In the refinery considered in the study, most of the HCO is used to make No. 6 fuel oil. Hence, the HCO is not recycled to the FCC feed in the model. Light gas produced in the FCC unit is the main resource of light gas in the refinery. Light gas is sent to the gas plant to produce fuel gas, liquidified petroleum gas (LPG), propylene, and butane. Light gas also provides the feedstock to the alkylation unit in the refinery. From the block flow diagram ofthe refinery in Figure 3.1, it can been seen that the FCC unit receives atmospheric gas oil (AGO), light vacuum gas oil (LVGO), heavy vacuum gas oil (HVGO) and deasphalted oil (DAO) from the crude unit. In many refineries, FCC feed goes through a hydrotreater before it enters the FCC unit if the FCC

68

feed has a high content of sulfur and metals. Sulfur in the feed may enter the flue gas of the FCC unit to cause environmental pollution. Sulfiir also enters the product streams of the FCC unit such as gasoline, LCO, and HCO that have upper limits on sulfur content in the products. Metals in the FCC feed are catalyst poisons. Since the crude oils processed in the refinery considered in this work belong to light, low sulfur crude type, the FCC feed does not have high content of sulfur and metals. Therefore, a hydrotreater for the FCC feed is not required in this particular refinery. The FCC unit in the refinery considered in the work is a Model IV FCC unit. The flow diagram of a Model IV FCC unit is shown in Figure 4.1. The gas oil from the crude unit is first preheated in a fiimace and then mixed with the regenerated catalyst and enters the reactor riser. Most ofthe cracking reaction occurs in the riser. The residence time of the gas oil in the riser is about 2 seconds (Sadeghbeigi, 1995). Short contacting time is required to prevent secondary cracking that cracks high-value products such as gasoline into light gas. The catalyst is separated from the product vapor in the disengaging zone on the top ofthe reactor and flows to the regenerator. The coke deposited on the catalyst is bumed in the regenerator. After regeneration, catalyst regains its activity and flows to the riser again. The product vapor exits the reactor from the top and enters the main fractionator. In the main fractionator, the mixed product stream is separated into several products. The liquid stream withdrawn from the overhead condenser is FCC gasoline. The vapor steam from the overhead condenser flows to the wet gas compressor and on to the gas plant for ftirther treatment. LCO is withdrawn from a side-draw tray ofthe tower. After steam stripping, LCO flows to the diesel storage tank. HCO or slurry is withdrawn from the bottom ofthe main fractionator and the bottom ofthe sidestripper. Most of HCO or slurry is used as the feedstock for No. 6 fuel oil.

69

G o
00

c
o
c

;-<

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13 13 O
T3
<U N

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C/3

3 GO

70

The distinguishing feature of a model IV FCCU is that it does not have a slide valve on the catalyst circulation line like most of modem FCCU does. Hence, there is no direct control of catalyst circulation rate between the reactor and regenerator. Only indirect control is possible by varying the driving force for catalyst flow (Huq and Morari, 1995). The model IV FCCU also has low metallurgical limit, about 1000 F for the riser temperature, while modem FCCUs may have the riser temperatures as high as 1050 F(Arbeletal., 1995).

4.2 Model IV FCC Unit Modeling McFarlane et al. (1993) developed a dynamic Model IV FCC unit model. The model uses a continuous stirred-tank reactor (CSTR) for the riser and does not include a yield model. Ellis(1996) developed a steady-state model based on McFarlane's dynamic simulator. Plug-Flow Reactor (PFR) model is used to describe the flow and reaction in the reactor. The ten-lump yield model proposed by Jacob et al.(I976) is used in the steady-state model to calculate the product distribution. This model characterizes the gas oil feed on the basis ofthe molecular stmcture and the molecular weights. The ten-lump reaction network is shown in Figure 4.2. The boiling ranges ofthe individual lumps are shown in Table 4.1. Among the ten lumps, the lump of aromatic substituent molecules represents the branches ofthe aromatic rings. Since they have completely different cracking characteristics from the aromatic rings that they attach to, they form separate lumps. The aromatic substituent group can be paraffin chains or naphthenic groups (Jacob et al., 1976). The FCC feed components with boiling points (I) greater than 650F and (2) between 430 F and 650 F are each grouped in four lumps: paraffins, naphthenics, aromatics, and aromatic substituent groups. All eight lumps are cracked into gasoline, and light gas in the riser. Four lumps with boiling point greater than 650F compose HCO. Four lumps with boiling point between 430F and 650F compose LCO. Gasoline contains Cs's up to a boiling point of 430F. The "C" lump contains coke and light gases

71

(C1-C4). Gasoline lump and "C" lump are the products ofthe cracking reactions. The kinetic models used for this reaction network were taken from Jacob et al. (1976) and Arbel et al. (1995) and assumefirst-orderreactions with Arrhenius rate constants for each ofthe 20 reactions between the ten lumps as shown in Figure 4.2.

I-

PI

NI

As! - 1

Arl ,

Ph - "

Nh -I

I-Ash

Asl

Figure 4.2 Ten-Lump Reaction Network.

72

Table 4.1 Boiling Range of Lumps in Ten-Lump FCC Reaction Network. Lump Ph Nh Ash Arh Pi Ni Asi Ari G C Description Wt. % paraffinic molecules Wt. % napththenic molecules Wt. % aromatic substituent molecules Wt. % carbon atoms among aromatic rings Wt. % paraffinic molecules Wt. % napththenic molecules Wt. % aromatic substituent molecules Wt. % carbon atoms among aromatic rings Wt. % gasoline Wt. % coke and 1. Butane 4. Propene Boiling Range T>650F T>650F T>650F T>650F 430F<T<650F 430F<T<650F 430F<T<650F 430F<T<650F C5's-430F (C1-C4, and coke)

2. Isobutane 5. Propane 3. Butane 6. Gases<C2

4.3 FCC Feed Characterization Feed information is an input to the FCC model. Feed information required by the FCC model includes volumetric flow rate, API gravity, and the weight fractions ofthe eight lumps in the feed. 4.3.1 Volume and Weight of FCC Feed FCC feed is composed of AGO from the rerun unit bottom, LVGO, HVGO, and DAO. The volume and weight of these four streams have been calculated in the cmde unit model described in Chapter 3. The volume and weight ofthe FCC feed is the summation of these of four streams:

^FCC

~ ^.-iGO "'" ^LVGO

"* ''^HVGO + ''^DAO '

(4.1) 73

^fCC

= ^AGO + WUGO + KvGO

+ ^OAO >

(4-2)

where Vpcc, VAGO,

VLVGO, VHVGO, VDAQ-

volumetric flow rates of FCC feed, AGO, LVGO,

HVGO, and DAO, respectively, BBL/D,

WFCC. WAGO, WLVGO, WHVGO, WDAO-

weight flow rates of FCC feed, AGO, LVGO,

HVGO, and DAO, respectively, MLB/D. The API gravity ofthe FCC feed is calculated using the weight and the volume of the FCC feed using the formula below:

APIpcc=

141 5 13^-5, (Wp,.,. 0.454)/(Vp^c-0.159)

(4.3)

where
APIFCCWFCC-

API gravity ofthe FCC feed,

weight flow rate ofthe FCC feed, MLB/D,

Vpcc- volumetric flow rate ofthe FCC feed, BBL/D. 4.3.2 FCC feed Characterization To use the ten-lump yield model, the weight percentages ofthe lumps in the FCC feed must be known. Only the first eight lumps are in the feed: Ph, Nh, Ash, Arh, Pi,N| Asi,and Ari Lump gasoline and lump "C" are not in the feed. Some industrial data of FCC feed obtained from the refinery considered in this work are listed in Table 4.2. Although the given data can not be directly used to calculate the weight percentage ofthe eight lumps in the FCC feed, at least they provide the general composition ofthe FCC feed which can be used to validate the correlations used in the feed characterization.

74

Tabel 4.2 Industrial Data of FCC Feed. Feed Property Aniline point, F Viscosity, centipoise Refractive Index, 60F API Light Components, <650F Plant Data, Typical FCCU Combined Fresh Feed Analysis, May through August, 1998 197-224 6.4 1.5067-1.5082 22.0-23.3 10% TBP, 606-622F 20% TBP, 678-694F Paraffins Naphthenes Aromatics 56.9-59.1 (vol.%) 22.2-24.8 (vol.%) 18.1-18.7 (vol.%)

To make the comparison between the feed characterization and the limited industrial data, the operating conditions in the cmde unit must be the same for the model and as for the industrial data because the operation of cmde unit significantly affects the properties ofthe FCC feed. Since the given data for the FCC feed is for the Summer Mode Operation, typical operating conditions in the summer are used. They are the same as the normal values ofthe operating variables listed in Table 3.7 in Chapter 3. The weight percent ofthe four light lumps in the FCC feed can be determined from the boiling point ofthe light lumps. The light lumps all have a boiling point less than 650F. Among the four streams of FCC feed, AGO is the lightest and DAO is the heaviest. The portion ofthe FCC feed on the whole cmde TBP curve begins with the IBP of AGO and ends with EBP of DAO. From the whole cmde TBP-volumetric curve, the cmde volume with the boiling point between the IBP of AGO and 650 F is obtained. The volume fraction of light lumps in the total FCC feed is then calculated as below:

VT
_ '^ light lump "^lighilump jrj. ' y.^-^)

y i fcc

75

where Viight lump- volume fraction ofthe light lumps in the FCC feed, VTiight lump- volumetric flow rate ofthe four light lumps in the FCC feed, BBL/D,
VTFCC-

volumetric flow rate ofthe FCC feed, BBL/D.

The API gravity ofthe light lumps is estimated from the API-volumetric curve ofthe whole cmde. Then, the specific gravity of light lumps is calculated. The weight fraction ofthe light lumps in the FCC feed is calculated as blow:

^ """""""

_SPG^,-Vi,i,ii.np-01S9 WTp,,-0.4536 ' ^ ^

where SPGiight lump- specific gravity ofthe light lumps in the FCC feed, Wiightiump- weight fraction ofthe light lumps in the FCC feed,
WTFCC-

weight flow rate ofthe FCC feed, MLB/D.

To calculate the weight percentages ofthe eight lumps in the feed, the weight percentages of paraffins, naphthenes, and aromatics (PNA) in the FCC feed must be known. The TOTAL method (Dhulesia, 1986) and n-d-M method (ASTM, 1985) are used here. TOTAL method is used to calculate the refractive index (RI) at 20C and 60C. TOTAL method is also used to calculate the fraction of carbon in the aromatic ring in the FCC feed. It is claimed that TOTAL method is more accurate than other methods in predicting refractive index (Dhulesia, 1986) and aromatic carbon content (Sadeghbeigi, 1995). The correlations in the TOTAL method were developed from multiple linear regression of 33 feedstocks (Dhulesia, 1986). RI is an important index of FCC feed. It shows how refractive or aromatic a FCC feed is. The higher the RI, the less crackable the FCC feed is (Sadeghbeigi, 1995). The correlations of TOTAL method are given below:

76

RI(20) = 1 + 0.8447-SPG""'' RI(60) = 1 + 0.8156 SPG"'''

-(VABP^ + 273.16)'"'"'' -MW'"""'', -(VABP^ + 273.16)-""''' -MW'""""',

(4.6) (4.7)

where RI (20)- refractive index at 20C, RI (60)- refractive index at 60C, SPG- specific gravity of FCC feed, VABPc- volumetric average boiling point, C, MW- molecular weight of FCC feed. For consistence reason, the molecular weight ofthe FCC feed used in the equations 4.6 and 4.7 are also calculated from the correlation in the TOTAL method as below:

MW = 7.8312 -10-' - SPG'""''' - VABPc'"'' AP"'"',

(4.8)

where AP- Aniline point, C. VABP is calculated from the ASTM boiling curve ofthe FCC feed. The ASTM boiling curve is converted from TBP curve of FCC feed. Please refer to Chapter 3 for the details ofthe calculations. The aniline point ofthe FCC feed uses the average value ofthe aniline point ofthe FCC feed in industrial data, 99.2C. The moles ofthe FCC feed is the summation ofthe moles of AGO, LVGO, HVGO, and DAO. The molecular weight of FCC feed is then calculated using the moles and the weight ofthe FCC feed. The RI (20) and RI (60) calculated in equations (4.6) and (4.7). Only RI (60) of the FCC feed is measured in the refinery considered in the work. The RI (60) predicted by the TOTAL method, 1.49982, is just a little smaller than the normal range of FCC feed 1.5067-1.5082. However, the n-d-M method which is used to calculate the

77

naphthene content and the paraffin content ofthe FCC feed is very sensitive to the value of refractive index (RI). Small differences in RI may cause a large error in PNA prediction when using the n-d-M method. It was reported that a 35%) drop in the aromatic content was observed when the RI (20) dropped from 1.5105 to 1.5000 (Sadeghbeigi, 1995). Hence, accurate values of RI(20) and RI(60) are required. Here, a bias is used to adjust the calculated RI(60). The bias between the average value of RI (60) ofthe FCC feed in the industrial data, 1.50745, and the calculated RI (60) of normal operating condition is calculated as below:

dRI(60) = 1.50745 - RI(60)^,^,,

(4.9)

where RI(60)normai- Calculated RI(60) under normal operating conditions using TOTAL method, dRI (60)- the bias of RI(60). The dRI (60) calculated here is then used in adjusting the calculated RI (60) thereafter as shown below:

RI(60)^,j^,^, = RI(60),o,^ +dRI (60),

(4.10)

where RI(60)adjusted- adjusted value of RI(60), RI (60)TOTAL- refractive index at 60C calculated by TOTAL method. The TOTAL method and the n-d-M method use the value of RI (20) in composition calculations instead of RI (60). Now the question is how to estimate the difference between RI (20) and RI (60). It is assumed that TOTAL method is consistent in predicting RI (60) and RI (20) for one feed. Hence, the RI (60) and RI (20) calculated from the TOTAL method is used to estimate the difference between RI (60) and RI (20). The final value of RI (20) is calculated using the following formula:

78

RI(20)^,,..,,,, = RI (60),,j^,,, - (RI(60),orAL - Rl(20)rorAL ) , where RI(20)adjusted- adjusted value ofthe RI(20), RI
(20)TOTAL-

(4-11)

refractive index at 20C calculated by TOTAL method.

The correlation in TOTAL method is used to calculate the aromatic carbon content in the FCC feed. The correlation has the formula as below:

%C, = -814.136 + 635.192 RI(20)^,j^^,^, -129.266 - SPG + 0.013 MW -0.340- SUL + 0.757 In(VIS)

where %)CA- aromatic carbon content ofthe total carbons in the FCC feed, wt.%), SPG- specific gravity ofthe FCC feed, SUL- sulftir content ofthe FCC feed, wt.%, VIS- viscosity of FCC feed, centistoke. The viscosity in the industrial data has the units of centipoise. The conversion between centistoke and centipoise uses the following formula:

, centipoise centistokes = . density

(4.13)

The n-d-M method is an ASTM (D-3238-85) method used to estimate the carbon distribution in aromatic ring stmcture, naphthenic ring stmcture, and paraffin chains. Only the correlation of refractive ring, which includes aromatic ring and naphthenic ring, is used here. The formulas are as follows:
V = 2.5-[RI(20)-1.4750\-(SPG,O^^

-0.8510),

(4.14)

79

m = (SPG,o,c -0.8510)-1.11-[RI(20)-I.4750]

(4.15)

where V, Tu- n-d-M method parameters, SPG20''c- specific gravity at 20C.

If T!j is negative: %C =820-m-3-SUL If tu is positive: %C = 1440-m-3-SUL

+^ ^ ^ , MW + ^^^ MW ,

(4.16) (4.17)

where % C R - weight percentage ofthe carbons of refractive ring stmcture in the total carbons in the FCC feed, wt.%. Using the aromatic carbon content calculated in equation 4.12, the naphthenic carbon content cin be calculated as below:

%C^=%C^-%C^ %Cp=100-%C^ where

(4.18) (4.19)

% C N - weight percentage ofthe carbons of naphthenic rings in the total carbons in the FCC feed, wt.%, %)Cp- weight percentage ofthe carbons of paraffin chains in the total carbons in the FCC feed, wt.%. CA, CN, and C? calculated above are the weight percentage ofthe carbon atoms in a certain molecular structure in the total weight of carbon atoms. The weight percentage of aromatic rings, naphthenic rings, and paraffin chains are calculated next. For aromatic ring, the carbon/hydrogen ratio is 1:1 while the carbon/hydrogen ratio in naphthenic ring is 1:2. Considering the fact that the paraffin molecules in the FCC feed are big molecules 80

with long paraffin chains, most of carbon atoms are in the middle of paraffin chains. Hence, carbon/hydrogen ratio in the paraffin chains is also set at 1:2. The weight fraction of paraffins, naphthenic rings, and aromatic rings are then calculated as below:

WT, = %C, - "^^^''"-'-^^^^^^^ny-o^'"' AW,^,,,-RATIO, where I-paraffin, naphthene ring, and aromatic ring,

(4.20)

C]- weight percentage of carbons of molecule type I in the total carbons in the FCC feed, wt.%), RATIOi- the carbon/hydrogen ratio in the molecule type I, WTi- weight fractions ofthe molecule type I in the FCC feed, AWcarbon- atomic weight of carbon, 12, AWhydrogen- atomic weight of hydrogen, 1. The comparison between the industrial data and the weight percentages ofthe paraffin, naphthene rings, and aromatic rings in the FCC feed calculated by equation 4.20 are listed in Table 4.3. The industrial data do not include the volume percentage ofthe light lumps. However, it can be estimated that the volume percentage of light lumps is between 10 vol.%> and 20 vol.%) since 650F, the cut point for light lumps, is greater than the highest possible point for 10 vol.%, 622F, while less than the lowest possible point for 20 vol.%, 678F. It can be seen from Table 4.3 that the calculated value, 12.8 vol.%, is in this range. Since the specific gravity values of paraffin, naphthene, and aromatics in the FCC feed are unknown, the volumetric percentage of these components can not be calculated in the feed characterization. However, the calculated weight percentages of paraffin, naphthene and aromatics are close to the volume percentages of corresponding components in the industrial data. The wt.% of aromatics is 1.3% higher than its vol.%.

81

which is expected because aromatics have heavier density than other species. The opposite is true for paraffins.

Table 4.3 Comparison between the Industrial Data and Feed Characterization ofthe FCC Feed. Feed Property Plant Data, Typical FCCU Combined Fresh Feed Analysis, May through August, 1998 10% TBP, 606-622 F 20% TBP, 678-694 F Paraffins Naphthenes Aromatics 56.9-59.1 (vol.%) 22.2-24.8 (vol.%) I8.I-I8.7 (vol.%) Model prediction

Light Components, <650 F

13.4 (vol.%) 12.5 (wt.%) 56.1 (wt.%) 23.8 (wt.%) 20.0 (wt.%)

The weight percentage ofthe aromatics from the feed characterization, 20.0 wt.%, is higher than the values ofthe volume percentage ofthe aromatics in industrial data, 18.1-18.7 Vol.%). This is expected because aromatics have higher specific gravity than those of paraffins and naphthenes with the same boiling point. Hence, the weight percentage ofthe aromatics in the FCC feed is greater than its volume percentage from the absolute value. The comparison made here is not rigorous due to the lack of detailed FCC analysis from industrial data. General speaking, the calculated values from feed characterization are in good agreement with the industrial data considering that empirical correlations are used in the calculations. 4.3.3 Weight Fractions ofLumps in the FCC Feed According to the 10-lump model, the weight percentage of aromatic rings is the summation ofthe weight percentage of Arh and Ari. Arh and Ari have the same molecular stmcture. The only difference between the two is their boiling range. This is also tme for each pair of Ph and Pi, Nh and Ni, and Ash and Asi. An assumption is made that the weight percentage ofthe heavier lump in the total heavy lumps is equal to the weight percentage of lighter lump in the same pair in the total light lumps. The assumption is based on the 82

fact that the composition of FCC feed does not change dramatically with respect to its boiling range. The relative small amount of light lumps, which is about 15 vol.%) ofthe FCC feed, causes an insignificant error due to this assumption. The weight percentage of Arh and Ari are calculated using following formula: WT W,= --!-!WT^+WT^+WT/ W,=W^,,,,^^-W,, ^/. = ^ / - ^ v

(4.18) (4.19) (4.20)

where I - aromatic rings, naphthene rings, and peiraffin, Wi- weight fraction ofthe molecular type I in the FCC feed, Wii- weight fraction ofthe light lump ofthe molecular type I in the FCC feed, Wih- weight fraction ofthe heavy lump ofthe molecular type I in the FCC feed, Wiightiump- weight fraction of total light lumps in the FCC feed. The weight fractions of lump Arh and lump Ari are equal to WArh and WAFI, respectively:

%Ar,=W,,^, %An=W,^^,

(4.21) (4.22)

where %Arh, %)Ari- weight fractions of lump Arh and lump Ari in the FCC feed, respectively. Only the weight fractions of lump Ath and lump Ari can be directly obtained from equation 4.18 to 4.22. Since the lump Ash and Itimp Asi can be the paraffin chains or the naphthenic group, the remaining six lumps belong to either naphthenic molecules or

83

paraffin molecules. No correlation is given in literature to calculate the weight percentage of aromatic substituent lumps, Ash and Asi. Ellis (1998) provided the composition of an FCC feed with an API gravity of 23, which is close to the API gravity ofthe FCC feed, 22.0 to 23.3, studied here. The weight fractions of eight lumps in the FCC feed of API=23 given by Ellis (1998) are listed in Table 4.4. Table 4.4 Weight Fractions of Eight Lumps in an FCC Feed of API=23. Lump Name Weight Fraction Ph 0.36 Nh 0.15 Ash 0.25 Arh 0.14 Pi 0.04 Ni Asi
Ari

0.02 0.02

0.02

Assuming the same ratios of Ash to Arh and Asi to Ari in the feed given in Table 4.4 and the FCC feed studied here, the weight fractions of Ash and Asi are calculated as below:

o/oAs,=o/oAr,-y'''^'-",

(4.23)

o/oAs,=%Arr2.,'^'-'\

(4.24)

where %Ash, %)Asi- weight fractions of lump Ash and lump Asi in the FCC feed, respectively, %Arh,APi=23, %)Ari, APi=23, %Ash,APi=23, %Asi,APi=23 -Weight fractions of lumps Arh, Ari, Arh, and Ari in the FCC feed of API=23, respectively. The weight fractions of lumps Ph, Pi, Nh, and Ni are calculated using the following formula: W <^^*^
paraffin .heavy naphlhene .heavy

%n=(I-fl'.,..,

-%As, -%ArO--

(4.25)

84

w
%N =(1-W^,,,^ -o/oAs, -%ArJ-W %P, = (W,^ ,,^ - %As, - %Ar,) paraffin,light

".^mUf!^
paraffin .heavy naphlhene .heavy

, ,

(4.26) (4.27)

'-^^rsff^
naphlhene .light

w
%N, = (W^,^ - o/oAs, - o/oAr,) paraffin.lighl

"-^^!^
naphlhene .lighl

(4.28)

where %Ph, %)Pi ,%Nh, %Ni -weight fractions of lump Ph, lump Pi, lump Nh, lump Ni in the FCC feed, respectively, Wparaffm.heavy- Weight fraction of the hcavy paraffin in the FCC feed, Wparaffinjight- weight fraction ofthe light paraffin in the FCC feed, Wnaphthene.heavy- Weight fraction of heavy naphthene in the FCC feed, Wnaphthenejight- weight fraction of light naphthene in the FCC feed. In order to determine if the feed characterization procedure gives reasonable results in the operating ranges which are used in the optimization studies, the feed characterizations were carried out in the operating ranges and the results were compared with the base case calculated above. The two main operating variables that affect the composition of FCC feed are the heavy distillate ASTM 95% point and the HVGO TBP 100%) point. The heavy distillate is the adjacent lighter side-draw product ofthe FCC feed in the atmospheric tower. The heavy distillate ASTM 95% point determines the amount ofthe light components in the FCC feed. HVGO is the heaviest side-streams among the four streams composing ofthe FCC feed. The HVGO TBP 100% will affect the composition of heavy lumps in the FCC feed. The weight fractions of eight lumps and other properties of FCC feed under different operating conditions are listed in Table 4.5.

85

Table 4.5 Weight Fractions ofthe Eight Lumps in the FCC feed across the Operating Range. Base Case Operating conditions HD ASTM 95%, F HVGO TBP 100%, F Feed properties Light lump, vol.% Aromatics, wl.%o 13.4 20.0 18.9 19.3 7.4 20.7 13.7 19.8 13.0 20.4 10%-20% 18.I-I8.7 (vol.%) Naphthenes, wt.% 23.9 23.0 25.0 25.2 22.5 22.2-24.8 (vol.%) Paraffins, wt.% 56.1 57.7 54.3 55.0 57.1 56.9-59.1. (vol.%) Weight fraction of lump Ph Nh Ash Arh P, Ni Asi An 0.272 0.115 0.313 0.175 0.053 0.022 0.025 0.025 0.272 0.108 0.284 0.159 0.078 0.031 0.034 0.034 0.269 0.124 0.345 0.193 0.028 0.013 0.014 0.014 0.268 0.123 0.308 0.172 0.054 0.025 0.026 0.026 0.272 0.107 0.320 0.179 0.051 0.020 0.025 0.025 1050 1050 1050 1010 1090 1050 650 630 670 650 650 650 Case 1 Case 2 Case 3 Case4 Industrial data

In Case 1 and Case 2, the heavy distillate ASTM 95% point is perttirbed by 20F. It is observed from Table 4.5 that light lump content increases with the decrease ofthe heavy distillate ASTM 95%o point and vice versa. It is expected because if the heavy

86

distillate ASTM 95% point drops, more light components are left in the FCC feed. The opposite is tme when the heavy distillate ASTM 95% point increases. In Case 3 and Case 4, the HVGO TBP 100% point is perturbed by 40F. It is observed from Table 4.5 that the light lump content decreases with the increase ofthe HVGO TBP 100%) point and vice versa. The change is small compared to the light components change caused by perturbing the heavy distillate 95% point. This is expected because the HVGO have a small fraction in the heavy lumps. 4.4 Model Benchmarking The steady-state model developed by Ellis et al. (1998) is used in the present study. The steady-state model has been quantitatively benchmarked against published results. These results show a good representation ofthe available data. However, the FCC unit in the refinery considered in this work is slightly different from what was described in the model. The biggest difference is that the FCC unit studied here has only about 70% of throughput ofthe original model. The feed qualities are also different. The feed quality significantly affects the product distribution predicted from the FCC model. The FCC model using the FCC feed characterized above show significant difference in product distribution than the industrial data. This may be explained by the different catalysts used. The type of catalyst in the original reaction system that the model is based on is unknown. Since there are many types of FCC catalysts, it is very likely that catalyst used in the FCC unit considered in this work is different from catalyst in the unit described by the original model. In order to represent the FCC unit accurately, ftirther benchmarking ofthe original model is required. The original model was benchmarked against the industrial data obtained from the refinery considered in the work. Only the industrial operating data for one day of operation is available. The industrial data are listed in Table 4.6.

87

Table 4.6 FCC Model Benchmarking: Industrial Data and Model Prediction. Process variable FCC Feed, MLB/D Reactor temperature, F Regenerator temperature, F O2 in flue gas, mol%) FCC gasoline, MLB/D LCO, MLB/D HCO, MLB/D Light Gas, MLB/D Industrial Data 6378 987 1284 0.011 3433 1096 450 1201 3434 1097 454 1206 0.03 0.09 0.89 0.42
-

Model Prediction

Relative error
(%)
-

The most important fiinction ofthe FCC model is to correctly predict the product distribution. The values ofthe reaction parameters directly affect the product distribution. Only the activation energy ofthe reactions are used in parameterization because product distribution is more sensitive to the activation energy than to the frequency factor. Since only bulk volumes of four products from industrial data are available for the parameterization, three adjustable factors are used to adjust the values of activation energy ofthe cracking reactions. Each adjustable parameter corresponds to the formation of one ofthe three products: FCC gasoline, LCO, and light gas. It can been seen from Figure 4.2 that HCO is not formed in the FCC cracking. Hence, there is no adjustable parameter for HCO. Each original value of activation energy is adjusted by one of three parameters based on the observed products ofthe reaction. For example, the activation energy ofthe reactions from lump Ph, an component of HCO, to Pi, an component of LCO, is multiplied by the adjustable parameter of LCO formation and becomes the new value ofthe activation energy. The adjustable parameters that are used in the parameterization and their values are listed in Table 4.7.

88

Table 4.7 Adjustable Variables in FCC Model Benchmarking. Adjustable parameter

^^gasoline

Description Adj ustable parameter for activation energy of gasoline formation reactions

Parameter value 0.8576

^LCO

Adjustable parameter for activation energy of LCO formation reactions

0.8507

Alightgas

Adj ustable parameter for activation energy of light gas formation reactions

1.0198

ki,(lboil)(s)/lb catalyst

Kinetic frequency factor for the formation of gasoline from gas oil

8.626699E5

kc,

Frequency factor for the formation of coke Ratio of heat transfer coefficient of preheat box versus gas oil specific heat

0.48

(lb coke/lb catalyst) 0.4

A3, Btti/lb

14.33

Hcrack, BTU/(lb oil)

Heat for cracking reaction

-326.86

Oa.ref, Mole oxygen/mole air

reference O2, in estimating coke on regenerated catalyst

0.01197

ko2, (lbcoke)(s)/ft^

Frequency factor in the rate ofthe depletion of oxygen

2.55644E9

89

The process constraints are also parameterized to prevent the violations of process constraints. For this purpose, some process adjustable parameters are also included in the parameterization. These adjustable parameters have been used to develop the original model. Their values are also listed in Table 4.7. The values ofthe process constraints are from the design documents ofthe refinery and the original model. Personnel from the refinery agreed on the values of these process constraints. The values of process constraints are listed in Table 4.8. For the details of FCC model, adjustable parameters, and process constraints, the reader can refer to Ellis (1996). FCC model parameterization is an optimization problem. The least square type objective function is used in the parameterization. The objective function is shown below:

Objfparameterization

~ LI'^I V^model,I ~^base,I) /

'

(4-29)

where Objfparamterization- objective ftuiction of the FCC modcl parameterization, Wi- weighting factor, Wmodeij- weight flow rates of product I predicted by the FCC model, MLB/D, Wbase,!- weight flow rates of product I in industrial data, MLB/D. NPSOL optimization package (Gill et al., 1986) was used in the parameterization. Table 4.6 shows the comparison ofthe industrial data and model predictions. For this set of data, the model predictions fit the industrial data very well. The largest relative error is less than 1%.

90

Table 4.8 Process Constraints of FCC Unit. Constraint number 1 Lower Bound 500.0 Process Variable Description Temperature of fresh feed exiting preheat furnace, F 0.0 Flow rate of fuel to preheat furnace, SCM 14.7 Reactor pressure, psig 30 39.5 Upper Bound 700

14.7

Regenerator pressure, psig

30

5100

sa

Actual speed of lift air blower, RPM

6100

0.0

r'sucn.lift" 1" surge,! ift

Difference between suction

flow

None

and surge flow for lift air blower, ICFM

-5.0

P6-P4

Reactor-regenerator pressure difference, psi

2.0

0.0

t^sp

Level of catalyst in standpipe,

ft

20.0

35000

Fsucn.comb

Combustion air blowcr inlet suction flow, SCFM

42000

10

0.0

Fwg

Flow rate ofwet gas to wet gas compressor, (lbmol)/s

0.67

91

4.5 FCC Gasoline Octane Model Modification Since the FCC gasoline has about 45 vol.% ofthe gasoline pool, the changes of the properties ofthe FCC gasoline have great effect on gasoline blending. It is highly desirable to predict the properties of FCC gasoline accurately. In the original model, Ellis (1996) developed an empirical correlation to related the motor octane number to the riser temperature and conversion as below:

MON = MON,^, + a, (T, - 7;,,; + a,(Com - Conv,^,^),

(4.30)

where a i - constants, MON/F, ai- constants, MON/conversion Conv- weight conversion, lb (gasoline+light gas)/ lb gas oil, Convbase- base weight conversion, lb (gasoline+light gas)/ lb gas oil, MON- motor octane number ofthe FCC gasoline, MONbase- motor octane number ofthe base FCC gasoline, Tf- riser temperature, F Tr, base- basc riscr temperature, F. The values of base case and constants are listed in Table 4.9. It is found that MONs calculated from this correlation were about 2 octane number higher than the corresponding industrial data. In order for this correlation to fit the industrial data, modification is necessary. One set of data from the industrial data was selected as the base case. The value ofthe constant al is also changed based on the industrial data. The new values ofthe base case and constants are listed in Table 4.9.

92

Table 4.9 FCC Octane Model. Parameter Convbase MONbase,

Tr.base ai

Unit (gasoline+light gas)/ lb gas oil None

F MON/F

Original Model 0.55 72.5

900 0.05

Current Model 0.80 80.7

995 0.022

a2

MON/conversion

0.17

0.17

93

CHAPTER 5 REFORMER FEED CHARACTERIZATION AND MODEL BENCHMARKING

5.1 Process Overview Catalytic reformer is an important unit in gasoline production. The reformate, the product from the catalytic reformer, is a major blending stock in gasoline pool. Catalytic reformate furnishes approximately 40% ofthe United States gasoline requirements (Gary and Handwerk, 1984). The reformer in the refinery considered in this work provides about 30 vol.% blending stock for the gasoline pool. To appreciate the importance of catalytic reforming in gasoline production, the octane number must be understood. Octane number is an index used to measure the antiknock quality ofthe gasoline. Higher the octane number, the better the antiknock quality. Octane number is the most important specification for gasoline. Gasoline with higher octane number normally sells at higher price in the market. Two values of octane number, research octane number (RON) and motor octane number (MON), are used. Octane rating is the arithmetic average of MON and RON. Octane rating is used to refer the general antiknock quality ofthe gasoline in the United States. The octane ratings ofthe typical gasoline blending stocks in the refinery are shown in Table 5.1. Table 5.1 Octane Ratings ofthe Typical Gasoline Blending Stocks. Gasoline blending stock Low severity reformate High severity reformate FCC gasoline Alkylate Light sfraight-run (LSR) gasoline Butane Octane rating, (R0N+M0N)/2 92.3 94.5 87.1 91.1 69.0 91.5

94

Low severity reformate is the reformate produced when the severity ofthe catalytic reformer is low and high severity reformate is the reformate produced when the severity ofthe catalytic reformer is high. The inlet bed temperatures usually indicate the severity of the operation. The higher the inlet bed temperature, the more severe the operation. It can been seen from Table 5.1 that the reformate has the highest octane number among all the blending stock. Considering the large quantity ofthe reformate, it is clear that the reformate is the major octane booster in gasoline blending. It is not economical to process the Light straight-mn (LSR) gasoline (C5-180F) as feed to the reformer as this fraction is largely composed of low-molecular-weight paraffins that tend to crack to low-value butane and light fractions (Gary and Handwerk, 1984). The typical feedstock to the catalytic refomer is the heavy naphtha with a boiling range from 180 to 375F. The heavy naphtha produced from the cmde unit has an octane rating around 70, which is too low for gasoline blending. The reformer converts the heavy naphtha to the high-octane reformate. Reforming Process are classified as continuous, cyclic, or semiregenerative depending upon the frequency of catalyst regeneration. In a continuous process, the catalyst is removed and replaced during normal operation. In a semiregenerative process, the unit is shut down periodically to regenerate the catalyst. The normal intervals is 3 to 24 months. The cyclic process is a compromise between these extremes and is characterized by having a swing reactor in addition to those on-stream in which the catalyst can be regenerated without shutting the unit down (Gary and Handwerk, 1984). The catalytic reformer in the refinery considered in this work is a semi-regenerative type. The semi-regenerative type reformer has the advantage of minimal capital costs compared to continuous and cyclic type reformers (Gary and Handwerk, 1984). The disadvantage ofthe semi-regenerative type reformer is that the reformer needs to be taken off-stream periodically to regenerate the reforming catalyst that looses its activity during the operation. The reformer plays a key role in the hydrogen usage in the refinery. The reformer is the main provider ofthe hydrogen that is used in several hydrotreaters in the refinery to

95

treat feeds and final products. Without a reformer, a refinery has to rely on either a steam reforming unit or purchased hydrogen from resources outside the refinery. The flow diagram ofthe reformer in the refinery is shown in Figure 5.1. The reaction system consists of three fixed-bed reactors in sequence. The heavy naphtha from the cmde unit goes through a naphtha desulfurizer to eliminate the sulfiir and other impurities in the feed. Then the heavy naphtha is mixed with the hydrogen stream and exchanges heat with the product stream from the third reactor. The heavy naphtha is further heated in the preheat fiimace to reach the reaction temperature, about 890 to 980 F. Since the main reactions taking place in the reactor are endothermic, the temperature drops sharply in the reactor. The temperature drops to such a level that no reforming reaction can take place near the exit ofthe reactor. The effluent stream is withdrawn from the reactor and is heated in an intermediate heater to the reaction temperature. The hot stream flows to the next reactor. The product stream exits the third reactor and exchanges heat with incoming naphtha. The product stream then flows to a separator, which is a flash dmm, to separate the hydrogen in the product stream. The major part of hydrogen is returned to the reaction system. The extra hydrogen is used in other units in the refinery. After the separator, the product stream flows to a stabilizer to separate the C4 and lighter from the heavier components. C4 and lighter components are fed to the gas plant for ftirther treatment. The bottom stream ofthe stabilizer is the main product, reformate, which goes to the storage tank for gasoline blending. 5.2 Reformer Modeling The reformer modeling has been studied by many researchers. Taskar (1996) gave an exhaustive literature survey on reformer modeling. The steady-state model developed by Taskar (1996) was used in this work. The core of Taskar's model is a detailed kinetic scheme involving 35 pseudo-components connected by a network of 36 reactions in C5Cio range using Hougen-Watson-Langmuir-Hinshelwood-type reaction rate expressions. The compositions of pseudo-components in a typical reformer feed (Lin, 1988; are listed in Table 5.2.

96

u
C O
nj
QL

0)

,o <+3
J5 H- J3

ca
OH

z o
-*->
. ^ j

ca

ca ca
(U

>^

>
ca
kH

1)

c
fti

1)

00
(U
l-H

C/2

(U

ca
l+H

o <D
JS

a < u
CJ

C/2

fa
a

^ o
c/3
1/3

>!:

0) 0)

(U

O <!. (U C D) < C U 3 TO

o kH fa ' ' in
kH

-S
(J C D (U

a:

97

Fig

0 y o <"

Table 5.2 Chemical Components ofthe Reformer Feed. Chemical components Volume fraction of chemical component in a typical reformer feed 0 0 0 0 0 0 0.011533793 0.005766896 0 0.034154728 0.068309457 0.03902341 Molar specific volume. cm^/mole Molar fraction of chemical component in a typical reformer feed 0 0 0 0 0 0 0.0136791382 0.00676383225 0 0.0353870741 0.071473286 0.0553827156

Hydrogen CI C2 C3 C4 C5n-Pentane Iso-Pentane Multi-branched hexanes Single-branched hexanes n-Hexane Five-carbon ring C6 naphthenes Benzene Multi-branched heptanes Single-branched heptanes n-Heptane Five-carbon ring C7 naphthenes Six-carbon ring C7 naphthenes Toluene

31.0 52. 68. 84. 101.4 116.1 116.1 117.4 I3I.6 132.9 131.6 113.1 89.4 147.5 147.5 147.5 128.8

0.005057543 0.02882307 0.02882307 0.093747762 0.028779382

0.0076970243 0.026907108 0.026907108 0.0875160473 0.0358655286

0.052533793

128.3

0.0657239621

0.023964035

106.8

0.0305287825

98

Table 5.2 Continued. Chemical components Volume fraction of chemical component in a typical reformer feed 0.123659717 0.030914929 0.030914929 0.028199327 0.056398654 Molar specific volume. cm^/mole Molar fraction of chemical component in a typical reformer feed 0.104142811 0.0262767739 0.0258931714 0.0312810878

n-Octane Single-branched octanes Multi-branched octanes Five-carbon ring C8 naphthenes Six-carbon ring C8 naphthenes C8 Eiromatics n-nonane Single-branched nonanes Multi-branched nonanes Six-carbon C9 naphthenes C9 aromatics n-decane Single-branched decanes Multi-branched decanes Six-carbon ring CIO naphthenes C10 aromatics

163.5 162 164.4 144.7

143

0.0633059217

0.050215496 0.055560406 0.013890101 0.013890101 0.080274821 0.03693356 0.01043014 0.00521507 0.00521507 0.024351882

123.1 179.6 178.2 170.4 159.8 139.6 196 194.5 191.5 176.3

0.0555009602 0.0425968892 0.0107328858 0.0112241799 0.0806332576 0.0359961908 0.00732745014 0.00369198002 0.00374981783 0.0221713355

0.013418857

156.8

0.0116436799

It is worth noting that some pseudo-components are real chemical species, such as n-pentane and iso-pentane. The important difference between pseudo-components in the reformer and lumps used in the FCC model is that all the chemical species in a pseudocomponent ofthe reformer model has the same carbon number while the chemical

99

species of a lump in the FCC model do not have the same carbon number. One reason for this modeling difference is that the FCC feed is much heavier than the reformer feed. The FCC feed is so complicated that it is very difficult to use the same approach as the reformer model. Using detailed pseudo-components in the reformer provides much required information for the gasoline blending while the feed characterization of reformer becomes more difficult. Deactivation ofthe catalyst in the reformer was also modeled. The model was parameterized by benchmarking against the industrial data obtained from Phillips Petroleum Company. The reader can refer to Taskar (1996) for detailed discussion ofthe kinetics ofthe reforming reactions.

5.3 Reformer Feed Characterization 5.3.1 Naphtha Desulfiirizer In the refinery considered in this work, the reformer feed is composed of heavy naphtha, a side-draw stream ofthe atmospheric tower and the bottom stream ofthe naphtha splitter. The reformer feed flows through a naphtha desulfurizer before entering the reformer. The metals, hydrogen sulfide, ammonia, organic nitrogen and sulfur compounds will deactivate the catalyst in the reformer and must be removed before the feed enters the reformer (Gary and Handwerk, 1984). Hydrotreating is used to remove these impurities from the feed. The feed to the naphtha desulfurizer includes reformer feed from the cmde unit and the hydrogen stream from the reformer. The products ofthe naphtha desulfiirizer consist ofthe stripper overhead gas, desulfurizer separator overhead gas, liquidified petroleum gas (LPG), and sweetened naphtha. Stripper overhead gas and separator overhead gas flow to the gas plant for further treatment. The LPG flows to the debutanizer in the cmde unit. A detailed model was not built for the naphtha desulfurizer. Instead, material balance and fixed ratios are used to calculate the amotmts ofthe hydrogen, the stripper overhead gas, the separator overhead gas, LPG, and the sweetened reformer feed. The

100

ratios of each operation mode. Summer Mode or Winter Mode, are based on the industrial data of a typical day in each operation mode. The ratios are listed in Table 5.3. Table 5.3 Ratios in the Calculation ofthe Naphtha Hydrotreater. Rates H2/Feed, MLB H2/MLB feed H2/Feed, BBL H2/BBL feed Reformer feed/total feed, MLB reformer feed/MLB total feed Reformer feed/total feed, BBL reformer feed/BBL total feed Overhead gas/total feed, MLB overhead gas/MLB total feed Overhead gas/total feed, BBL overhead gas/BBL total feed LPG/total feed, MLB LPG/MLB total feed LPG/total feed, BBL LPG/BBL total feed 0.0623
0.0255 0.0024

Summer Mode
0.06997 0.07756 0.9108

Winter Mode
0.06366 0.07553 0.8920

0.9020

0.9035

0.0029

0.0017

0.0016 0.0183

0.0509

The amount ofthe hydrogen required by the naphtha desulfurizer is calculated using the formulas given below:
^H2 ^Hl = ^reformerfeed ' ^TIO^j21 reformer feed, W ' reformer feed, V ' (5.1) (5.2)

= Reformer feed " ^^10^^21

where WH2- mass flow rate ofthe hydrogen used in the naphtha desulfurizer, MLB/D, VH2- volumetric flow rate ofthe hydrogen used in the naphtha desulfurizer, BBL/D,

101

Wreformer feed" niass flow rate of the reformer feed from the crude unit, BBL/D, Vreformer feed- volumctric flow rate of the reformer feed from the cmde unit, BBL/D, RatioH2/reformer feed, w" niass ratio between the hydrogen and the reformer feed from the crude unit, RatioH2/reformer feed, v" volumctric ratio between the hydrogen and the reformer feed from the crude unit. The volume and the weight ofthe total feed are the summations ofthe volumes and the weights of incoming streams, reformer feed and hydrogen. For each product stream, the volume and the weight are calculated by the formulas given below:

W,=W,,,,-RATIO,, V,=V^^^,-RATIO^,.,

(5.3) (5.4)

where i- stripper overhead gas, separator overhead gas, LPG, sweetened reformer feed, RATIOi,v- volumetric ratio between the product i and the total feed to the naphtha desulfiirizer, RATIOi,w- mass ratio between the product i and the total feed to the naphtha desulfurizer, Vi- volumetric flow rate ofthe product stream i, BBL/D, Vfeed- volumetric flow rate of total feed to the naphtha desulfurizer, BBL/D, Wi- mass flow rate of product stream i, MLB/D, Wfeed- mass flow rate of total feed to the naphtha desulfurizer, MLB/D. The volumefric flow rate and mass flow rate ofthe sweetened reformer feed calculated above are then used as the inputs to the reformer model.

102

5.3.2 Paraffins-Naphthenes-Aromatics (PNA) in the Reformer Feed The molar flow rates ofthe pseudo-components in the feed are required by the reformer model. The feed characterization is to calculate the molar flow rates of these pseudo-components in the feed. It can been seen from the FCC feed characterization that feed characterization is a complicated process. For a much more complicated reformer pseudo-component system, no simple empirical correlation is available to calculate the molar flow rates. Taskar (1996) divided the reformer feed into several cuts based on boiling range and used empirical correlations (Daubert, 1994) to calculate the physical properties of each cut. Using the boiling point and the physical properties ofthe pseudo-components in the feed, the molar percentages ofthe pseudo-components are calculated by using Nelder-Mead optimization algorithm (Riggs, 1994) to find the composition which will give the same physical properties of each cut ofthe feed. One disadvantage of this approach is that the boiling point and the physical properties of each cut are not accurate because ofthe inaccuracy ofthe empirical correlations. Another disadvantage is that there may be several combinations of pseudocomponents which can give the same physical properties. In addition, local minimums exist in the optimization searching which means that the unique solution is not guaranteed in every optimization searching. If this approach were used in the refinerywide model, it will cause erroneous results in the reformer model when the optimization routine gives unreasonable reformer feed compositions. Although the paraffinnaphthenes-aromatics (PNA) calculated from the pseudo-component molar flow rates are close to the industrial data, the molar flow rates of pseudo-components calculated using the approach above can not be verified due to the lack of industrial data. The attempts to use the above approach failed in this work. The optimization algorithm did not give a reasonable solution. This may be due to the inaccuracy ofthe empirical correlations used to calculate the physical properties. However, some data from laboratory analysis ofthe portion ofthe cmde oil in the reformer feed boiling range are

103

available in the industrial data. It is more accurate to calculate the reformer feed information from these laboratory analysis than from empirical correlations. The industrial data are listed in Table 5.4 through Table 5.7. Table 5.4 Industrial Data of Crude A. Property Unit Light naphtha I50-200F 2.5 67.69 1.515 37.93 Heavy naphtha 200-360F 16.0 55.597 5.692 54.195 Extra heavy naphtha 360-385F 3.1 46.688 9.474 74.459

Yield API Gravity Aromatics Naphthenes+2x Aromatics (vol.%)) RON MON Sulfiir

Vol.% API Vol.% Vol.%

None None wt.%)

71.832 67.992 0.007

49.193 48.730 0.009

33.907 34.407 0.014

Table 5.5 Industrial Data of Cmde B. Property Unit Light naphtha 150-200F 1.9 73.961 8.556 40.037 Heavy naphtha 200-360F 9.7 55.534 18.169 60.471 Extra heavy naphtha 360-385F 2.8 44.077 23.499 78.858

Yield API Gravity Aromatics Naphthenes+2x Aromatics, (vol.%)) RON MON Sulftir

Vol.% API Vol.% Vol.%

None None Wt.%

71.832 67.992 0.013

42.657 41.863 0.028

34.648 34.408 0.037

104

Table 5.6 Industrial Data of Crude C. Property Unit Light naphtha 155265F 10.33 63.1 62.3 31.9 5.8
-

Heavy naphtha 265-350F 9.35 51.7 55.4 28.5 16.1

-

Extra heavy naphtha 350-400F 4.86 45.8 42.4 42.6 15.0

Yield API Gravity Paraffins Naphthenes Aromatics RON MON Sulfiir

Vol.% API Vol.% Vol.% Vol.% None None Wt.%

<.02

0.03

0.05

5.7 Industrial Data of Cmde D. Property Unit Light naphtha 155265F 9.18 60.9 57.4 34.3 8.3
-

Heavy naphtha 265-350F 9.78 51.7 55.8 27.6 16.7

Extra heavy naphtha 350-400F 5.44 46.1 41.8 45.8 12.4

-

Yield API Gravity Paraffins Naphthenes Aromatics RON MON Sulftir

Vol.% API Vol.% Vol.% Vol.% None None Wt.%

0.02

0.02

0.02

The naphtha desulfurizer that treats the reformer feed mainly removes the sulfur from it. Hydrocarbon in the reformer feed does not react in the naphtha desulfurizer. Hence, the PNA ofthe sweetened reformer feed after the naphtha desulfurizer is considered to be the same as the reformer feed entering the naphtha desulfurizer. The

105

normal boiling range ofthe reformer feed is 180 to 375F. It can be seen from Table 5.4 through Table 5.7 that all or part of light naphtha, heavy naphtha, and extra heavy naphtha is in the boiling range ofthe reformer feed. Therefore, the PNA ofthe reformer feed can be calculated from the PNAs of these cmde cuts. The cmde cut ofthe light naphtha is the source for both the light straight-mn (LSR) gasoline and the reformer feed. The portion of light naphtha in the reformer feed is calculated from the volume corresponding to the EBP ofthe light naphtha and the volume corresponding to the cut point ofthe LSR, which has been calculated in the naphtha splitter model in Chapter 3. The calculation uses the follow formula: V
n .,. '^ EBP.In

-V
' cul poinl. LSR / c ^N

Portion^^j^^j^^j,= where

(5.5)

PortioUreformer feed. In- volumetric portion of the light naphtha in the reformer feed,
VEBP.III-

volume percentage corresponding to the EBP ofthe light naphtha on the whole crude TBP- volumetric curve, vol.%,

Vcut point, LSR- volumc percentage corresponding to the cut point ofthe light naphtha on the whole crude TBP- volumetric curve, vol.%), Vin- volume percentage the light naphtha in the total cmde oil, vol.%. It is to be noted that the EBP ofthe light naphtha ofthe cmde A and cmde B is 200F while the EBP of cmde C and cmde D is 265F. It can been seen from Table 5.4 and Table 5.5 that the industrial data ofthe cmde A and cmde B have the volumetric percentages ofthe aromatics and naphthenes+2x Aromatics. The volumetric percentages ofthe naphthenes and paraffins can be calculated by the following equations: %naphthene = %N2A - %aromatics, %paraffin = 100 - %aromatics - %naphthene, (5.6) (5.7)

106

where %)paraffin, %naphthene, %aromatics- the volume percentages of paraffin, naphthene, aromatics, respectively, vol.%, %)N2A- the volume percentages of naphthene+2xaromatics, vol.%). Now we have the PNA information of all the cmde types in the cmde feed. The PNA ofthe reformer can be calculated as the summation ofthe PNAs ofthe cmde cuts in the reformer feed:

(Portion
0/ ^ V^O/T/ ^^^^ 'reformer feed.ln.i

-V
'^ In.i

-V

+\
'^X.ln.i^

A)Ji = /

/OV: -

(5.7)

^-'
I

V
V hn.i

-V
' X.hn.i^

+V
' ehn.i

-V
" X.ehn.i

where i- cmde type A, B, C, and D, X - molecule type, paraffin, naphthene, and aromatics, %)X- volume percentage of molecule type X, paraffin, naphthene, aromatics, vol.%, %)Vi- volume percentage of cmde type i in the total cmde, vol. %, Vin,i- volume fraction ofthe light naphtha in the cmde type i, Vx,in,i- volume fraction ofthe molecule type X in the light naphtha in the cmde type i, Vhn,i- volume fraction ofthe heavy naphtha in the cmde type i, Vx,hn,i- volume fraction ofthe molecule type X in the heavy naphtha in the cmde type i, Vehn,i- volume fraction ofthe extra heavy naphtha in the cmde type i, Vx,ehn,i- volumc fraction ofthe molecule type X in the extra heavy naphtha in the cmde type i. The typical PNA ofthe reformer feed is available in the industrial data. The comparison between the PNA calculated above and the typical industrial data of the refinery considered in this work are shown in Table 5.8. The operating variables ofthe cmde unit use the normal values in Table 3.7 in Chapter 3. It can be seen from Table 5.5

107

that the average absolute difference between the results ofthe feed characterization and typical industrial data is 1.3 vol.%. The biggest difference exists in naphthene with 1.9%. Table 5.8 Comparison of Volume Percentages of PNA from Feed Characterization and the Industrial Data. Molecule Type Paraffin, vol.% Naphthene, vol.% Aromatics, vol.% Average difference Feed Characterization 5Z9 34.9 12.2 Industrial Data 53 33 14
_

Difference, vol.% 0.1 1.9 1.8 1.3

5.3.3 Molar Flow Rates ofthe Pseudo-Components in the Reformer Feed The calculation ofthe molar flow rates ofthe thirty-five pseudo-components in the reformer feed follows the steps given below: a. Constmct a typical reformer feed. The volume fractions ofthe pseudo-components in the typical reformer feed are obtained from literature (Lin, 1988; Turpin 1994; Taskar, 1996). b. Assume the ratios ofthe pseudo-components in each molecule type, the paraffins, the naphthenes, and the aromatics, do not change. Calculate the volume fractions ofthe pseudo-components in the reformer feed using the formula given below:

p^..=F,..^^^^,

(5.8)

where j - paraffins, naphthenes, and aromatics, Vi j - volume fraction of a pseudo-component i which is a molecule type j , Vij,typicai- volume fraction of a pseudo-component I which is a molecule type j in the typical reformer feed. 108

Vj- volume fraction of a molecule type j , Vj.typicai- volume fraction of a molecule type j in the typical reformer feed,

c. Calculate the molar flow rate of each pseudocomponent using the molar specific volume ofthe pseudo-component and its volumetric flow rate using the formula given below:

/wo/,.=^,
" Vmol^j

(5.9)

where molij- molar fraction of a pseudo-component i which is a molecule type j , Vmolij- molar specific volume of a pseudo-component i which is a molecule type j . The volume fractions ofthe pseudo-components are listed in Table 5.2. The molar specific volumes of pseudo-components are also listed in Table 5.2. The volume fractions and molar fractions of pseudocomponents calculated in equations 5.8 and 5.9 are normalized after all the pseudo-components have been calculated. The total molar flow rate ofthe reformer feed is calculated following the steps as given below: a. Calculate the mass flow rate of each cmde cut using the API gravity ofthe cmde cut, the volume percentage with respect to the particular cmde, and the volumetric flow rate ofthe particular cmde. b. Calculate the molecular weight ofthe each cmde cut using the approach described in the Chapter 3 of this dissertation. c. Calculate the molar flow rate of each cmde cut using the molecular weight and the mass flow rate ofthe cmde cut. d. Calculate the molar flow rate of reformer feed by summing the molar flow rates of the individual crude cuts.

109

The molar flow rate of a pseudo-component in the feed is then calculated as below:

Fmol,j=mol,j-V.

-Fmol^^^,,

(5.10)

where Fmolij- molar flow rate of a pseudo-component i which is a molecule type j , mol/s, Fmolfeed- total molar flow rate ofthe reformer feed, mol/s. The calculated molar flow rates ofthe pseudo-components in the reformer feed then become the input to the reformer model. 5.4 Reformer Model Benchmarking The reformer model developed by Taskar (1996) is based on a reformer in Phillips Petroleum Company. The reformer in the refinery considered in this work is slightly different from the reformer in Phillips Petroleum Company. For example, the throughput and catalyst load ofthe reformer considered in this work are significantly less than those in the Phillips's unit. Some minor modifications in the model have been made to enable the reformer model to represent the reformer considered in this work. The amounts of catalyst in each bed ofthe reformer unit considered in this work have been obtained from the industrial data. They are shown in Table 5.9. Table 5.9 Catalyst Weight in Each Reactor Bed. Bed number 1 2 3 4 Total Catalyst weight in the original Model, lb. 25000 25000 25000 50000 125000 Industrial Data, lb, 10781 21965 44652 0 77398

110

It can be seen from Table 5.9 that the reformer in the refinery considered in this work loads has about 40% less catalyst in the reactor than the unit described by the Taskar (1996). In addition, there are four beds in the Phillip's unit while only three beds are used in the reformer considered in this work. The reaction system also needs to be modified to fit the industrial data. The reformer operation in the refinery considered here has two operation modes: low severity and high severity. The typical operation data ofthe low-severity operation mode and the high-severity operation mode were used in the model benchmarking. The industrial data are listed in Table 5.10. Table 5.10 Comparison ofthe Industrial Data and Model Prediction after Benchmarking. Operation Mode Low severity Conversion Research Octane number Aromatics in the reformate. vol.% Hydrogen Production, SCF H2/BBL feed Benzene in the reformate, wt. % High severity Conversion Research Octane number Aromatics in the reformate, vol.% Hydrogen Production, SCF H2/BBL feed Benzene in the reformate, wt. % Average Error 1260 3.5 1150.43 3.45
-

Industrial data 0.802 95.

Model prediction 0.797 94.9

Relative error, % 0.62 0.11

59 1176.54 2.7 0.757 99.7

55 1011.74 2.5 0.756 100. 62.4

6.78

14.01 7.41 0.13 0.30

63

0.95 8.70

1.43 4.04

111

The activation energy and frequency factor ofthe thirty-six reactions were considered as adjustable parameters to benchmark the model against industrial data. All these thirty-six reactions belong to four reaction types: hydrocracking, ring closure, dehydrogenation, and isomerization. The reader can refer to Taskar (1996) for detailed description ofthe reaction system. It is found that the model predictions are not sensitive to the activation energy and frequency factor ofthe isomerization reactions. Therefore, only the activation energy and the frequency factor ofthe reactions of hydrocracking, ring closure, dehydrogenation are adjusted in the benchmarking. In order to simplify the parameterization, two adjustable parameters are used to adjust the activation energy and frequency factor of all the reactions belong to one reaction type. Therefore, there are total six adjustable parameters were used in the benchmarking. These parameters adjust the activation energy and the frequency factor ofthe reactions by multiplying the original values to form the new values. The values ofthe adjustable parameters that were obtained in the benchmarking are listed in Table 5.11.

Table 5.11 Adjustable Parameters in the Reformer Model Benchmarking. Adjustable parameter
^hydrocracking

Description Adjustable parameter for the activation energy of hydrocracking reactions

Parameter value
1.7996

r hydrocracking

Adjustable parameter for the frequency factor of hydrocracking reactions

1.000248EI7

Aring closure

Adjustable parameter for the activation energy of ring closure reactions

0.6993

F ring closure

Adjustable parameter for the frequency factor of ring closure reactions

5.004975E-6

Adehydrogenation

Adjustable parameter for the activation energy of dehydrogenation reactions

l.OOI

F dehydrogenation

Adjustable parameter for the frequency factor of dehydrogenation reactions

1.000261

112

The parameterization is an optimization problem. The optimization routines try to find a set of values ofthe adjustable variables to minimize the difference between the model predictions and the corresponding industrial data. Like the FCC model benchmarking, a least square error type function is used as the objective function for the optimization problem. The formula is given below:

^bjJparamelerizalion

~ 2-1

'^

"'"del.!

~-^hase.I

'

('i^J

where I - operation variables, such as conversion, RON, etc., Objfparamterization- objcctive functiou valuc of the reformer model parameterization, Wj- weighting factor, Xmodei,!- valuc of the operation variable I predicted by the reformer model, Xbase,!- value ofthe operation variable I in industrial data. NPSOL optimization package (Gill et al., 1986) was used in the parameterization. Table 5.10 shows the comparison ofthe industrial data and model predictions. The average relative error ofthe model predictions compared to the industrial data is 4.04%. The largest error exists in hydrogen production with 14.01% in Summer Mode and 8.70% in Winter Mode. Since the refinery produces more hydrogen than what it needs, the extra hydrogen is sent to the fuel gas. Therefore, the error on the prediction of the hydrogen production has insignificant effect on the economy ofthe refinery-wide operation. The difficulty in the reformer model benchmarking is that one set of adjustable parameters was used to benchmark against the data of both operation modes. Using two sets of adjustable variables for two operation modes may make the model predictions agree with the industrial data better. However, it is incorrect theoretically to use two sets of adjustable parameters. The reason is that the basic kinetics are the same for both the high severity mode and the low severity mode. Hence, the same reaction constants, activation energy and frequency factor, should be used for both modes. To conclude, the model

113

predictions reasonably agree with the industrial data after benchmarking using one set of adjustable parameters.

5.5 Average Reformer Operation The reformer is operated at low severity mode and high severity mode altematively. Low severity mode uses lower inlet bed temperature which produces reformate with research octane number (RON) around 95. High severity mode uses higher inlet bed temperature which produces reformate with RON around 100. Which severity the reformer is operated is decided by gasoline blending situation. When the average octane number ofthe whole gasoline pool is high, the reformer is operated at low severity. On the contrary, the reformer is operated at high severity when the average octane number ofthe whole gasoline pool is low. The reformer is also not operated continuously. The reformer is shut down periodically to regenerate the catalyst which loses it activity during the operation. The regeneration time is about 2 weeks. The regeneration costs about $450,000 each time. The reformer is not operated at the same operation mode and is not operated continuously. However, the refinery-wide model of which the reformer is one unit is a steady-state model. Hence, the operation shifting and periodical shut down ofthe reformer must be accounted. 5.5.1 Operation Time Fraction of Low Severity In order to represent the fact that the reformer altemates operation mode during each reformer operation cycle, two executions ofthe reformer are carried out in one execution ofthe refinery-wide model. One execution is for the high severity mode and the other execution is for the low severity mode. In order to represent the fact that different mode is used for different time, the product rates from each execution of reformer model are multiplied by the time fraction discussed above. According to the engineers from the refinery, the reformer is operated at low severity about 70%) ofthe total operation time. This operation time fraction of low severity becomes a handle for adjusting reformer operation. Hence, this fraction is a decision variable for the refinery-

114

wide optimization. The upper limit ofthe operation time fraction of low severity is set at 0.8 and the lower limit is set at zero according to engineers in the refinery.

5.5.2 On-Stream Factor The On-stream factor is the fraction of time that the reformer is at operation in the total time. The cycle length ofthe reformer can be approximately calculated using the formula given below:

C
rn _ coke .final ^cycle - - ^
coke .average

'

/c i '^\ P - i^;

where Tcycie- cycle length, hr, Ccoke,fmai- cokc contcut at the end of a cycle, kg coke/kg catalyst, ACcoke,average- the average coking rate in a cycle. A cycle usually ends when the octane number ofthe reformate can not be maintained at a certain level even using the highest inlet bed temperature and maximum H2 recycle ratio. Since octane requirement ofthe reformate for the low severity mode is different from that ofthe high severity mode, the corresponding coke contents are different. In this study. Lower limit of octane requirement for each operation mode, the highest inlet bed temperature and maximum H2/Hydrocarbon recycle ratio are listed in Table 5.12.

115

Table 5.12 Reformer Operation Limit. Low severity Research octane number (RON) Highest Inlet bed temperature, F Maximum H2/Hydrocarbon recycle ratio, mol H2/mol Hydrocarbon 7.5 7.5 95 980 High severity 99.5 980

Ccoke.finai is the cokc contcut at the end of a cycle defined by these operating conditions. It is known the coke contents on catalysts are not the same across the three reactor. There are three reactors in the reformer unit. Each reactor is divided into several regions according to coke content and the coke content in each region is assumed to be the same (Taskar, 1996). An example ofthe coke contents in different regions is shown in Table 5.13. The coke contents shown in Table 5.13 are the coke contents at the end of the cycle ofthe low severity mode. Table 5.13 Coke Contents in Dfferent Regions. Section number Low severity, coke content, kg coke/kg catalyst High severity, coke content, kg coke/kg catalyst

la lb Ic 2a 2b 3a 3b (la+2a+2b+3a+3b)/5

3.31 E-2 8.02 E-3 3.90 E-3 6.36 E-2 8.42 E-2 9.07 E-2 1.02 E-1 7.47 E-2

2.41 E-2 5.76 E-3 2.91 E-3 4.58 E-2 6.21 E-2 6.71 E-2 7.55 E-2 5.49 E-2

116

The first digit ofthe section number indicate which reactor the section belongs to. The second digit indicates the location of section in the reactor. For example, section 1 b is the section behind section la and section Ic is the section behind section lb, all in reactor 1. It can be observed from Table 5.13 that coke contents in section la, 2a, 2b, 3a, 3b have the same order and are much higher than the coke contents in section lb and Ic. The phenomena have been explained in detail in Taskar (1996). To simplify the calculation, an average coke content is calculated using the coke contents in section 1 a, 2a, 2b, 3a, and 3b. This average coke content is used as the Ccoke.fmai. The steady-state model ofthe reformer used in the refinery-wide model has zero coke content on the catalyst, which represents the catalyst condition at the beginning of each cycle. The coking rate, with an unit of kg coke/kg catalyst/hr, under this condition is calculated in the model. However, equation 5.12 requires the value of average coking rate in one cycle. The relations between the coking rates at zero coke content and the average coking rates in one cycle was also obtained from the above tests and are listed in Table 5.14. Again, the average coking rate of section la, 2a, 2b, 3a, 3b is used for both coking rates. The average coking rate in one cycle is calculated as the product of the coking rate at zero coke content and coking rate ratio for either the low severity mode or the high severity mode. Table 5.14 Ratios between Aerage Coking Rate and Coking Rate at the Beginning of a Cycle. Section number Coking rate ratio Low severity Coking rate ratio High severity

la 2a 2b 3a 3b (la+2a+2b+3a+3b)/5

4.19 5.19 12.2 4.85 8.25 6.94

1.92 2.10 3.22 2.01 2.61 2.37

117

After the cycle length is calculated, the on-stream factor is calculated using the formula given below:

=
T cycle

^-^^
T regeneralion

(5.13)

on-slream

where Tregeneration- reformer shut down time or catalyst regeneration time, hr. According to engineers in the refinery considered in this work, the regeneration time is about two weeks. Hence, the total hours in two weeks, 336, is used for Tregeneration for both low severity mode and high severity mode. In order to account for periodically shut down ofthe reformer, the product rates from the reformer model are discounted by multiplying each product rate by the onstream factor and operation time fraction using the equation given below: V
product

=v
produci .model

- F T
on-slream operalion lime fraclion '

rs M"*
v*-^'-*- ' /

where Vproduct- volumetric flow rate of a product from the reformer as an output to other units, bbl/day, Vproduct, model- volumctric flow rate of a product calculated from the reformer model, bbl/day, Toperation time fraction" Operation time fraction of either the low severity mode or the high severity mode.

5.5.3 Regeneration Cost The cost of each regeneration ofthe reformer catalyst is normally $450,000. Refinery-wide optimization requires the regeneration cost for each day. For each

118

operation mode, low severity and high severity, the regeneration cost for each day is calculated by dividing the total cost of each regeneration by the cycle length calculated in equation 5.12. The regeneration cost for each day for the reformer as a whole is then calculated using the equation given below:

regeneralion.reformer regeneralion.high .severity \

regeneralion Jow severily low severily ^

low severity

,^

^ C\

where
L-OStregeneration,reformer, C^OStregeneration,low severity, C^OStregeneration,high severity rCgncratlOn COStS 01

the reformer as a whole, low severity, high severity, respectively, Tiow severity- Operation time fraction ofthe low severity mode.

119

CHAPTER 6 MODELING OF GAS PLANT, ALKYLATION UNIT AND DIESEL HYDROTREATER

Besides the models ofthe four main processing units presented in the previous chapters, there are other processing units in the refinery, whose models are required to carry out plant-wide optimization studies. The models ofthe gas plant, the alkylation unit, and the diesel hydrotreater are discussed here. 6.1 Gas Plant The gas plant processes all the light gases generated by various units in the refinery. The main sources of light gases are the cmde unit, the FCC unit, and the reformer. The naphtha desulfurizer and diesel hydrotreater also produce some light gases as by-products. All the light gases are combined together and sent to the gas plant. The product streams coming out ofthe gas plant include fiiel gas, propylene, and alkylation feed. The fuel gas is used as fiiel in the furnaces in the refinery. Propylene is sold directly in the market. The alkylation feed stream flows to the alkylation unit to make alkylate, a gasoline blending stock. Simplified models were built for the units in the gas plant based on material balances. The gas plant is very complicated in the sense that the light gas streams come from multiple sources and the streams are mixed in several places. It is very difficult to calculate the flow rates ofthe light gas components in all the streams in the gas plant. To simplify the modeling, the gas plant is divided into two blocks, fuel gas production and depropanizer. Only the compositions ofthe streams around these two blocks are calculated. All the light gas streams from other units in the refinery enter the fuel gas production block. The fuel gas and the heavier hydrocarbon are two streams exiting the fuel gas production block. The heavier hydrocarbon stream goes to the depropanizer. Propylene, known as C3 product in the refinery considered in this work, exits from the

120

top ofthe depropanizer and is sold as a final product. The stream that exits from the bottom ofthe depropanizer becomes the feed stream to the alkylation unit. The schematic ofthe gas plant is shown in Figure 6.1. 6.1.1 Sources of Light Gas Light gas mainly comes from the cmde unit, the FCC unit, and the reformer unit. The light gas produced in the cmde unit was calculated based on the LP reports obtained from the refinery considered in this work. The light gases from the cmde unit are listed in Table 6.1. The same product rates are used to calculate the amounts of light gases from the cmde unit in the model disregarding the operating conditions in the cmde unit.

Fuel gas C3 product

Light gas from crude unit Light gas from FCC Light gas from reformer Fuel gas production block C3/C4 stream Depropanizer

Alicylation feed

Figure 6.1 Schematic ofthe Gas Plant in the Fuel-Oriented Refinery.

121

Table 6.1 Light Gas Production Rates in the Cmde Unit. Light gas Ethane, lb/lb cmde feed Propane, lb/lb crude feed Isobutane, lb/lb cmde feed Normal Butane, Lb/lb crude feed Summer Mode 0 0.00175 0.00202 0.00593 Winter Mode Difference

0
0.00054 0.00217

0
0.00121 0.00015 0.00032

0.00625

The largest amount of light gas produced in a refinery comes from the FCC unit. In the original FCC model of Ellis (1996), the light gases are calculated by the empirical correlations based on the API gravity ofthe FCC feed and the conversion ofthe FCC feed. However, the predictions from the empirical correlations are not consistent with the industrial data obtained from the refinery considered in this work. Hence, the industrial data for light gas production rates in the FCC unit are used here. The percentages ofthe light gas components in the total light gas ofthe FCC unit are shown in Table 6.2. It can be seen from Table 6.2 that both modes have similar light gas production exception propane. This is because the operation ofthe FCC unit in the Winter Mode is almost the same as that ofthe Summer Mode. The average values listed in Table 6.2 are used to represent the components of light gases modeled for both operation modes. The FCC model can only predict the total amount ofthe light gas, but not individual components present in the light gas. Assuming the same weight percentages ofthe light gas components in the total light gas as those in the industrial data, the weights ofthe light gas components from the FCC unit are calculated using the formula given below:

^ti

= ^ttotal

-^i^

(6.1)

Where wti- the weight ofthe light gas component i, v^totai- the total weight ofthe light gas.

122

Xi- the weight fraction of light gas component i in the total light gas. Table 6.2 Compositions of Light Gas from FCC Unit. Light gas Summer Mode wt.%) Gases < C2 Propane Propylene Isobutane Butylene Normal Butane 9.3 29.3 17.1 21.7 9.0 13.6 Winter Mode wt.% 9.5 29.2 16.9 21.6 9.1 13.6 Average wt.%) 9.4 29.2 17.0 21.6 9.1 13.6

The light gas components from the reformer have already been calculated by the detailed reformer model discussed in Chapter 5 of this dissertation. However, the reformer model only predicts the total amount of butane, which includes both normal butane and isobutane. Therefore, it is assumed that isobutane is about 42 wt.% ofthe total butane according to the industrial data obtained from the refinery considered in this work. 6.1.2 Fuel Gas Production The fuel gas mainly contains the hydrocarbons with carbon number less than three and hydrogen. The light gas stream from the reformer contains some hydrogen. The fuel gas also contains a small amount of heavy hydrocarbons with carbon number equal to or greater than three. These heavier hydrocarbon components enter the fuel gas due to incomplete separation in the gas plant. Since we do not have rigorous models for each separation units in the gas plant, the average industrial data ofthe loss of heavier hydrocarbons in the fuel gas shown in Table 6.3 are used in the model. These losses are assumed to be constants for each operation mode and do not change with operating conditions. The total amotmt ofthe fuel gas is the sum ofthe light hydrocarbons and the losses of heavy hydrocarbons in the fuel gas.

123

Table 6.3 Losses of Heavy Hydrocarbons in the Fuel Gas. Light gas Propane, wt.% Propylene, wt.%o Isobutane, wt.% Butylene, wt.%) Normal Butane, wt.%) 6.1.3 Depropanizer The depropanizer separates the heavier hydrocarbon stream into C3 product and alkylation feed. The C3 product, the overhead stream, contains propylene and propane. The alkylation feed, the bottom stream, contains mainly normal butane and isobutane. It also contains some propylene and propane due to incomplete separation in the depropanizer. Propylene can also react in the alkylation unit to form alkylate. From the industrial data obtained from the refinery considered in this work, the C3 product stream does not contain any C4 hydrocarbons while the alkylation feed stream contains some C3 hydrocarbons. If the distributions ofthe C3 hydrocarbons in the two streams are known, the compositions ofthe two streams can be calculated. The industrial data for propylene entering the C3 product stream shown which are in Table 6.4 are used in the model. These values do not change with respect to operating conditions. Summer Mode 33.4 26.3 16.9 6.2 11.4 Winter Mode 32.0 26.1 16.8 6.2 8.2

Table 6.4 Portion ofthe Propylene in the C3 Product. Mode Summer Mode Portion of total propylene entering C3 product, wrt.% 60.7 79.4 Winter Mode

The mass flow rate ofthe propylene in the C3 product can then be calculated from the total mass flow rate ofthe propylene in the depropanizer feed and the values in Table 6.4. There is no industrial data about the portion of propane entering the C3 product

124

stream available. However, it is known from the industrial data that the propane is about 40 vol.%) and the propylene is about 60 vol.%) in the C3 product. This value is valid for both operation modes. Hence, the amount of propane entering the C3 product stream can be calculated from the amount ofthe propylene entering the C3 product stream using the formula given below:

V
TT/ _ propane y propane _^ n ^ propane

- ^PC
propane y propylene ^p^ propylene ' ^ g 2^) \ )

propane '

W
propylene

= I-W
propane''

(6 3\
v"--"/

where Wpropane, Wpropyiene- weight percentages of propane, propylene in the C3 product, respectively, Vpropane, Vpropyiene- volumc percentages of propane, propylene in the C3 product, respectively. The densities of propane and propylene are from literature (Edmister and Lee, 1984). The mass flow rate ofthe propylene can be calculated from its weight percentage and the mass rate ofthe propane using the formula given below:

WT
' propylene

=WT
propane

W ._p^py!f!!L
rry propane '

(f.A)
v"'^^

where WTpropane, WTpropyiene- mass flow ratcs of the propanc and propylene in the C3 product, respectively. The mass flow rates of propane and propylene in the alkylation feed are obtained by subtracting the propane and propylene in the C3 product from the total propane and propylene in the feed to the depropanizer. 125

6.2 Alkylation Unit In the alkylation unit, the propylene and butylene react with isobutane to form isoheptane and isooctane, respectively. Isoheptane and isooctane are two major components ofthe alkylate. Isooctane and isoheptane are excellent gasoline blending stocks with high octane number and low Reid Vapor Pressure (RVP). The normal paraffins, such as propane and normal butane, do not react in the alkylation unit. They are separated from the alkylate in the separation train ofthe alkylation unit. Although the alkylation reactions can take place at high temperature and pressures without catalysts, the only processes of commercial importance involve low-temperature alkylation conducted in the presence of either sulfuric or hydrofluoric acid (Gary and Handwerk, 1984). The refinery considered in this work uses hydrofluoric acid as the catalyst in the alkylation unit. In the alkylation unit, high isoparaffin/olefin ratios (4:1 to 15:1) are used to minimize polymerization and to increase product octane (Gary and Handwerk, 1984). The isobutane produced inside the refinery is not enough to satisfy the requirement ofthe alkylation reactions. Isobutane purchased in the market is added to alkylation feed before it enters the alkylation unit. A simplified schematic ofthe alkylation unit is shown in Figure 6.2. In the reaction part ofthe alkylation unit, the alkylation feed is mixed with hydrofluoric acid in an acid settler. Since the acid phase is heavier than the hydrocarbon phase, the reaction mixture settles into two liquid layers in the settler. The acid is withdrawn from the bottom ofthe settler and then recycled and mixed with more fresh feed. The hydrocarbon layer is a mixture of propane, isobutane, normal butane, and alkylate. The hydrocarbon layer is withdrawn from the top ofthe settler and flows to a depropanizer.

126

0)

3 K . 5 .N a> C

c c o
td p t-

(u F ^ o
OH

y
I>

X)

Q
0)

c >~ 5

'C o
o

CO

a. o

'o U

<
ca
C N S o

i>

ca

a
J3
(U

o x> <u o

1)

S) f
<u c f) m
^
1/3

<u
3 XI O
H-

Rec sob

>. ^

c .2
5
C O

X3 T3 "^
ai

<

fa

<

127

The propane is withdrawn from the top ofthe depropanizer and becomes a final product. The bottom stream withdrawn from the depropanizer goes to a deisobutanizer. The isobutane exits the deisobutanizer from the top and is recycled to react with more fresh feed. Normal butane and alkylate exits the deisobutanizer from the bottom and flows to debutanizer. The butane is withdrawn from the top ofthe debutanizer and goes to the gasoline blending unit as a blending stock. The alkylate is withdrawn from the bottom ofthe debutanizer and goes to the gasoline blending unit as a blending stock. A simplified model was developed for the alkylation unit. The model is based on the stoichiometric relations ofthe alkylation reactions. Three major alkylation reactions are given below:

CH3

CH3

CH3

CH3

CH3-C=CH2 + CH3-CH-CH3 -^ CH3-C-CH2-CH-CH3 CH3 Isobutylene Isobutane CH3 2,2,4-trimethylpentane (Isooctane) CH3 CH3

CH3-CH2-C=CH2 + CH3-CH-CH3 - CH3-CH2-C-CH2-CH-CH3

butylene

Isobutane

2,4-dimethylhexane

:H3

CH3

CH3=C-CH3 + CH3-CH-CH3 ^ CH3-C-CH2-CH2-CH3 Propylene Isobutane 2,2-dimethylpentane (Isoheptane)

The first two reactions can be considered as one reaction in the model since the properties ofthe reactants and the product of both reactions are very similar since they are isomers. The model does not distinguish between the normal butylene and the isobutylene in the alkylation feed. 128

Another path in propylene alkylation is the combination of propylene with isobutane to form propane plus isobutylene. The isobutylene then reacts with more isobutane to form isooctane (Gary and Handwerk, 1984). The reaction of propylene with isobutane is shown below:

CH3

CH3

CH3=C-CH3 + CH3-CH-CH3 -^ CH3-CH2-CH3 + CH3-C=CH2

Propylene

Isobutane

Propane

Isobutylene

It is assumed that all the propylene and the butylene in the alkylation feed react with isobutane to form the alkylate. Since there is only one reaction path for the butylene, the amount of isobutane required and the amount of isooctane produced from butylene can be calculated from the stoichoimetric relation ofthe butylene alkylation. There are two reaction paths for the propylene to form alkylate. The amount of propylene for each reaction path needs to be determined. The weight percentage of propylene that reacts in the second reaction path based on industrial data is listed in the Table 6.5. The difference between two modes is 0.0029 wt.%. hence, the average value listed in Table 6.5 is used for both operation modes in the model. It is assumed that this average weight percentage is constant and does not change with operating conditions. Table 6.5 Weight Percentage ofthe Propylene that Reacts in the Second Reaction Path in the Alkylation Unit. Propylene going though the second reaction path, wt.%o Summer Mode Winter Mode Difference Average 0.0458 0.0429 0.0029 0.0444

The amount ofthe isooctane and the isoheptane in the alkylate can be calculated from the stoichoimetric relations. Since all the stoichoimetric constants in all the 129

alkylation reactions are equal to unity, the stoichoimetric constants do not appear in the equations of calculating the isooctane and the isoheptane in the alkylate. The calculations use the following formula:

W
j-fT isooctane

MW

W
, "propylene

-X

. .-MW
i.sooctane ' (f,A\ V /

_ "butylene ^'-"'isooctane ~ H/flJ/ ^ ' ^ butylene

^'^ sec ond path * A/fW ^ ' ^ propylene

isoheplane

propylene

second path) i rwrr MW I propylene

^^

isoheptane '

rr r\ v * /

where Wisooctane, Wisoheptane" Hiass flow ratcs of isooctauc and isoheptane, respectively, MLB/D, Wbutyiene, Wpropyiene- mass flow ratcs of butylcnc and propylene in the alkylation feed, respectively, MLB/D,
MWisooctane, MWisoheptane, MWbutylene, MWpropylene" m o l c C u l a r W C i g h t S o f isOOCtaUC,

isoheptane, butylene, and propylene, respectively, g/mole, Xsecond path- Weight fraction of propylene that reacts in the second reaction path. The alkylate formed by butylene is called butylene alkylate and the alkylate formed by propylene is called propylene alkylate. The octane number ofthe butylene alkylate and the propylene alkylate are listed in Table 6.6. These numbers come from Gary and Handwerk (1984). Table 6.6 Octane Number ofthe Butylene AH kylate and Propylene Alkylate. Type Butylene alkylate Propylene alkylate RON 96 93 MON 94 91

The octane number ofthe alkylate is calculated as the volumetric average value using the formula given below:

130

alkylate

butylene alkylate

propylene alkylate

propylene alkylate

propylene alkylate '

V /

where Ouaikyiate- MON Or RON ofthe alkylate product, Oubutyiene alkylate, Oupropyiene alkylate" MON Or RON of the butylcne alkylate and the propylene alkylate, respectively, Vbutyiene alkylate, Vpropyiene alkylate- volumctric fractions of the butylcnc alkylate and the propylene alkylate in the alkylate product stream, respectively. The volumetric fractions ofthe butylene alkylate and the propylene alkylate are calculated from corresponding mass flow rates and the densities ofthe two components. The amount ofthe isobutane required in the reactions can be calculated using the formula given below:

W
J-.-, _ isobutane, reaction

- HfW

butylene isobutane A/fJJ/ ^ ' ^ butylene - ' - ' ' ' isobutane . , _.

propylene

( J

' - ^ second path / propylene

where Wisobutane, reaction- mass flow rate of the isobutane required in the alkylation reactions, MLB/D, MWisobutane- molccular weight of isobutane, g/mole. It should be noted that one mole of propylene that reacts in the second path consumes two moles of isobutane. Hence, one mole of propylene in the alkylation feed consumes (1+Xsecondpath) moles of isobutane.

131

The isobutane can not be completely separated from the normal butane in the deisobutanizer. Some isobutane enters the mixed butane product stream. The weight percentage of the unreacted isobutane in the total isobutane in both operation modes is obtained from the industrial data from the refinery considered in the work. These values are listed in Table 6.7. It can been seen from Table 6.7 that the difference between two modes is only 0.0003 wft.%. Hence, the average value is used for both operation modes in the model and it is assumed that the weight percentage does not change with the operating conditions ofthe alkylation unit. Table 6.7 Weight Percentage ofthe Unreacted Isobutane in the Alkylation Unit. Unreacted isobutane, wt.%) Summer Mode Winter Mode Difference Average 0.0211 0.0208 0.0003 0.0209

The total amount ofthe isobutane required by the alkylation unit is calculated using the formula given below: W
-J. " isobutane. total ~ ~, isobutane. reaction 7^ ' isobutane, unreacted ,-. Q , t^-Oj

where Wisobutane, total- total mass flow rate of isobutane required by the alkylation unit, MLB/D, Xisobutane,unreacted- weight fraction of the unrcacted isobutane in the total isobutane required by the alkylation unit. The volumetric flow rate ofthe isobutane is calculated from the mass flow rate and the density of isobutane. The amount ofthe isobutane purchased on the market is the

132

calculated as the difference between the total isobutane required by the alkylation unit and the available isobutane in the alkylation feed:

W
isobutane. purchased

=W
isobutane. total

-W
isobutane. feed ^

(6.9)
^ ^

where Wisobutane, purchased- mass flow rate of isobutauc purchased in the market, MLB/D, Wisobutane, feed- mass flow rate of isobutanc in the alkylation feed, MLB/D. The total amount ofthe mixed butane is the sum ofthe butane in the alkylation feed and the unreacted isobutane calculated using the following formula:

W
bulane.lolal

=W
normal butane

-^W.
isobutane .total

-X
isobutane .unreacted '

('6 10)
V /

where Wbutane, total" mass flow rate of mixed butane, MLB/D. The volumetric flow rate ofthe mixed butane is calculated from the mass flow rate and the density of butane. The amount ofthe propane formed in the second path of propylene can be calculated using the formula given below:

W
. propane. reaction propylene

-X
second path h/fJJf/
IVI rr p^QpyigfjQ

-MW
propane ' /"/: 1 1 \ V^*^^/

where Wpropane, reaction- mass flow rate of propauc formed in the alkylation unit, MLB/D, M Wpropane- molccular weight of propane, g/mole.

133

The total mass flow rate ofthe propane is the sum ofthe propane in the alkylation feed and the propane formed in the alkylation unit. The volumetric flow rate ofthe propane is calculated from the mass flow rate and the density of propane. 6.3 Diesel Hydrotreater The purpose ofthe diesel hydrotreater is to eliminate most ofthe sulfiir in the diesel to satisfy the diesel product specification. The diesel produced in the refinery considered in this work is composed of three diesel streams. These streams are the sidedraw diesel from the atmospheric tower in the cmde unit, the overhead diesel from the remn colunm in the cmde unit, the light cycle oil (LCO) from the main fractionator of the FCC unit. The mass flow rates and volumetric flow rates of these three streams have been calculated in the cmde unit model and FCC model, respectively. The diesel hydrotreater model calculates the hydrogen required and the quantities ofthe product streams. There are three product streams coming out ofthe diesel hydrotreater: diesel, naphtha, and sour gas. The diesel goes to the storage tank. The naphtha goes to the cmde unit and is combined with the light naphtha stream. The sour gas goes to Amine treater for further treatment. The average values ofthe industrial data from the refinery considered in this work shown in Table 6.8 and Table 6.9 are used in the model. It can been seen from Table 6.8 and Table 6.9 that the values for the summer mode and the winter mode are close, with the largest difference of 0.003 in weight ratios and 0.005 in volumetric ratios. Hence, the average values are used for both operation modes in the model. These ratios are constants and do not change with the operating conditions. Table 6.8 Weight Ratios ofthe Hydrogen and the Products in the Diesel Hydrotreater. Summer Mode Hydrogen/Charge Diesel/Charge Naphtha/Charge Sour Gas/Charge 0.018 0.970 0.024 0.025 Winter Mode 0.018 0.973 0.022 0.022 Difference 0.0 0.003 0.002 0.003 Average 0.018 0.971 0.023 0.024 ~"

134

Table 6.9 Volumetric Ratios ofthe Hydrogen and the Products in the Diesel Hydrofreater. Summer Mode Hydrogen/Charge Diesel/Charge Naphtha/Charge Sour Gas/Charge 0.027 0.978 0.030 0.018 Winter Mode 0.026 0.983 0.029 0.015 Difference 0.001 0.005 0.001 0.003 Average 0.027 ~ 0.981 0.030 0.016

Since the diesel hydrotreater has a capacity of 13,000 barrels charge per day, not all diesel streams go through the diesel hydrotreater. Part of diesel withdrawn from the atmospheric tower in the cmde unit directly goes to the storage tanks without the treatment. About 20 vol.% in the Winter Mode and 24 vol.% in the Summer Mode of diesel from the atmospheric tower do not go through the treatment in the diesel hydrotreater. These values are used as constants in the model directly. The refinery considered in this work produces two diesel products: low sulfur diesel fuel and No. 2 diesel fiiel. There is not a strict limit on the quantities of no. 2 diesel and low sulfur diesel. In the winter, the market demand for low sulfur diesel is high. Thus, maximum low sulftir diesel is produced while reaching the upper limit of diesel hydrotreater capacity. The rest ofthe diesel which is not processed by the diesel hydrotreater is sold as No. 2 diesel fuel. In the summer, however, the low sulfiir diesel demand is down and there is no need to reach the HDS limit to produce the maximum amount ofthe low sulfiir diesel. The low sulfur diesel is about 76 vol.%) ofthe entire diesel produced in the refinery. The rest ofthe diesel, whether processed by the diesel hydrotreater or not, is sold as No. 2 diesel fiiel. That portion of low sulfur diesel in the summer, 76 vol. %, is assumed as a constant in the model.

135

CHAPTER 7 GASOLINE BLENDING MODELING

7.1 Process Overview Gasoline is the primary product in a fuel-oriented refinery. In the refinery considered in this work, the volume ofthe gasoline is about half of the total volume of all products produced in the refinery. From the point of view of economics, about 60-70%) of a typical refinery's total revenue comes from the gasoline sale (Singh et al., 2000). Gasoline blending is the final step in making gasoline product. The gasoline blending operation often determines the operating conditions ofthe upperstream units. Due to the importance ofthe gasoline blending, a gasoline blending model must be included in the refinery-wide model. Gasoline blending is the process of blending several gasoline blending stocks that are produced in upperstream units or purchased from the market to make several grades of gasoline according to the specifications. The objective ofthe gasoline blending is to allocate the available gasoline blending components in such a way as to meet product demands and specifications at the least cost and to produce products which maximize the overall profit. Different gasoline blending stocks have different properties. Different grades of gasoline also have different specifications. The core of a gasoline blending model is the prediction of gasoline properties from the properties ofthe blending stocks. Table 7.1 lists the volumes and sources ofthe gasoline blending stocks in the typical Summer Mode operation. In Table 7.1, the first seven blending stocks are produced and blended in the refinery while the ethanol is off-site. The high solvability of the water in ethanol makes it inconvenient to blend ethanol in the refinery and transport the gasoline with ethanol in it. Water may enter the gasoline during the transportation. It can be seen from Table 7.1 that the refinery itself makes more than 97 vol.% percent of gasoline blending stocks. Therefore, adjusting the operating conditions of upstream units according to the gasoline blending is essential to make the refinery operation profitable.

136

Table 7.1 Volumes and Sources ofthe Gasoline Blending Stocks in Typical Summer Mode Operation. Gasoline blending stock FCC gasoline Low-severity reformate Alkylate Light straight-run gasoline High-severity reformate Butane Volume, BBL/D 10915 5934 4000 1783 1244 288 Vol. Vo 44.11349 23.98254 16.16619 7.206078 5.027685 1.163966 0.808309 1.531746 Source FCC unit Reformer Alkylation unit Cmde unit Reformer Gas plant and/or market purchase Toluene Ethanol 200 379 Market purchase Market purchase

The refinery makes three grades of regular gasoline: super unleaded (SNL), unleaded (NL), and sub. octane with ethanol. The super unleaded gasoline has an octane rating of 93 and the unleaded gasoline has an octane rating of 87. The sub. octane with ethanol gasoline has an octane rating of 84 inside the refinery and its octane rating is increased to 87 when ethanol is blended into the gasoline at the pump. The refinery does not make any reformulated gasoline (RFG) at present. The specifications of these three grades of gasoline are listed in Table 7.2. The octane number of a fuel is defined as the percentage of iso-octane (assigned an octane number of 100) in a blend with n-heptane (assigned an octane number of 0) that exhibits the same resistance to knocking as the test fuel under standard conditions in a standard engine (Palmer and Smith, 1985). Two standard test procedures are used to characterize the antiknock properties of fuels for spark engine: (I) the ASTM D908 test gives the research octane number (RON) and (2) the ASTM D357 gives the motor octane number (MON). The RON represents the antiknock properties under the condition of low

137

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speed and frequent accelerations while the MON represents the engine performance under more severe high speed conditions (Singh et al., 2000). In RON test, the engine runs at 600 r/min and with 125 F intake air temperatiire. In MON test, the engine mns at 900 r/min and with 300 F intake air temperatiire (McKetta, 1992). The arithmetic mean ofthe RON and MON, (R0N+M0N)/2, is called octane rating and is posted at gasoline stations. Both the octane rating and MON are used in the gasoline specification. Automobile engine performance is affected by gasoline volatility. A vapor pressure that is too high for the given ambient temperature will result in vapor locking and motor stalling, while a vapor pressure which is too low will lead to difficulties in engine start-up (Palmer and Smith, 1985). Reid vapor pressure (RVP) is widely used as a criterion to measure the volatility of gasoline. RVP test is defined by the American Society for Testing and Materials (ASTM) under the designation ASTM D323-56. The American Petroleum Institute (API) describes the RVP test procedure in detail, including the apparatus (API, 1955). The boiling range also affects the engine during start-up and driving, and is particularly important for good performance during quick acceleration and high speed operations (Singh et al., 2000). The 10, 50, and 90 vol.% distilled are used in the gasoline specifications. The 10 vol.% distilled affects the start-up and vapor blocking. The 50 vol.%) distilled affects the acceleration and smoothness. The 90 vol.% represents the completeness of gasoline combustion (Lin, 1988). ASTM D86 standard test is used to measure the 10, 50, and 90 vol.% distilled ofthe gasoline. The volatility of fuels is varied for seasonal climatic changes and conformance to U.S. EPA volatility regulations by providing six vapor pressure/distillation classes and six vapor lock protection classes for fuel (ASTM, 1997). The volatility of fuels is also varied for different geographical regions. According to the market locations ofthe refinery considered in this work, the volatility specifications of gasoline grades SI and S4 are applied for RVP and 10, 50, and 90 vol.% in the summer and the winter, respectively. It is to be noted that the upper limit of RVP ofthe gasoline sub. octane with ethanol is I psi higher than other two grades of gasoline. The additional 1 psi RVP is an incentive to

139

use the replaceable ethanol in the gasoline. The ethanol content in the gasoline sub. octane with ethanol is about 10. vol.%. The auto and oil industry accepts a driveability index (DI) based on the ASTM D86 distillation curve to protect against the performance problems related to volatility. It is suggested that the DI should not exceed 1,200 to assure satisfactory performance (Unzelman, 1996). The Driveability index is calculated using the following formula:

DI = I.5-Tj+3-T,+T,o,

(7.1)

where DI- driveability index, Tio, T50, T90- temperature at 10, 50, and 90 vol.%) distilled, respectively, F. The specification ofthe O2 wt.% is to control the oxygen content in the gasoline. The super unleaded gasoline and the unleaded gasoline are conventional gasoline. The gasoline sub. octane with ethanol is an oxygenated gasoline. The lower limit of oxygen wt. % for the oxygenated gasoline is defined in 1990 Amendment to the clear air act. The upper limit of O2 wt.% is set to control the Nox emission from the gasoline. It is noted that the upper limit of O2 wt.% for the super unleaded gasoline and the unleaded gasoline is lower than that of gasoline sub. octane with ethanol. The specific gravity specification is to control the density ofthe gasoline. The lower limit of specific gravity can prevent the gasoline from getting too light. A heavy gasoline usually yields better mileage than a lighter gasoline. In gasoline blending, the lower limit is mainly used to limit the content of alkylate, a light high-octane gasoline blending stock, in the super unleaded gasoline. However, a gasoline that is too heavy usually has low volatility, which may cause ignition problem. A upper limit of specific gravity is also set in the gasoline specifications. The sulfur specification is to limit the emission of SOx from the gasoline. SOx is harmful to the environment and considered to be responsible for acid rain. The upper limit of benzene wt. % in the gasoline specifications is to limit the emission of CO from >

140

the gasoline. Since the hydrogen/carbon ratio is low in benzene, gasoline with high content of benzene tends to have high emission of CO. The benzene content, O2 content, and sulfur content can be easily calculated by summing the corresponding contents in the gasoline blending stocks. The specific gravity ofthe gasoline can be easily calculated from the volume and the weight ofthe gasoline. It is assumed that there is no volume loss in gasoline blending. Hence, the volume of one grade of gasoline is the summation ofthe volumes of gasoline blending stocks blended into the gasoline. The weight ofthe gasoline is calculated by summing the weights of gasoline blending stocks blended into the gasoline. The calculations of octane number, RVP, and percent distilled are more complicated and will be described in detail in the following text. After the 10, 50, and 90%) distilled are calculated, the driveablity index can be calculated using equation 7.1. 7.2 Properties ofthe Gasoline Blending Stocks In order to calculate the properties ofthe gasoline blends, the properties ofthe gasoline blending stocks must be known. Some properties ofthe gasoline blending stocks are calculated in the unit models. Average industrial data are used for other properties. The properties ofthe blending stocks required by the gasoline blending model includes twelve items: volumetric flow rate, mass flow rate, MON, RON, saturates (paraffin+naphthene) vol.%), aromatics vol.%, olefins vol.%), RVP, ASTM D86 curve, benzene w^.%, sulfur wt.%, and O2 wt.%). There are all together eight blending stocks: light straight-run (LSR) gasoline, FCC gasoline, low-severity reformate, high-severity reformate, alkylate, butane, toluene, and ethanol. The eight blending stocks will be introduced in the following text.

7.2.1 Light Straight-Run (LSR) Gasoline Recall that in the cmde unit the overhead product of naphtha splitter becomes the LSR. The LSR flows direct from the crude unit to the gasoline storage tank for blending without going through any treatment in between. Therefore, the properties ofthe LSR can be calculated directly from the information ofthe portion ofthe cmde feed in the LSR 141

boiling range, which are listed in Table 7.3 and Table 7.4. The LSR consists the whole gasoline cut and part of light naphtha cut in the cmde feed. The rest of light naphtha cut becomes reformer feed. The portion of light naphtha cut entering the LSR is calculated using the formula given below:

Portion,,^, = 1 - Portion ^^j^,^^j^^,,, where PortiouLSR, In- volumetric fraction ofthe light naphtha in the LSR, Portionreformer feed. In" volumctric fraction of the light naphtha in the reformer feed. Recall that the Portionreformer feed, In is calculated in the reformer model. Table 7.3 Industrial Data of Cmde A and Cmde B. Property Item Unit Cmde A Gasoline C5-150F Yield API Gravity Aromatics Naphthenes+2x Aromatics RON MON Benzene Sulfiir None None wt.% wt.% 72.479 71.684 O.I 0.001 71.832 67.992 4.2 0.007 70.325 69.318 O.I 0.003 71.832 67.992 4.2 0.013 Vol.% API vol.% vol.% 2.5 88.687 0.223 6.447 Light naphtha 150-200F 2.5 67.69 1.515 37.93 CmdeB Gasoline C5-150F 3.1 91.041 1.151 5.705

(7.2)

Light naphtha I50-200F 1.9 73.961 8.556 40.037

142

Table 7.4 Indusfrial Data of Cmde C and Cmde D. Property Item Unit CmdeC Gasoline 68-155 F Light naphtha 155-265 F Yield API Gravity Paraffins Naphthenes Aromatics RON MON Aromatics Sulfiir Vol.% API vol.% vol.% vol.% None wt.% wt.% Wt. % 3.98 86.5 92.8 6.2 0.1 69.5 68.3 1.0 <.02 10.33 63.1 62.3 31.9 4.2
-

CmdeD Gasoline C5-150F Light naphtha 150-200 F 2.88 83.6 90.8 6.6 O.I 71.4 69.8 2.7 0.02 9.18 60.9 57.4 34.3 4.2
-

5.8 <.02

8.3 0.02

The volumetric flow rate and the mass flow rate ofthe LSR are calculated in the naphtha splitter part ofthe cmde unit model. The MON and RON ofthe LSR can be calculated using the formula given below:

2^/oVi

- \ygasoline,i

' ^gasoline,! "^ "^^^^^^LSR.In.i

' '^ln,i ' ^ln,i )

Y
~

_i
E ^ ^ / (^gasoline,i + Portion^^j,,,,, - V,, ) '

(7.3)

where i- cmde types of A, B, C, and D, Y - MON or RON, %Vi- volume percentage of crude type i in the total cmde, vol. %, Vgasoiine,i- volumc fraction ofthe gasoline cut in the cmde type i,

143

Vin,i- volume fraction ofthe light naphtha in the crude type i, Ygasoiine,i- MON Or RON of the gasoline cut in the cmde type i, Y|n,i- MON or RON ofthe light naphtha in the cmde type i. It can be seen from Table 7.4 that the MON and RON ofthe light naphtha cut in the cmde C and cmde D are not available in the industrial data. It was assumed that the MON and RON ofthe light naphtha cut in these two cmde types are the same as the MON and RON ofthe gasoline cut in the same cmde type, respectively. The saturates include paraffins and naphthenes. The volume percentages ofthe saturates in the gasoline cut and light naphtha cut ofthe cmde A and cmde B can be calculated by summing corresponding volume percentages ofthe paraffins and naphthenes. The volumetric percentage ofthe olefins in the gasoline cut and the light naphtha cut are set to zero based on industrial data. The volume percentages ofthe saturates, the aromatics, and the olefins in the LSR can be calculated from the volume percentage of these components in the gasoline cut and light naphtha cut of four cmde oils using the formula given below:

X ^ ^ '

(^gasoline.i " ^x.gasoline.i + Portion,^jj

- V,j -

V^j)

"^oX = ^

v^TTTT-rr^ ^T-TT 7^ Y^oV. (V^asoiinci + Portion,SR,, V,J

'

(7-4)

where i- cmde type A, B, C, and D, X - component type, saturates, aromatics and olefins, %X- volume percentage of component type X, saturates, aromatics and olefins, vol.%, Vx,gasoiine,i- volumc fraction ofthe molecule type X in the gasoline cut ofthe cmde type i, Vx,in,i- volume fraction ofthe molecule type X in the light naphtha ofthe cmde type i. The benzene content and the sulfur content in the LSR can also be calculated from the corresponding contents of gasoline cut and light naphtha cut of four cmde oils using the formula given below:

144

Y:/ow,
%Z = -

*^gasoline.! ''^"^gasoline.i

'" Z.gasoline.i ''^

"0rtl0n[^n,^j

V^SPG,rW.. ^ - ^ '^^-^
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where i- cmde types of A, B, C, and D, Z - benzene or sulfur, %)Wi- weight percentage of cmde type i in the total crude, wt. %, % Z - benzene content or sulfur content, wt.%, Wz,gasoiine,i- weight fraction ofthe benzene or sulfiir in the gasoline cut ofthe cmde type i, Wz,in,i- volume fraction ofthe benzene or sulfiir in the light naphtha ofthe cmde type i. The RVP, and the O2 wt.% in the LSR are assumed to be constants in the model. They are set at the average industrial data. According to the operation personnel in the refinery considered in this work, the ASTM D86 curves of gasoline blending stocks change little during the operation. Hence, the average industrial values are also used for the ASTM D86 curve ofthe light naphtha. These constants are listed in Table 7.5. 7.2.2 Other Gasoline Blending Stocks The mass flow rate, MON, and RON ofthe FCC gasoline are calculated in the FCC model introduced in the Chapter 4 of this dissertation. However, the FCC model does not predict the volumetric flow rate ofthe FCC gasoline. The API gravity ofthe FCC gasoline is assumed to be a constant and is set at the average API gravity ofthe FCC gasoline in the industrial data. The FCC model can not predict the volumetric percentages ofthe chemical components in the FCC gasoline, either. The industrial average values are used for the volumetric percentages ofthe saturates, the aromatics, and the olefins in the FCC gasoline. The RVP, ASTM D86 curve, benzene wt.%, the sulftir wt.%, and the O2

145

wt.% in the FCC gasoline also can not be predicted from the FCC model. Their values are set at the average industrial data. For both the low-severity operation and high-severity operation ofthe reformer, the detailed reformer model provides the volumetric flow rate and the mass flow rate of the reformate. The reformer model also provides the contents ofthe saturates, the aromatics, and the olefins in the reformate. In addition, the model provides the benzene content in the reformate. The RVP, ASTM D86 curve, sulfur wt.%), and the O2 wt.% in the reformate can not be predicted from the refomate model. Their values are set at the average industrial values. The alkylation model provides the volumetric flow rate, mass flow rate, MON and RON ofthe alkylate. Other properties are not calculated in the model and they are set as the average industrial values. The volumetric flow rate and the mass flow rate ofthe butane are calculated in the gas plant model. Other properties ofthe butane are obtained from literature (Edmister and Lee, 1984; Gary and Handwerk, 1984) and from industrial data. While all the gasoline blending stocks introduced above are produced inside the refinery, the toluene and the ethanol are only purchased from the market. The refinery also purchases some butane from the market in the winter. The butane purchased is assumed to have the same properties ofthe butane produced in the refinery. The volumetric flow rate and mass flow rate ofthe toluene and the ethanol are assumed to be at the upper limit ofthe purchase at the beginning ofthe calculations. The real amount of the toluene and the ethanol used are calculated in the gasoline blending model. Other properties ofthe toluene and ethanol are obtained from literature (Edmister and Lee, 1984; Unzelman, 1996) and from industrial data.

146

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147

All these industrial data and literature data for the properties ofthe gasoline blending stocks mentioned above are listed in Table 7.5. After all the properties ofthe gasoline blending stocks are known, they are used as inputs to the gasoline blending model.

7.3 Gasoline Blending Model 7.3.1 Octane Model The Octane Model is to calculate the MON and RON of three grades of gasoline from the MONs and RONs ofthe gasoline blending stocks. It is well known that the octane blending is not linear. In other words, the octane number ofthe gasoline is not equal to the volumetric average ofthe octane numbers ofthe blending stocks. One way to account for the nonlinearity is using interaction parameters. Morris et al. (1975) proposed an equation for binary blending as below:

a = Xjaj +x^a,+b,2X,X2,

(7.6)

where a- RON or MON of a blend, ai, a2- RON or MON ofthe blending component 1 and 2, respectively, bi2- binary interaction parameter between component 1 and 2, xi, X2- the volume fractions ofthe blending component 1 and 2, respectively. The disadvantage of Morris' approach is that the interaction parameter between each pair of gasoline cut has to be known for the blending. These interaction parameters can only be obtained from the regression of industrial blending data. For example, in the refinery considered in this work, blending of seven stocks needs twenty-one binary parameters for MON and RON calculation each. Twu and Coon (1996) proposed a method which only needs three interaction parameters for RON and MON each for blending any number of gasoline blending stocks. Twu and Coon's approach uses the concept of interaction parameter and also the compositions of gasoline cuts. It was

148

claimed that the correlation describes blending behavior accurately throughout the entire composition and it works not only for binaries, but also for multicomponent systems (Twu and Coon, 1996). The average absolute deviation ofthe model predictions is 1.00% for RON and 1.19% for MON in a gasoline blending test on a total of 161 blends from 157 gasoline cuts (Twu and Coon, 1996). Because of its simplicity and accuracy, the approach of Twu and Coon (1996) has been used in this work. In Twu and Coon's method, each gasoline blending stock consists three components: aromatics, olefins, and saturates. The saturates include paraffins and naphthenes. The approach uses several assumptions stated below: Each ofthe three components in a blending stock has the same octane number as the blending stock. For example, if the RON ofthe FCC gasoline is 87, then the RONs of the olefins, the aromatics and the saturates in the FCC gasoline are all assumed to be 87. a. The values ofthe interaction parameters between components inside the same gasoline blending stock are zero. b. If i and j are both the same hydrocarbon type (e.g., aromatics in cut A and aromatics in cut B), the binary interaction parameter between i and j is assumed to be zero. c. Gasoline blending is symmetric blending. That is, the binary interaction parameters between two gasoline components i and j , kij and kji, have the same value. d. The binary interaction parameters in the pairs with same components are the same. For example, the binary interaction parameter between aromatics in cut A and olefins in cut B is equal to that between the olefins in cut A and the aromatics in cut B. The total number ofthe binary interaction parameters for blending two 3component gasoline cuts is only three (i.e., binary interaction parameters between aromatics A and olefins in B, aromatics in A and saturates in B, olefins in A and saturates in B). The binary interaction parameters between components are derived from regressing blending data of gasoline blending stocks. The universal set of binary interaction parameters between components were given by Twu and Coon (1996). They were obtained from the regression of 161 blends from 157 gasoline cuts. The values of the universal set of binary interaction parameters are listed in Table 7.6. Subscripts O, A,

149

and S represent olefins, aromatics and saturates, respectively. For example, KQA represents the binary interaction parameters between olefins and aromatics. Table 7.6 Universal Set ofthe Binary Interaction Parameter between Components. Interaction Parameter Twn and Coon RON
KQA KQS

Model Regression MON 0.0354 -0.0800 0.0271 RON -0.00274 -0.1439 0.1841 MON 0.07014 -0.1385 0.1066

0.0670 -0.1021 -0.0232

K-AS

The binary interaction parameters between two gasoline blending stocks can be calculated from the binary interaction parameters between components in these two gasoline blending stocks. Assume that gasoline blending stock X is a mixture of three components with compositions xi, X2, and X3, and the gasoline blending stock Y is a mixture ofthe same three components with compositions yi, y2, and y^. For two threecomponent gasoline blending stocks, the binary interaction parameter between gasoline blending stocks X and Y is calculated using the following formula:

YJl(^>yj+^jy'^
K^ -1
I J

-^(^i+^j)

(1-k,)
(7.7)

(a^+aj)

where ai- RON or MON ofthe component i, kij- binary interaction parameter between the component i and j , KxY- binary interaction parameter between the gasoline blending stocks X and Y, Xi, yi- volume fraction ofthe component i in gasoline blending stocks X and Y, respectively.

150

After generating the binary interaction parameters between gasoline blending stocks, the octane numbers ofthe a gasoline blend with several gasoline blending stocks are calculated using the formula given below:

where Zi,Zj- volume fractions of gasoline blending stocks i and j , respectively, a- RON or MON ofthe gasoline, aij- the blending parameter. The aij is calculated using the formula below:

ci,j=^(a,+aj)(l-k,j),

(7.9)

where ai, aj- RON or MON ofthe gasoline blending stocks i and j , respectively, kij- binary interaction parameter between the gasoline blending stocks i and j . Ethanol is very different from the other gasoline blending stocks. The ethanol does not belong to any ofthe three molecule types of saturates, aromatics, and olefins. Hence, the ethanol is treated different from the other seven gasoline blending stocks in the octane model. Instead of using the real octane numbers ofthe ethanol, the blending octane numbers are used for the ethanol. The ethanol only exists in the gasoline grade of sub. octane with ethanol. The ethanol in this grade is fixed at IO.vol% according to practice in the refinery considered in this work. After obtaining the octane number ofthe gasoline blend of other seven blending stocks, the final octane number ofthe sub. octane with ethanol gasoline is calculated as the volume average ofthe blending octane number ofthe ethanol and the octane number ofthe gasoline blends of other seven gasoline blending stocks. 151

In order for the octane model to match the blending in the refinery considered in this work, the three interaction parameters for RON and the three interaction parameters for MON are regressed using the industrial blending data. The industrial blending data used in the regression include 11 super unleaded blends, 67 unleaded blends, and 17 sub. octane with ethanol blends. The properties of gasoline blending stocks in each blend are unknown. Therefore, the average properties ofthe industrial data are used for the gasoline blending stocks in each blend. These blends include both the blends in the summer and in the winter. The regression is an optimization problem. A least square error type fimction is used as the objective function for the optimization problem given below:

^W

parameterization ~ 2^^

^model.i ~ ^base.i ) ' ^base.i I '

(' ' ^ j

where Objfparamterization- objcctivc fiinction of the octane model parameterization, Omodei.i- MON or RON predicted by the octane model, Obase,i- MON or RON in the industrial data. NPSOL optimization package (Gill et al., 1986) was used in the parameterization. The average relative difference between industrial data and model prediction is 0.67% for RON and it is 0.72% for MON. The maximum relative difference is 2.3% for RON and it is 2.7% for MON. Considering the use of average properties for gasoline blending stocks in each blend and different blends in the regression, the gasoline blending correlations predict MON and RON accurately using only three interaction parameters each. The interaction parameters obtained in the regression are listed in Table 7.6.

7.3.2 RVP Blending Model Reid vapor pressure (RVP) is widely used as a criterion to measure the volatility of gasoline. Theoretical approaches (Stewart, 1959; Vazquez-Esparragoza et al., 1992)

152

use pseudo-components to represent the gasoline blending stocks. Empirical correlations are used in the theoretical approaches to calculate the properties of pseudo-components, which deteriorate the accuracy ofthe theoretical approaches. In addition, the computations required in the theoretical methods are complex in comparison to those required in other approaches (Singh et al., 2000). Chevron's vapor pressure blending indices (VPBI) method uses empirical correlations. VPBI method has a simple form and has been proved to have reasonable accuracy (Gary and Handwerk, 1984). It has been widely used in industry (Singh et al., 2000). In the present work. VPBI method is used in the RVP calculation. The VPBI method converts the RVP of each gasoline blending stock to the VPBI. The VPBI ofthe gasoline blend is calculated as the volumetric average ofthe VPBIs of all the gasoline blending stocks. The RVP ofthe gasoline blend is obtained by converting the calculated VPBI ofthe gasoline blend to RVP. The relation between the VPBI and the RVP of a gasoline cut is given below:

VPBI = RVP"\ where VPBI- vapor pressure blending index, RVP- Reid vapor pressure. Equation 7.11 can be modified to calculate RVP from VPBI.

(7.11)

153

Start Boiling points of butane, toluene, and ethanol ASTM D86 curves of mixed blending stocks Calculate the volume distilled for the mixed blending stocks using Cubic Spline method Calculate the total volume distilled from the mixed blend stocks

Initial Guesses ofthe T

Calculate the new temperature using the Secant method Add the volume of pure component i to the total volume distilled, i=i+l

J^Q_

Figure 7.1 Flowchart for the Calculation ofthe Tio/, T5o/o, T9oo/ of Gasoline Blends.

154

7.3.3 Percent Distilled Model The percent distilled model is to calculate the temperatures at 10%), 30%) and 90% distilled ofthe gasoline based on the ASTM D86 curves ofthe gasoline blending stocks. It is assumed that the gasoline is an ideal mixture in this work. The temperatures at 10%, 30% and 90%o distilled are represented by Tio%, or T5o%, or T9o%, respectively. The flow chart for the above iterative procedure is shown in Figure 7.1. The calculation of Tio%, or T5o%, or Tgoo/, follows the steps given below: a. Make an initial guess of Tio%, or T5o%, or T9oo/. Use the estimated value and the ASTM D86 curves ofthe mixed blending stocks to calculate the volume percentages ofthe mixed blending stocks distilled. Nine intermediate points are used to represent each ASTM D86 curve. Cubic spline method (Riggs, 1994) is used to interpolate between the known points on the ASTM D86 curves. b. Calculate the total volume distilled by summing the volume distilled of each mixed blending stocks. c. Compare the temperature with the boiling points of three pure blending components: butane, toluene, and ethanol. If the temperature is higher than one ofthe boiling points, the corresponding component is assumed completely distilled. Then the volume of this component is added to the total volume distilled. Repeat the procedure until all three boiling points have been compared with. d. Calculate the volume percentage that is vaporized. Compare the volume percentage with 10 vol.%, 50 vol.%, or 90 vol.%). If they do not match, calculate the new temperature using Secant method (Riggs, 1994) and return to step a.

155

CHAPTER 8 REFINERY-WIDE OPTIMIZATION In the previous chapters, the single-unit models in the overall refinery-wide model and the feed characterizations that connect the single-unit models are presented. Till now, the overall refinery-wide model has been built. This chapter discusses the optimization analysis that was conducted on this refinery-wide model.

8.1 Formulation ofthe Optimization Problem 8.1.1 Formulation of the Obj ective Function Although optimization can be stated in many different ways, the common optimization to an industrial process is to maximize the profitability ofthe process. In this work, the whole refinery is considered to be one process. This process uses the given cmde slate to produce various petroleum products to achieve economic objectives. The objective of optimization in hand is to reach the maximal profitability given the cmde slate and refining facilities. No major hardware change in the current facilities is considered in the optimization. The optimization tries to find the optimal operating conditions that maximize the overall profit ofthe whole refinery while observing all the process constraints. In the objective fimction, only the feed cost, operating cost and revenue from product sales are taken into account. The fixed costs, such as the capital cost and salaries, are excluded from the objective fimction, since we can not influence these costs by optimizing the operating variables. The feed cost includes the cost of cmde oil feeds and the cost of other chemicals purchased from the market. Four types of cmde oils are used in the refinery. These four types of crude oils have been discussed in Chapter 3. It is assumed that each type of crude oil has a fixed fraction for each operation mode. The compositions ofthe cmde feed are shown in Table 3.1 of Chapter 3. The composition ofthe cmde oil for each operation mode is fixed. Hence, a single cmde price is calculated from the prices of four

156

types of crude oils and this single crude price is used as constant in each operation mode. The chemicals purchased from the market and their usage are listed in Table 8.1.

Table 8.1 Chemicals Purchased by the Refinery Considered in This Work. Chemicals Butane Isobutane Toluene Ethanol Usage Gasoline blending stock Alkylation feed Gasoline blending stock Gasoline blending stock

The operating cost includes the costs in four categories: catalyst and additives, natural gas, power, and cooling water. To calculate the exact usage of each category in every unit in the refinery requires very detailed models for each unit, which is not in the scope ofthe present work. Hence, all four categories are combined into one category called utility. Since the operating costs are much smaller compared to other items in the objective function, this simplification has an insignificant effect on the optimization results. The utility cost is calculated based on the data in the linear programming (LP) reports obtained from the refinery considered in this work. The utility costs are calculated using the formula given below:

Utility i = ^ Utility i^Lp,

^i,LP

(8.1)

where Utilityi- utility cost for unit i, UtilityiLP- utility cost for unit i from LP report, Vi- throughput of unit i, Vi^Lp- throughput of unit i from LP report.

157

The income from the product sale includes the sales of all products produced in the refinery. These products are listed in Table 8.2. Table 8.2 Price Stmcture ofthe Refinery-Wide Optimization. Name Cmde Butane (purchase) Isobutane Toluene Ethanol Propane C3 product Butane (sale) Light Naphtha Gasoline, Sub. Octane with ethanol, rack Gasoline, Sub. Octane with ethanol, spot Gasoline, unleaded, rack Gasoline, unleaded, spot Gasoline, super unleaded, rack Gasoline, super unleaded. spot Jet Fuel A Jet Fuel 5 Low sulftir diesel No. 2 diesel No. 6 fuel oil Summer Mode 13.97 12.38 12.65 24.92 43.75 10.47 13.02 9.16 13.93 20.07 19.65 18.62 18.2 20.98 19.72 17.32 17.44 17.21 16.35 9.22 Winter Mode 14.54 14.55 11.33 23.47 43.29 11.85 13.96 11.33 14.60 18.90 18.48 17.17 16.75 18.30 17.04 17.01 17.28 16.65 16.04 13.2

158

The objective function has the formula given below:

objf = Y Vproduct I Ppruduct^

i

- 2_, VcrudCj - PcrudCj

J

- 2 J Vchemical/^ - Pchemical,^
k

- Utility - reformer regeneration cost (8.2)

where Vproducti, VcmdCj, Vchemicalk- volumetric flow rate of product i, cmde type j , and chemical k, respectively, BBL/Day, Pproducti, Pcmdcj, Pchemicalk- price of product i, cmde type j , and chemical k, respectively, $/BBL, Utility- utility cost, $/Day, Reformer regeneration cost- regeneration cost of reformer catalyst, $/Day, It is clear that the objective function will be computed as $/day. 8.1.2 Objective Function Evaluation Each objective function evaluation needs one execution ofthe re finery-wide model to calculate the volumetric flow rates ofthe products. The utility cost and reformer regeneration cost can only be evaluated through the execution ofthe refinery-wide model. The refinery-wide model essentially is a straight-through model. The sequence of model executions follows the material flow in the refinery. During the refinery-wide model execution, the cmde unit model is solved first. After that, the FCC model is solved. Then the reformer model is solved twice, one execution for the low severity 159

mode, the other execution for the high severity mode. The FCC model and the reformer model can be solved simultaneously. The gas plant are executed after the executions of the FCC model and the reformer model because the light gas products from the FCC unit and reformer becomes the feed to the gas plant. The alkylation unit is then executed after the execution ofthe gas plant model. Last, the gasoline blending model is executed. The execution sequence ofthe refinery-wide model is shown in Figure 8.1. Although there are recycle streams inside the single unit models, such as the hydrogen recycle in the reformer unit, there is no recycle stream among the major processing units in the refinery-wide model. In the refinery considered in this work, there are only a few streams flowing in the direction opposite the execution sequence. However, these recycle streams only have small quantities and are considered to have an insignificant effect on the accuracy ofthe refinery-wide model.

8.1.3 Price Structure The operation ofthe refinery considered in this work varies with seasons. This is also tme for most of refineries in U.S. The operation changes are necessary to cope with the market demands and price changes with respect to seasons. The price stmcture is greatly affected by the market demand. For example, the gasoline has a higher price in the summer when a lot of gasoline is consumed by travelers. The diesel has a higher price in the winter because the demand of heating oil is high and diesel can be used to make the heating oil. The two major operation modes are Summer Mode and Winter Mode. Each operation mode has its own price stmcture. The prices ofthe cmde oil, chemicals, and products for two operation modes are listed in Table 8.2. It can be observed from Table 8.2 that the price gap between the gasoline and the diesel is large in the summer while the same is small in the winter. This difference has great effect on refinery operation. Since the price stmcture directly affects the value ofthe objective function of refinery-wide optimization, optimization study is conducted for each mode separately.

160

Optimizer

Decision Variables 1r Refinery-wide Model Interface Crude Unit Decision Variables LSR Crude U n i t Model Crude Assays, Crude Makeup Gasoline Blending Decision Variables Reformer Decision Variables

FCC unit Decision Variables

''

"
Reformer M o d e l ( L o w Severity, H i g h Severity)

FCC M o d e l

Lit3ht Gas

''

''

Light Gas

Gas Plant Model

FCC Gasoline

Butane

''
A l k y l a t i o n Unit Model

Low Reformate, High Reformate

Alkylate

'
1 Gasoline Blending Model

Figure 8.1 Flowchart ofthe Execution ofthe Refinery-Wide Model.

161

8.1.4 Decision Variables In this study, the decision variables are those variables whose values have significant effect on the overall economics ofthe fuel-oriented refinery. These variables are normally the handles that an operator can adjust to change the operation ofthe refinery. For the point of view of modeling, the decision variables are the inputs to the model whose optimal values are sought by the optimization algorithm. The number ofthe decision variables is equal to the number of freedom degrees ofthe model used in the optimization study. The decision variables for the refinery-wide optimization are the collection ofthe decision variables of each unit in the refinery. Based on the characteristics ofthe decision variables, the decision variables can be divided into two groups: the decision variables ofthe processing units and the decision variables ofthe gasoline blending. The decision variables ofthe processing units include those process Vciriables, such as cut points, temperatures, recycle ratios, etc. The gasoline blending is different from other units ofthe refinery in the sense that it is only a mixing process. There is no chemical reaction or separation involved in the gasoline blending. The decision variables for the gasoline blending are the fractions of each gasoline blending stocks blended into three grades of gasoline products. Among the seven blending stocks in the gasoline blending, five geisoline blending stocks, FCC gasoline. Low severity reformate, high severity reformate, alkylate. Light straight-run (LSR) gasoline, come from the processing units inside the refinery. In other words, there is no purchase for these blending stocks from outside resources. Hence, the sum ofthe fractions of each gasoline blending stock in three grades of gasoline is equal to unity. In order to eliminate this equality constraint, only two fractions, instead of three, for each blending stocks among these five blending stocks are used as the decision variables for the refinery-wide optimization. The two fractions for each blending stock are the fractions ofthe blending stock in the Super Unleaded Gasoline and Unleaded Gasoline. The fraction ofthe blending stock in the Sub. Octane Gasoline, which now becomes a dependent variable, is calculated using the formula given below:

162

^Sub.0ct.i

'

^ Super Unleaded.!

-^Unleaded.!'

\^-^)

where Xsuper unieaded.i, Xunieaded.i, Xsub.Oct.i- fractions of blending stock i in Supct Unleaded, Unleaded, and Sub. Octane Gasoline, respectively. The refinery usually purchases some butane from outside resources in the winter and sells some butane on the spot market in the summer. This is because of different evaporation specifications for gasoline in different seasons. Gasoline in the winter has a higher RVP upper limit so that the refinery can purchase butane and blend it into the gasoline. Since butane has a lower market price than gasoline, it is beneficial to blend as much as butane into the gasoline. The refinery sells part of butane produced inside the refinery because the RVP upper limit is low and the amount of butane used in the gasoline blending is low. It is assumed initially that the total amount of butane used in the blending in the summer is equal to what is produced within the refinery. It is assumed initially that the total amount of butane used in the blending in the winter is equal to the sum ofthe butane produced plus five thousand barrels per day purchase of butane. The five thousand barrels per day purchase of butane is the maximum amount of butane that refinery usually purchases from outside resources. In both modes, the tme amount of butane used in the gasoline blending may not be equal to amount assumed initially. The assumed amount is used as the base to calculate the amount of butane in barrel per day used in three grades of gasoline from the fractions, which are the decision variables for the refinery-wide optimization. Since the total amount of butane used in the gasoline blending is unknown beforehand in the refinery-wide model, the sum ofthe fractions of butane in three grades of gasoline is not necessarily to be unity. Hence, three fractions must be used for butane. The toluene used in the blending comes only from outside resources since the refinery does not produce toluene. The maximum amount of toluene used in the blending is set at 200 barrels as per the operation department in the refinery. The 200 barrels per day is used to calculate the amount of toluene in barrel per day from the fractions in the

163

decision variable set. Three fractions for toluene are also used since the real amount of toluene used in the blending is unknown beforehand. One special decision variable in the gasoline blending is the fraction of Light Straight-run (LSR) gasoline for sale. The refinery considered in this work sells part of LSR on the spot market. LSR can be either sold or blended into the gasoline. The decision variables and their lower and upper bounds are listed in Table 8.3. The lower and upper bounds ofthe decision variables came from the normal operating range used in the refinery considered in this work. The engineers from the refinery have agreed upon the values of these lower and upper bounds.

Table 8.3 Decision Variables of Refinery-Wide Optimization. Decision variable No. Decision variable name Feed to cmde unit Atmospheric Tower furnace outlet temperature, F 3 4 5 6 7 FCC Unit: 8 9 Light naphtha ASTM 95% point, F Heavy naphtha ASTM 95% point, F Jet Fuel ASTM 95% point, F Diesel ASTM 95% point, F Heavy Vacuum Gas Oil TBP end point, F Regenerator temperature, F Reactor temperature, F Lower Bound
35,000

Upper Bound
50,000

Cmde Unit: 1 2

650 230 360 460 620 950

1,250 980.00 0.01 900.00 5.00

665 260 385 525 670

1,100 1,340 1,005 0.02 980.00 7.50

10 02% in the flue gas, mol% Reformer: 11 First bed inlet temperature, K, low severity 12 H2/Hydrocarbon recycle ratio, mol H2/mol Hydrocarbon, low severity 13 First bed inlet temperature, K, high severity

900.0

980.0

164

Table 8.3 Continued. Decision variable Reformer: No. Decision variable name 14 H2/Hydrocarbon recycle ratio, mol Hi/mol Hydrocarbon, high severity 15 Low severity operation time/total operation time Blending: Super Unleaded 18 Fraction of alkylate in Super Unleaded 19 Fraction of LSR in Super Unleaded 0.0 0.0 1.0 1.0 1.0 1.0 I.O I.O 1.0 I.O 1.0 I.O I.O 1.0 1.0 1.0 1.0 16 Fractionof FCC gasoline in Super Unleaded 0.0 17 Fraction of low reformate in Super Unleaded 0.0 1.0 1.0 0.1 0.80 Lower Bound 5.0 Upper Bound 7.5

20 Fraction of high reformate in Super Unleaded 0.0 21 Fraction of butane in Super Unleaded 22 Fraction of toluene in Super Unleaded Unleaded 23 Fraction of FCC gasoline in Unleaded 24 Fraction of low reformate in Unleaded 25 Fraction of alkylate in Unleaded 26 Fraction of LSR in Unleaded 27 Fraction of high reformate in Unleaded 28 Fraction of butane in Unleaded 29 Fractionof toluene in Unleaded Sub. Oct. 30 Fraction of butane in Sub. Oct. 31 Fraction of Toluene in Sub. Oct. Light Naphtha: 32 Fraction of Light naphtha sold directly 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0

165

8.1.5 Constraints There are many constraints in the operation of a fuel-oriented refinery. The optimization problem in this study includes 63 nonlinear constraints and 7 linear constraints. In this study, the nonlinear constraints are not expressed explicitly. Instead, all the nonlinear constraints are evaluated using the nonlinear refinery-wide model. These constraints can be divided into several categories: capacity limits, process variable constraints, and product specifications. A capacity limit is the maximum throughput of a unit. The capacity limits ofthe refinery-wide optimization were obtained from the Linear Programming (LP) reports obtained from the refinery considered in this work. Process variable constraints are the maximum or minimum value of a process variable. If the value of a process variable is outside the interval defined by its maximum and minimum values, violation of safety regulation or damage to the facility may happen. For instance, a temperature can not surpass the metallurgical limit ofthe contacting materials. The product specifications in this study are mainly the specifications for the three grades of gasoline products: Super Unleaded Gasoline, Unleaded Gasoline, and Sub. Octane Gasoline with Ethanol. The gasoline specifications from Designation D4814-96 of ASTM standards are used in this study. It includes eleven specifications for each grade of gasoline. It should be noted that there are different product specifications for gasoline vaporization in different seasons. The nonlinear constraints are listed in Table 8.4. Engineers in the refinery considered in this work have agreed upon the values ofthe upper limits and the lower limits of these nonlinear constraints.

166

Table 8.4 Nonlinear Constraints of Refinery-wide Optimization. Nonlinear Constraint No . Constraint name Summer Mode Winter Mode

Lower Bound Crude Unit: I 2 Diesel flow rate in Atmospheric tower Reduced cmde to vacuum 4,000 tower 3 Gasoline splitter bottom flow rate 4 5 6 7 Crude debutanizer Rose unit capacity Rerun unit capacity Naphtha hydrotreater capacity 8 Jet fuel tank capacity 0 0 0 0 0 0 0

Upper Bound 12,000

Lower Bound 0

Upper Bound 12,000

23,000

4000

23,000

1,000

1,000

10,000 6,500 5,000 10,000

0 0 0 0

10,000 6,500 5,000 10,000

5,800

5,800

FCC Unit:

Heater outlet temperature, 500

op

700

500

700

10

Fuel flow to furnace. SCM

39.5

39.5

11 Reactor pressure, psig 12 Regenerator pressure, psig 13 Actual speed of lift air blower (sa), RPM

14.7 14.7

30 30

14.7 14.7

30 30

5,100

6,100

5,100

6,100

167

Table 8.4 Continued. Nonlinear Constraint No. Constraint name Summer Mode Winter Mode

Lower Bound 14 Difference between lift-aii0 blower inlet suction flow and surge flow, ICFM 15 Regenerator reactor pressure difference (P6P4), psia 16 Level of catalyst in the standpipe. foot 17 Combustion air blower inlet suction flow, SCFM 18 Wet gas compressor inlet 0 suction flow, Ibmol/s 19 Combustion air blower flow rate (Ib/s) 20 FCCU charge 21 Reformer Charge 22 Research Octane of Low reformate 23 Research Octane of High 98.5 reformate Other 24 Distillate HDS 0 0 0 0 6,000 94 30 35,000 0 -5

Upper Bound Infinite

Lower Bound 0

Upper Bound Infinite

-5

20

20

42,000 0.67 65

35,000 0 30

42,000 0.67

65

20,000 10,000 96.5

20,000

6,000 94

10,000 96.5

100.5

98.5

100.5

14,500 8,000 4,000

0 0 0

14,500 8,000 4,000

constraints: 25 Alkylation unit charge 26 Alkylate product

168

Table 8.4 Continued.

Nonlinear Constraint No. Constraint name Summer Mode Winter Mode

Lower Bound 27 Blending: Super Unleaded Gasoline 28 29 C3 splitter MON (R+M)/2 0 83 93.1 6.4 0.72 0 0 0 170 0 0 0 82.1 87.1 6.4 0.72 0 0 0 170 0 0

Upper Bound 15,000 Infinite 94 7.8 0.784 O.I 1250 158 250 374 4 4.9 84 88.1 7.8 0.784 0.1 1250 158 250 374 4

Lower Bound 0 83 93.1 6.4 0.72 0 0 0 170 0 0 0 82.1 87.1 6.4 0.72 0 0 0 170 0 0

Upper Bound 15,000 infinite 94 12.5 0.784 O.I 1200 131 235 365 4 4.9 84 88.1 12.5 0.784 O.I 1200 131 235 365 4

30 RVP 31 32 33 Specific gravity SulftuDrivability index

34 10%) vaporized 35 50%) vaporized 36 90% vaporized 37 02 wt.% 38 Benzene, vft.Vo Unleaded Gasoline 39 MON 40 (R+M)/2 41 RVP 42 Specific gravity 43 Sulftir 44 Drivability index 45 10% vaporized 46 50%o vaporized 47 90% vaporized 48 02 wt.%

169

Table 8.4 Continued. Nonlinear Constraint No. Constraint name Summer Mode Winter Mode

Lower Bound 49 Benzene, wt.% Sub. Oct. 50 MON 0 82.1 87.1 6.4 0.72 0 0 0 170 0 3.7 0 3300 16000 3700

Upper Bound 4.9 84 88 8.8 0.784 0.1 1250 158 250 374 4 4.9 3300 16000 3700

Lower Bound 0 82.1 87.1 6.4 0.72 0 0 0 170 0 3.7 0 3300 16000 3700

Upper Bound 4.9 84 88 13.5 0.784 0.1 1200 131 235 365 4 4.9 3300 16000 3700

with ethanol 51 (R+M)/2 52 RVP 53 Specific gravity 54 Sulfiir 55 Drivability index 56 10%) vaporized 57 50% vaporized 58 90% vaporized 59 02 wt.% 60 Benzene, wt.% Gas Contract 61 Super Unleaded Rack 62 Unleaded Rack 63 Sub. Oct. with Ethanol

Linear constraints are only for the fractions ofthe gasoline blending stocks in the three grades of gasoline blending. They have a common formula given below:

l>Y^j,>0,

(8.4)

where j - Gasoline blending stocks.

170

i- grades of gasoline, Xji- fraction of gasoline blending stock j in the gasoline of grade i. Since there are seven gasoline blending stocks, there are seven linear constraints. It should be noted that for the linear constraints corresponding to those five blending stocks only produced inside the refinery, only two fractions are used in each linear constraint.

8.1.6 Optimization Algorithm Each objective fimction evaluation requires solving the refinery-wide model once. Solving the refinery-wide model is time consuming since the refinery-wide model is fairly large. Therefore, it is necessary to find an optimization algorithm that has fast convergence that requires less objective function evaluations. It is reported that successive quadratic programming (SQP) converges fast and it may be the best method in solving nonlinear problem (Edgar and Himmelblau, 1988). A software package using SQP algorithm, known commercially as NPSOL was used as the optimization engine. The documentation of NPSOL software was given by Gill et al. (1986). From a random starting point, NPSOL can not guarantee the convergence to the global optimum, nor does any other software package. The best that the NPSOL can do is to converge to a point that satisfies the first-order Kuhn-Tuck conditions, which is the necessary conditions for a local minimum. To increase the possibility of finding the global optimum, several random starting points are used for each case discussed below. The solution with the best value ofthe objective function is regarded as the global optimum and is used in the following analysis.

8.2 Optimization Case Studies 8.2.1 Base Case In the refinery considered in this work, unit operations follow the schedule determined by the linear programming (LP). However, the decision variables used by LP are not exactly the same as those used in nonlinear optimization studies. It is necessary to

171

know the normal operating values ofthe decision variables used in optimization studies in order for fair comparison. The normal values of some decision variables are obtained from normal operating conditions in the refinery. The normal values ofthe rest ofthe decision variables are found by trial and error to make the model prediction consistent with the product information in the LP reports. The complete sets ofthe normal values ofthe decision variables for both modes are listed in Table 8.6 and Table 8.9. Engineers from the refinery have agreed upon these normal values. These two sets of normal values are regarded as the base cases in this work. It is desirable to mn the refinery-wide model using these normal operation conditions and compare the product slate and purchase plan with the LP reports. The results are listed in Table 8.5 and Table 8.6. It can be seen from Table 8.5 and Table 8.6 that the average relative errors ofthe volumetric flow rates of products and purchases ofthe LP reports and model predictions under normal operating conditions are 1.36% for Summer Mode and 1.31% for Winter Mode. There are relative big difference for the quantitis of propane, ethanol, butane and C3 product in both modes or one mode. However, those streams have relative small amount. Therefore, the mismatch have an insignificant effect on the overall revenue of the refinery. 8.2.2 Summer Mode The refinery-wide optimization was conducted for Summer Mode. The optimum values ofthe decision variables of refinery-wide optimization are listed in Table 8.7. The active constraints in the optimum solution are listed in Table 8.8. The comparison ofthe product slates between the optimum solution and base case is shown in Table 8.9 and Figure 8.2.

172

Table 8.5 Comparison of Model Prediction ofthe Base Case with the LP report. Summer Mode. Item Purchase, bbl/day Cmde Toluene Ethanol Isobutane Sale, bbl/day Light naphtha Butane SNL spot NL spot Sub.Oct. spot SNL rack NL rack Sub. Oct. rack Propane C3 product Jet fiiel A Jet fiiel 5 Low sulfur diesel No. 2 diesel No.6 fiiel oil Average error Purchase, $/day Sale, $/day Utility, $/day Revenue, $/day 1017 950 0 1742 0 3300 16000 3700 371 1254 800 5000 10813 3419 2440
-

LP report

Model Prediction

Relative Deviation, %

50000 200 379 1377

50000 198 370 1,407.4

0.00 -1.00 -2.37 2.21

1009.5 927.17 0 1744.5 0 3300 16000 3700 311 1264 800 5000 10812 3418 2460
-

-0.74 -2.40 0.00 0.14 0.00 0.00 0.00 0.00 -16.10 0.80 0.00 0.00 -0.01 -0.03 0.82 1.36 -0.01 -0.07 -3.14 0.18

737529 881742 24671 119543

737470 881121 23897 119754

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Table 8.6 Comparison of Model Prediction ofthe Base Case with the LP Report, Winter Mode. Item Purchase, bbl/day Cmde Toluene Ethanol Butane Isobutane Sale, bbl/day Light naphtha SNL spot NL spot Sub.Oct. spot SNL rack NL rack Sub. Oct. rack Propane C3 product Jet fuel A Jet fiiel 5 Low sulfur diesel No. 2 diesel No.6 fiiel oil Average Error Purchase, $/day Sale, $/day Utility, $/day Revenue, $/day 595.000 0.000 3853.290 0.000 3300.000 16000.000 3700.000 129.000 1700.000 800.000 5000.000 13024.000 1339.000 1823.000
-

LP report

Model Prediction

Relative Deviation, %

50000.000 18.000 362.000 1044.300 945.000

50000.000 18.000 370.000 1041.630 945.440

0.00 0.00 2.21 -0.26 0.05

600.450 0.000 3839.810 0.000 3300.000 16000.000 3700.000 108.020 1754.770 800.210 5000.000 13000.000 1321.680 1819.520

0.92 0.00 -0.35 0.00 0.00 0.00 0.00 -16.26 3.22 0.03 0.00 -0.18 -1.29 -0.19 1.31

771508.105 865929.018 22843.928 71576.984

771821.816 865578.997 21932.920 71824.261

0.04 -0.04 -3.99 0.35

174

It should be noted that the revenue in the optimum solution shown in Table 8.8 does not include the reformer regeneration cost. The reason is that the reformer operation is not stable in the refinery considered in this work and the cycle length varies in the real operation. It is difficult to estimate the regeneration cost per day for the base case. Hence, the reformer regeneration cost is not included in the revenue ofthe base case. To make a fair comparison, the reformer regeneration cost is also not included in the revenue of the optimum solution. Same approach is used in the case of Winter Mode and the case of single unit optimization. It should be noted that the cmde throughput in both the optimum solution and the base case reached the upper limit ofthe cmde unit capacity. Hence, no benefit is obtained from incremental throughput in the optimum solution. The only thing the optimizer can do to improve the profitability ofthe refinery is to adjust the product slate and make more high-value products and less low-value products. It can be seen from Figure 8.2 that the significant differences between base case and the optimum solution are the gasoline production and diesel production. It should be noted that the refinery has contracts with retailing companies for all three grades of gasoline. These contracts become the lower limits for gasoline production. In other words, the refinery must produce certain amount for each grade of gasoline. Any amount of gasoline above the amount in the contract is sold on the spot market. In the optimum solution, more spot Unleaded Gasoline is produced them the base case. This is understandable because the Unleaded Gasoline has a relative high price in Summer Mode The question may be raised that why the optimizer does not try to make more spot Super Unleaded Gasoline which has a higher price than the Unleaded Gasoline. The answer is that to make more Super Unleaded Gasoline, either the reformer will be operated longer at high severity mode, or the FCC unit will be operated at higher severity, or more toluene is purchased. None ofthe three options is favorable from the economic point of view. Operating the reformer longer at high severity mode decreases the conversion from the feed to reformate and produces more low-value light gas. It also shortens the cycle length ofthe reformer, which results in decrease of on-stream factor

175

and increase ofthe regeneration cost. For FCC operation, since the FCC operation has already reached the upper limit ofthe wet gas compressor constraint in the optimum solution, decreasing throughput is necessary when the severity of FCC unit is increased. Increasing the severity of FCC unit also increases the production of low-value light gas. Purchasing more toluene is also not a good option because the toluene price is higher than that of gasoline. Therefore, it is a better choice to make more spot Unleaded Gasoline instead of spot Super Unleaded Gasoline. The extra spot Unleaded Gasoline produced in the optimum solution mainly comes from cutting more diesel components into the gasoil and blending all light naphtha in the gasoline. It is observed from Figure 8.2 that less diesel is produced in the optimum solution. The light naphtha has a relative low market price and it should be all blended into gasoline. The optimum solution also shows that low severity operation time/total operation time reaches the upper limit. It means the low severity operation should be longer than normal operation. This can be explained by the fact that high severity operation produces more low-value light gas and less high-value reformate, though the octane number ofthe reformate is higher. High severity operation also results in more coke deposited on the catalyst and consequently, shorter cycle length. The gain of operating reformer at high severity longer is that more Super Unleaded Gasoline can be produced. However, it seems that the cost of producing more Super Unleaded Gasoline is too high. The information sent by the optimum solution is that as long as there are enough octane number in the gasoline, the reformer should be operated at low severity in Summer Mode.

176

Table 8.7 Optimum Values ofthe Decision Variables of Refinery-wide optimization. Summer Mode. Decision variables Crude Unit: I 2 3 4 5 6 7 FCC Unit: 8 9 Feed to crude unit AT furnace outlet temperature, F Light naphtha ASTM 95% point, F Heavy naphtha ASTM 95% point, F Jet Fuel ASTM 95% point, F Diesel ASTM 95% point, F Heavy Vacuum Gas Oil TBP end point, F Regenerator temperature, F Reactor temperature, F No. Decision variable name Base Case Summer Optimum Summer

50000.000 50000.000 665.000 260.000 370.000 475.350 622.000 1091.000 1270.000 1000.000 0.013 900.000 6.000 664.999 230.228 384.824 489.021 634.983 1099.460 1250.013 1002.251 0.020 900.000 7.486

10 02%) in the flue gas, mol% Reformer: 11 First bed inlet temperature, K, low severity 12 H2/Hydrocarbon recycle ratio, mol/mol, low severity 13 First bed inlet temperature, K, high severity severity 15 Low severity operation time/total operation time Blending Super Unleaded 18 Fraction of alkylate in Super Unleaded 19 Fraction of LSR in Super Unleaded 16 Fraction of FCC gasoline in Super Unleaded 17 Fraction of low reformate in Super Unleaded

912.000

911.736 7.309

14 H2/Hydrocarbon recycle ratio, mol/mol, high 5.500 0.750

0.800

0.000 0.001

0.079 0.000

0.565 0.000

0.573 0.000 0.040 0.047

20 Fraction of high reformate in Super Unleaded 0.750 21 Fraction of butane in Super Unleaded
0.054

177

Table 8.7 Continued. Decision variable 22 Fraction of toluene in Super Unleaded Unleaded 23 Fraction of FCC gasoline in Unleaded 24 Fraction of low reformate in Unleaded 25 Fraction of alkylate in Unleaded 26 Fraction of LSR in Unleaded 27 Fraction of high reformate in Unleaded 28 Fraction of butane in Unleaded 29 Fractionof toluene in Unleaded Sub. Oct. 30 Fraction of butane in Sub. Oct. 31 Fraction of Toluene in Sub. Oct. Light naphtha 32 Fraction of Light naphtha sold directly No. Decision variable name Base Case Summer 0.990 0.991 0.705 0.176 0.321 O.I 00 0.187 0.000 0.034 0.000 0.363 Optimum Summer 1.000 0.910 0.710 0.236 0.600 0.922 0.106 0.000 0.035 0.000 0.000

Table 8.8 Active Constraints in Refinery-wide Optimization, Summer Mode. Active Constraint Name Jet Fuel Tank Capacity Wet gas compressor inlet suction FCC throughput Super Unleaded Gasoline, (R+M)/2 Super Unleaded Gasoline, RVP Super Unleaded Gasoline, Specify Gravity Unleaded Gasoline, MON Unleaded Gasoline, RVP Sub. Oct. Gasoline, (R+M)/2 Sub. Oct. Gasoline, RVP Sub. Oct. Gasoline volumetric flow rate flow Limit type Upper Upper Upper Lower Upper Lower Lower Upper Lower Upper Lower

178

Table 8.9 Comparison ofthe Decision Variables of Refinery-wide Optimization with Base Case, Summer Mode. Item Purchase, bbl/day Crude Toluene Ethanol Isobutane Sale, bbl/day Light naphtha Butane SNL spot NL spot Sub.Oct. spot SNL rack NL rack Sub. Oct. rack Propane C3 product Jet ftiel A Jet ftiel 5 Low sulftir diesel No. 2 diesel No.6 fuel oil Summary Purchase, $/day Sale, $/day Utility, $/day Revenue, $/day 737470 881121 23897.00 119754 736338.6 884888.93 23467.00 125083.33 -0.15 0.43 -1.80 4.45 1009.5 927.17 0 1744.5 0 3300 16000 3700 311 1264 800 5000 I08I2 3418 2460 0 976 72 3009 0 3300 16000 3700 306 1192 800 5000 10539 3332 2464 -100.00 5.27
-

Model Prediction

Optimum Solution

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50000 198 370 1,407.4

50000 200 370 1314

0.00 I.Ol 0.00 -6.64

72.48
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0.00 0.00 0.00 -1.69 -5.70 0.00 0.00 -2.52 -2.51 0.17

179

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Some spot Super Unleaded Gasoline is produced in the optimum solution of Summer Mode. This increase in Super Unleaded Gasoline is realized by blending gasoline closer to its lower limit of octane specifications. In the gasoline blending process ofthe refinery considered in this work, the octane number ofthe gasoline is usually blended to about 0.1 to 0.4 octane number higher than its specifications. This is a common industrial practice to avoid disqualification and reblending. Since the refinery considered in this work has not implemented advanced control system, which is a necessity for tight gasoline blending, the octane giveaway can not be decreased. In the optimum solution, either one ofthe two octane specifications, (R0N+M0N)/2 or MON, reaches the lower limit. By blending the gasoline closer to the octane specification, more Super Unleaded Gasoline can be produced. It is found that gasoline blending agrees with the common industrial practice by hitting the lower limits of octane number specification and the upper limits of RVPs. The upper limits of RVPs are always active because by doing so, more low-value butane can be blended into high-value gasoline. 8.2.3 Winter Mode The refinery-wide optimization was conducted for the Winter Mode. The optimum operating conditions that maximize the revenue were found. The optimum values ofthe decision variables of refinery-wide optimization are listed in Table 8.10. The active constraints in the optimum solution of Winter Mode are listed in Table 8.11. The comparison ofthe product slates ofthe optimum solution with the base case is shown in Table 8.12 and Figure 8.3. It can be seen from Figure 8.3 that the significant differences between base case and optimum solution are also the gasoline production and diesel production. In the optimum solution, the refinery produces significant amount of spot Super Unleaded Gasoline where there is no spot Super Unleaded Gasoline in the base case. The optimizer adjusts the operating conditions ofthe processing units and the gasoline

181

blending to maximize the Super Unleaded Gasoline, which has the highest market value among all the grades of gasoline. More cmde has been cut into diesel in the optimum solution than in the base case. This can be explained by the fact that diesel has high market value in the Winter Mode. Although diesel price is still lower than the gasoline price in the winter in this case, there is more volumetric lost in gasoline production route. The loss mainly happens in the FCC unit and the reformer where large amount of low-value light gases is produced. Considering both the price gap and the volumetric loss, it is more beneficial to produce more diesel in Winter Mode. However, there is also a limit of increasing diesel production. Increasing diesel product means less feed for the FCC unit. Further decrease in FCC feed may result in overcracking in FCC unit if the riser temperature remains high. Overcracking produces more light gases, which result in more volumetric loss for gasoline production. If the riser temperature is lowered to avoid overcracking, the octane number ofthe FCC gasoline will drop, which results in less Super Unleaded Gasoline that can be produced since the octane number of FCC gasoline drops. The optimizer makes a compromise between diesel production and gasoline production and chooses an appropriate value for the ASTM 95% point ofthe diesel that maximizes the profitability ofthe refinery. Again, the light naphtha has a relative low market price. The optimum solution shows that it should be all blended into gasoline. The optimum solution also shows that low severity operation time/total operation time reaches the upper limit. It means the low severity operation should be longer than normal operation in the Winter Mode. This can be explained by the factor that the gasoline pool has a higher average octane number because more high-octane butane has been blended into the gasoline pool. Hence, there is less demand on the high octane reformate produced by high severity reformer operation.

182

Table 8.10 Comparison ofthe Decision Variables of Refinery-wide Optimization with Base Case, Winter Mode. Decision variable Crude Unit: Feed to cmde unit AT fiimace outlet temperature, F Light naphtha ASTM 95% point, F Heavy naphtha ASTM 95% point, F Jet Fuel ASTM 95% point, F Diesel ASTM 95% point, F Heavy Vacuum Gas Oil TBP end point, F FCC Unit: 8 9 Regenerator temperature, F Reactor temperature, F No. Decision variable name Base Case Optimum Winter Winter

50000.000 50000.000 665.000 250.000 370.000 465.280 593.000 1055.000 1270.000 1000.000 0.013 900.000 6.000 650.000 246.669 364.123 460.000 620.000 1070.000 1300.531 1004.997 0.012 900.000 7.500

10 02% in the flue gas, mol% Reformer: 11 First bed inlet temperature, K, low severity 12 H2/Hydrocarbon recycle ratio, mol/mol, low severity 13 First bed inlet temperature, K, high severity 14 H2/Hydrocarbon recycle ratio, mol/mol, high severity 15 Low severity operation time/total operation time Blending Super Unleaded 18 Fraction of alkylate in Super Unleaded 19 Fraction of LSR in Super Unleaded 16 Fraction of FCC gasoline in Super Unleaded 17 Fraction of low reformate in Super Unleaded

910.101 5.500

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0.053

183

Table 8.10 Continued. Decision variables 22 Fraction of toluene in Super Unleaded 23 Fraction of FCC gasoline in Unleaded 24 Fraction of low reformate in Unleaded 25 Fraction of alkylate in Unleaded 26 Fraction of LSR in Unleaded 27 Fraction of high reformate in Unleaded 28 Fraction of butane in Unleaded 29 Fraction of toluene in Unleaded 30 Fraction of butane in Sub. Oct. 31 Fraction of Toluene in Sub. Oct. 32 Fraction of Light naphtha sold directly No. Decision variable name Base Case Optimum 1. Winter 0.090 0.900 0.999 0.267 0.526 0.025 0.209 0.000 0.045 0.000 0.224 2. Winter 0.000 0.862 0.888 0.000 0.694 0.000 0.186 0.000 0.042 0.000 0.000

Table 8.11 Active Constraints in Refinery-wide Optimization, Winter Mode. Active Constraint Name Jet Fuel Tank Capacity Wet gas compressor inlet suction Super Unleaded Gasoline, (R+M)/2 Super Unleaded Gasoline, RVP Super Unleaded Gasoline, Specify Gravity Unleaded Gasoline, MON Unleaded Gasoline, RVP Sub. Oct. Gasoline, MON Sub. Oct. Gasoline, RVP Sub. Oct. Gasoline volumetric flow rate flow Limit type Upper Upper Lower Upper Lower Lower Upper Lower Upper Lower

184

Table 8.12 Comparison ofthe Product Slates ofthe Optimum Solution with the Base Case, Winter Mode. Base Case Purchase, bbl/day Crude Toluene Ethanol Butane Isobutane Sale, bbl/day Light naphtha SNL spot NL spot Sub.Oct. spot SNL rack NL rack Sub. Oct. rack Propane C3 product Jet ftiel A Jet ftiel 5 Low sulfiir diesel No. 2 diesel No.6 fuel oil Summary Purchase, $/day Sale, $/day Utility, $/day Revenue, $/day 771821.816 769691.3814 865578.997 866186.1954 21932.920 71824.261 22097.12 74397.694 -0.28 0.07 0.75 3.58 600.450 0.000 3839.810 0.000 3300.000 16000.000 3700.000 108.020 1754.770 800.210 5000.000 13000.000 1321.680 1819.520 0 1495.56 1656.24 0 3300.000 16000.000 3700.000 113.98 1579.99 800 5000 13000 2755.94 1806.76 -56.87 0.00 0.00 0.00 0.00 5.52 -9.96 -0.03 0.00 0.00 108.52 -0.70 0.92 50000.000 18.000 370.000 1041.630 945.44 50000 0 370 1047.78 818.68 0.00 -100.00 0.00 0.59 -13.41 Optimum Solution Relative Deviation, % >

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It is found from Table 8.11 that gasoline blending also agrees with the common industrial practice by hitting the lower limits of octane number specification and the upper limits of RVPs. The upper limit ofthe wet gas compressor is also an active constraint. This means that even in the Winter Mode, the highest severity ofthe FCC unit is favorable. This can be explained by the fact that the higher the FCC riser temperature is, the higher the octane number ofthe FCC gasoline, and the more super unleaded gasoline can be produced. The wet gas flow rate is a function of FCC feed rate and riser temperature. The optimizer suggests keeping the riser temperature at the upper limit ofthe riser temperature while adjusting feed rate to keep the wet gas flow stay at the upper limit of the wet gas compressor flow. This is different from the Summer Mode, in which the FCC throughput reaches the upper limit while adjusting the riser temperature to keep the wet gas flow stay at the upper limit ofthe wet gas compressor flow. 8.2.4 Optimal Solution Analysis The optimization problem at hand is a complexed problem with 32 decision variables and 70 constraints. The optimizer can not find a feasible solution each time. It was estimated that the optimizer failed to give a feasible solution in about 40 percent of all trials. Even the a feasible solution was found, it is not necessarily the optimal solution. The mean and standard deviation of feasible solutions from random starting points are listed in Table 8.13. Table 8.13 The Mean and Variance ofthe Feasible Solutions. Operation Mode No. of feasible solutions Summer Mode Winter Mode 100 100 Tme Solution -1.24169' -0.73421' -1.16709 -0.69699 Mean Standard Deviation 0.053868 0.035588

1: The the objective function used in the optimization is equal to dividing the revenue per day by-10'

187

The magnitude ofthe standard deviation indicates that the solutions found by the optimizer scatter around the real optimum in a fairly large area. In this work, about 200 sets starting points were used as starting points for each operation mode and the best solution was regarded as the tme solution. In order to have some confidence in the optimal solutions found in previous studies, a depth test was condcuted to find out the shape of objective fiinction surface around the optimal solutions. Tests were done to the optimal solutions of both Summer Mode and Winter Mode. Tests were carried out by choosing some random points around the optimal solution and calculating the objective fiinction value of each random point. A random point was selected by perturbing the values of decision variables using the formula given below:

X, = x^p,j + (0.5 - rand) - factor - {bu, - bl,),

(8.5)

where Xi- the i"^ decision variable ofthe random point, Xopt,i- the i"' decision variables ofthe optimal solution, rand- random number between 0 and 1, factor- the factor, 0.04. bui- the upper limit of i"^ decision variable, bli- the upper limit of i* decision variable. Since only the nearby surface was studied here, the change of a decision variable was limited in the interval of 2% of normal operating range. Since the optimization problem at hand is a constrained problem, it is obvious that some random points generated by equation 8.5 will have constraint violations. These random points were discarded in the study. The Euclidean distance between each random point and the optimal solution and the relative change in objective function value were calculated. The decision variables were nomalized in calculating euclidean distances. It is found in the tests that there is no random point that has a better objective fimction value than the

188

corresponding optimal solution. This indicated that the optimal solutions found in previous studies are at least the local optimums. The average euclidean distances and average relative changes of objective fiinction are listed in Table 8.14. Table 8.14 Change ofthe Objective Function Value around Optimal Solutions. Operation Mode Summer Mode Winter Model Average Euclidean distance 0.049355 0.049834 Average relative change of objective function -0.00086 -0.00418

It can be seen that the change ofthe objective fiinction values around the optimal solution of Winter Mode is one magnitude larger than that of Summer Mode. Considering the stopping criteria of l.E-6 for the optimizer, the changes of objective fimction values for both modes are significant. Hence, it is concluded that the surface around each optimal solution has enough steepness which will not cause the optimizer to stop before it reach the vinicity ofthe solution. Why the optimizer stops in the vinicity of a tme optimum remains unknown and ftirther is needed on this issue. 8.2.5 Profitability Improvement The profitability improvements ofthe two operation modes are shown in Table 8.15. The average profitability improvement is 4.1%. The total revenue increase is about 1.3 million dollars per year. The refinery considered in this work is a small refinery with a capacity of 50,000 barrels cmde oil per day. Considering the fact that some big refineries have a capacity of 400,000 barrels cmde oil per day, the absolute profitability improvement can be more significant. This profitability improvement is also comparable to the profit of implementing advanced process control, 3-5% (Ellis, 1998), and that of implementing real-time optimization, 3-5% (Ellis, 1998). For the refinery considered in this work, the throughput ofthe FCC unit has an upper limit of 20,000 barrels per day determined by environment regulations. Hence, no

189

benefit ofthe throughput increase, which is common to other optimization projects, can be obtained from the refinery-wide optimization.

Table 8.15 Profitability Improvement ofthe Refinery-wide Optimization. Operation Mode "~~~~~ Mode Summer Winter Model Average Annual Incremental Revenue NLP vs. Base Case +4.5% +3.6% +4.1% Incremental Revenue $973,000/six months $468,000/six months $72I,000/sixmonths $1,341,000/year

8.3 Single-Unit Optimization Currently, on-line optimizer has been implemented in several units in the refineries to push the operation to against the most profitable constraints. The units which already have the on-line optimizer implemented include crude unit, FCC unit, reformer, etc. However, the optimizer implemented on a single unit only considers the economics of that single unit instead ofthe economics ofthe whole refinery. It is very difficult for a single-unit optimizer to generate an optimum solution which is consistent with those given by a refinery-wide optimizer. This is because it is difficult to obtain appropriate prices for the intermediate streams ofthe single umt. Cmde Unit is used as the example to show the difference between the solutions of single-unit optimization and refinery-wide optimization. Cmde unit is the first major processing unit in the refinery. It produces several side-draw products that are the feeds to the downstream processing units in a refinery. Usually the side-draw products are not final products sold in the market. The prices ofthe side-draw products from the cmde unit ofthe Summer Mode are estimated from Linear Programming (LP) shadow prices and market prices. LP shadow prices and market prices are two main resources for estimating the prices of intermediate streams. For a side-draw product, market price is used whenever it is available. Otherwise, LP shadow price from the LP reports is used. The prices ofthe side-draw products are listed in Table 8.16.

190

Table 8.16 Prices ofthe Side-draw Products from the Cmde Unit, Summer Mode. Side-draw Product Price, $/bbl Source Cmde LSR Heavy Naphtha Jet Fuel Diesel Gas Oil Residue 13.97 13.93 17.45 17.44 16.35 11.95 9.22 Market Price Market Price LP shadow price Market Price of Jet-5 Market Price of No. 2 diesel fuel LP shadow price Market Price of No. 6 fuel oil

Using the same objective fimction form as that of refinery-wide optimization shown in equation 8.2, optimization was conducted using the same cmde unit model which has been used in the refinery-wide model. The subset of decision variables and constraints ofthe refinery-wide optimization corresponding to the cmde unit were also used for the single-unit optimization ofthe cmde unit. The values of decision variables in the optimum solution ofthe single-unit optimization ofthe cmde unit are shown in Table 8.17. It can be observed from Table 8.17 that the optimization solution ofthe singleunit optimization ofthe cmde unit always reaches the upper limit ofthe ASTM end point of those high-value side-draw products such as heavy naphtha, jet ftiel and diesel. This means the optimum solution simply maximizes the side-draw product with higher value. It can be explained by the fact that side-draw product production has the dominating role in revenue calculation. The utility usage in the cmde unit has secondary importance in the optimization (Xu, 1998). In addition, the utility usage does have big change even when the ASTM 95%o points vary. Hence, the maximizing the size-draw product with higher value is the obvious solution ofthe single-unit optimization.

191

Table 8.17 Prices ofthe Side-draw Products from the Cmde Unit, Summer Mode. Side-draw Product Price of side-draw product, $/bbl 13.97 Optimum value of single-unit optimization 50,000.000 650.000 Active Limit

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In order to make a fair comparison between single-unit optimization and refinerywide optimization, the optimization is conducted for the rest ofthe refinery while fixing the decision variables ofthe cmde unit at the optimum value given by the single-unit optimization. In other words, the subsets of decision variables and constraints corresponding to the cmde unit are not included in the decision variable set and constraint set of this optimization study. The solution of this optimization is compared to that of refinery-wide optimization shown in Table 8.18 and Figure 8.4. It can be observed from Table 8.18 and Figure 8.4 that the single-unit optimization produces more diesel and less gasoline than the refinery-wide optimization. This product slate change makes the revenue ofthe solution ofthe single-unit optimization about 1.6% less than the revenue ofthe refinery-wide optimization. This case shows that single-unit optimization may result in suboptimal solution for the point of view of refinery-wide economics. Single-unit optimizer normally will maximize the

192

volume of the product with highest estimated price, which may not be the optimum for the plant-wide operation. In order to make the single-unit optimization generates solution consistent with refinery-wide economics, appropriate prices for the intermediate streams are necessary. Sometimes, external constraints from refinery-wide economics are also needed (Jones, 1999). This also shows that refinery-wide optimization is superior to single-unit optimization in the sense refinery-wide optimization eliminates the need to evaluate the prices of intermediate streams. The refinery-wide optimization only uses market prices. In order to realize the full potential ofthe refinery. It is beneficial to carry out refinerywide optimization.

Table 8.18 Comparison of Single-unit Optimization with Refinery-wide Optimization, Summer Mode. Refinery-wide Opt. Purchase, bbl/day Cmde Toluene Ethanol Isobutane Sale, bbl/day light naphtha Butane SNL spot NL spot Sub.Oct. spot SNL rack NL rack Sub. Oct. rack Propane 0 976 72 3009 0 3300 16000 3700 306 0 943 151 1564 12 3300 16000 3700 341 0.00 -3.40 109.04 -48.02 0.00 0.00 0.00 0.00 11.48 50000 200 370 1314 50000 200 371 901 0.00 0.00 0.33 -31.44 Single-unit Opt. Relative Deviation, %

193

Table 8.18 Continued. Refinery-wide Opt. C3 product jet fiiel A Jet ftiel 5 low sulfur diesel No. 2 diesel No.6 fiiel oil Summary Purchase, $/day Sale, $/day Utility, $/day Revenue, $/day 736338.6 884888.93 23467.000 125083.33 731165.183 876975.827 22740.000 123070.644 -0.70 -0.89 -3.10 -1.61 1192 800 5000 10539 3332 2464 Single-unit Opt. 976 800 5000 11409 3607 2452 Relative Deviation, % -18.13 0.00 0.00 8.25 8.24 -0.47

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195

CHAPTER 9 CONCLUSIONS AND RECOMMENDATIONS

The two main objectives of this work were: 1. Develop an overall nonlinear refinery-wide model for a ftiel-oriented refinery that represents the refinery operation. 2. Carry out optimization studies to the overall refinery-wide model to find optimal operating conditions that are inline with the actual practice. This chapter is essentially a final commentary on how far successfiil we were in meeting these objectives, and what is left for ftiture work.

9.1 Conclusions Among the two major steps listed above, the first step required the maximum amount of investment of time and effort. A first-principle, nonlinear steady-state refinerywide model was developed by building individual models for all processes in a fueloriented refinery and integrating them into a refinery-wide model. A simplified model was developed for the cmde unit. The atmospheric tower and the vacuum tower in the cmde unit were modeled based on material balance, energy balance and empirical correlations. The main function ofthe cmde unit model is to predict the yields and properties ofthe side-draw products given the feed information and cut points. Predictions ofthe simplified model agree with a rigorous ChemCad cmde unit model on the volumetric flow rates ofthe side-draw products and the gains between volumetric flow rates and cut points. It is concluded that the gasoline blending model represents the actual process reasonably well. A complete set of gasoline properties with eleven properties is calculated in the gasoline blending model. In the octane blending model, interaction coefficient method using chemical compositions ofthe blending stocks are applied. The interaction

196

coefficients in the octane blending model were regressed from the blending data ofthe refinery considered in the work. The Chevron's VPBI method is used in the RVP blending model. Chevron's VPBI method is a proven method with reasonable accuracy. The vaporization properties are calculated from the ASTM curves ofthe blending stocks assuming ideal mixing. Other properties of gasoline are also calculated by summing the corresponding properties ofthe blending stocks. Basic on the proven methods used in the gasoline blending, it is concluded that the gasoline blending model represents the actual process reasonably well. The modeling ofthe FCC unit and reformer unit uses the existing models. Minor modifications to both models to accommodate the specific features of the processes in the concerned refinery. The kinetic parameters are used as the adjustable parameters to benchmark the models against indusfrial data. We could not find data points spread over the operating region since both processes are operated close to steady state. The FCC model was benchmarked at a base case operating point. Since the FCC model had already been proven to predict reasonably well in the full operating region in earlier studies (Ellis, 1996; Taskar, 1996) and only minor changes were made in this work. It is concluded that the FCC model can represent the FCC unit of this particular refinery reasonably well in the full operating range. The reformer model was benchmarked at two base case operating points corresponding to the low severity operation and the high severity operation. By benchmarking the reformer model against two operating conditions in different operating regions, it is expected that the reformer model should give reasonable predictions in the fliU operating range ofthe unit. The alkylation unit model was developed based on stoichiometric relations and data from linear programming (LP) reports. Simplified models are developed for other units in the refinery including rerun unit, ROSE unit, hydrotreater, gas plant, and diesel hydrotreater, based on the data from the LP reports. The data from the LP reports include the data of both operation modes. Summer Mode and Winter Mode. These units do not change much in each operation mode. Hence the models are considered adquate by using only normal operating data.

197

TOTAL method and n-d-M method are used to calculate paraffins, naphthenes, and aromatics (PNA) data ofthe FCC feed. These methods have been proven the most accurate methods available in the literature. The feed characterization ofthe reformer unit is based on the cmde assays, cut point ofthe reformer feed, and typical feed compositions. The prediction ofthe PNA information ofthe reformer feed should be more accurate than the prediction from empirical correlations. The cmde assays should be used whenever possible. There may be some model mismatch on the composition of individual chemical components in the reformer feed. The mismatch is deemed to have an insignificant effect on refinery-wide optimization because volumetric fiow rates instead of stream compositions have the utmost importance in refinery-wide optimization. The predictions from the overall refinery-wide model are close to the data in the LP reports for both operation modes. Because the refinery operation follows the LP reports, the model predictions are also close to the plant data. It is concluded that the refinery-wide model represents the fuel-oriented refinery reasonable well. The computational load is a big concern in refinery-wide optimization. The size ofthe refinery-wide model is huge, with more than 22,000 lines of Fortran code, among which 25%) are comment lines. Each objective function evaluation or each derivative evaluation requires the solving ofthe entire model. The computational efficiency is cmcial in obtaining a solution in reasonable time. With the computational issue in mind, the refinery-wide model is coded in a straight-through form to ease computational load. This simplification enables the model to be solved in the range of 3-5 seconds on a 400 MHz Pentium II machine. The optimization study of Summer Mode showed a profit improvement of 4.5% over the normal operating conditions. This is realized mainly by producing more gasoline and less diesel, and blending all light naphtha into gasoline. In addition, the FCC feed reaches the upper limit while the wet compressor flow upper limit is active. The optimization study of Winter Mode showed a profit improvement of 3.6% over the normal operating conditions. Contrary to the Summer Mode, the profit

198

improvement is realized mainly by producing more diesel and less gasoline. In the optimum solution of Winter Mode, all light naphtha is blended into gasoline. Although the total amount of gasoline decreases, the amount of Super Unleaded Gasoline increased in the optimum solution. The FCC unit is operated at the highest severity while the wet compressor flow limit is active. The most important characteristic of an optimization study is to that the optimum solutions make sense. By discussing with engineers from the refinery considered in this work, it is found that these results are consistent with the operation strategy ofthe refinery for both operation modes. One example is that the FCC unit in the refinery is usually operated against the wet gas compressor constraint. We concluded that the optimizer is able to find the optimum operating conditions that make the refinery operation more profitable. The average profit improvement is 4.1%, which is equal to about 1.4 million dollars per year for the particular refinery. This revenue improvement is consistent with 3-5%) expected profit improvement (Hendon, 2000). It can be argued that real profit improvement may not be exactly the same number showed here because the model is not perfect. Nevertheless, this work proves that refinery-wide optimization can generate reasonable optimum solutions that agree with the industrial practice and that is in a quantitative form with plant-wide consistence instead of vague feelings about the profit increase. The single-unit optimization on the cmde unit shows that the solution of a singleunit optimization may not be consistent with the optimum operation strategy for the entire refinery. The case study shows that single-unit optimization on the cmde unit resuhs in suboptimal operating conditions with 1.6% profit loss compared to the refinerywide optimization. The conclusion is that refinery-wide optimization is necessary in order to realize the maximum profit from the plant-wide perspective. The success of a singleunit optimization depends on the appropriate prices ofthe intermediate streams and appropriate extemal constraints. In conclusion, we would like to say that we completed the two major steps outlined at the beginning of this chapter.

199

9.2 Recommendations Considering that current work is the first attempt to study the refinery-wide optimization, following recommendations are made: 1. The effectiveness of process optimization is highly dependent on the quality ofthe models used to simulate the process. Considering the complexity of refining processes, to build detailed models for all the units in a refinery is out the scope of this work. The cmde unit model can be improved by using strict tray-to-tray models for the atmospheric tower and vacuum tower. The preheat train, preflash tower and heat exchanger can also be modeled to develop a complete cmde unit model. Although this kind of cmde unit model has not been seen in academia, this has been accomplished in industry using commercial simulation software package. 2. The FCC ten-lump yield model should be expanded in order to predict the FCC gasoline composition. The FCC gasoline is regarded as one lump in the ten-lump yield model. Hence, it is impossible to calculate the PNA information ofthe FCC gasoline, which is required by gasoline blending model. 3. A rigorous model needs to be developed for the main fractionator ofthe FCC unit in order to have a complete FCC model. The cut points ofthe side-draw products ofthe main fractionator are important decision variables, which are often adjusted by engineers to change the refinery operation. The flooding constraint in the main fractionator can be active sometimes during the operation. After the rigorous model ofthe main fractionator is developed, the cut points may be included in the decision variable set and the flooding constraint may be included in the constraint set. 4. Only simplified models were developed for units other than the four major units. Hence, the next logical step in this work would be to develop detailed nonlinear models for these units. The main benefit of doing this is that the constraints for these units can be accurately modeled. These constraints may become active in refinerywide optimization. In the current model, only capacity constraints are considered in

200

these units. Other constraints may be included in the optimization study after detailed models of these units are available. 5. All the models in current refinery-wide model are in sequential-modular form. Sequential-modular models have an inherent disadvantage of no accurate information ofthe derivatives due to nested convergence loops. The noisy derivatives cause the optimizer "wandering" during the search (AspenTech, 1998). It has been already observed that the SQP algorithm based NPSOL software package (Gill et al., 1986) often quitted searching without finding a solution in the present work. It is suspected that the difficulty is caused by inaccurate derivatives. Open form approach has become the standard in industry. One ofthe major advantages of open form approach is that accurate derivatives can be calculated since each process is modeled by equations without nested convergence loops. 6. More detailed refinery-wide model using sequential modular approach may not be computational efficient due to the iterations required in model solving because ofthe existence of recycle streams. The open form approach can solve the entire refinerywide model altogether without iterations. In addition, computational improvement techniques, like algorithm for sparse matrices, can be applied for large open equation model. 7. Building a detailed refinery-wide model with open form may include as many as one million equations (Hendon, 2000). It is recommended to build open form single-unit model as the first attempt. Using existing models in the process model libraries (PML) of commercial software packages, such as AspenPlus, may be the easiest way to constmct an open form refinery-wide model. 8. It is beneficial to include the specifications of all products produced in a ftiel-oriented refinery. Only the product specifications of gasoline are considered in this work. The specifications of other products, such as jet fiiel, diesel, No. 6 fliel oil, are not included. The constraints associated with these specifications, such as the freezing point of jet fuel, and the flash point and the pour point of diesel, are indirectly represented by cut points in the current model. Including these specifications in the

201

model should increase the accuracy of estimating the violations of product specifications. 9. Sulftir balance becomes important as the specifications of sulfur content in all products become more stringent. The capacity ofthe sulfiir recovering unit may become an active constraint in refinery operation. Hence, effort should be spent on modeling the sulfur fiow and distribution in a refinery. 10. Selecting appropriate cmde type according to market change can be important to improve the profitability of a refinery. Hence, it is beneficial to include cmde selection in the decision variable set ofthe refinery-wide optimization. 11. The comparison between nonlinear refinery-wide optimization and linear programming (LP) will be critical in convincing industrial people that nonlinear refinery-wide optimization is a better tool than LP in plainning and scheduling. To fiirther current work, effort should be spent on developing a linear model corresponding to the nonlinear model developed in this work.

202

BIBLIOGRAPHY American Petroleum Institute. Measuring , Sampling, and Testing Cmde Oil. Bulletin 2500, API, New York City, New York, January 1955. Arbel, A., Huang, Z, Rinard, I. H., and Shinnar R. Dynamic and Control of Fluidized Catalytic Cracker. I. Modeling ofthe Current Generation of FCC s. Ind. Eng. Chem. Res., Vol. 34, No. 4, 1995, 1228-1243. Aspen Technology Inc. Real-Time Optimization System Training Course Notes, Houston, TX, 1998. ASTM. Standard Specification for Automotive Spark-ignition Engine Fuel. ASTM Standard D4814-96, 1997. ASTM. Carbon Distribution and Stmctural Group Analysis of Petroleum Oils by the n-dM Method. ASTM Standard D3238-85, 1985. Beck, R. J. Resurgent Oil Demand, OPEC Cohesion Set Stage for Optimistic Outlook for Oil Industry at the Turn ofthe Centiiry. Oil & Gas Journal, 1999, 97(42), 49-62. Beck, R. J. Earnings Plunges along with Oil Price in 1998. Oil & Gas Journal, 1999, 97(18), 56-58. Bensabat, L. E. U.S. Fuels Mix to Change in the Next 2 Decades. Oil & Gas Journal, 1999, 97(28), 46-48, Hess, F. H., C. D. Holland, R. McDaniel, and N. J. Tetiow. Solve More Distillation Problems: 7. Absorber-Type Pipestills. Hydroc. Proc, 56(5), 1977, 241-249. Cutier, C. Personal Communication, Lubbock, TX, 1999. Chung, C. and J. B. Riggs. Dynamic Simulation and Nonlinear-Model-Based Product Quality Control ofa Cmde Tower. AIChE Journal, 41(1), 1995, 122-133. Dantzig, G. B. Linear programming and Extensions. Princeton University Press, Princeton, N J, 1963. Daubert, T. E. Petroleum Fraction Distillation Interconversions. Hydroc. Proc, 73(9), 1994,75-78. Dhulesia, H. New Correlations Predict FCC Feed Characterization Parameters. Oil & Gas Journal, Jan. 13, \9S6, 51-54.

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Edgar, T. F., and D. M. Himmelblau. Optimization of Chemical Processes. McGrawHill, Inc., New York City, NY, 1988. Edmister, W. C. Improved Integral Technique for Petroleum Distillation Calculations. Ind andEngr. Chem., 47(9), 1955, 1685-1690. Edmister, W. C , Lee B. I. Applied Hydrocarbon Thermodynamics. Gulf Publishing Company, Houston, TX, 1984. Ellis, R. Supervisory Optimization ofa Fluidized Catalytic Cracking Unit. Master's thesis, Texas Tech University, Lubbock, TX, 1996. Ellis, R. Personal Communication, Houston, TX, 1998. Ellis R. C , X. Li, and J. B. Riggs. Modeling and Optimization ofa Model IV Fluidized Catalytic Cracking Unit. AIChE J., 44(9), 1998, 2068-2079. Friedman, Y. Z. What's Wrong with Unit Closed Loop Optimization? Hydroc. Proc, 74(10), 1995, 107-116. Hendon, S. Personal Communication, Lubbock, TX 2000. Holland, C. D. Fundamentals of Multicomponent Distillation. McGraw-Hill, New York, 1981. Gary, J. H., and G. E. Handwerk. Petroleum Refining: Technology and Economics. Marcel Dekker, Inc., New York City, NY, 1984. Gill, P. E., W. Murray, and M. H. Wright. Practical Optimization, Academic Press, New York, 1981. Gill, P. E., W. Murray, M. H. Wright and M. H. Wright. User's Guide for NPSOL (Version 4.0): A Fortran Package for Nonlinear Programming. Technical Report SOL 86-2, Department of Operations Research, Stanford University, CA, 1986. Hartmann, J. C. M. Decision-making and Modeling in Petroleum Refining. Hydroc. Proc, 76(11), 1997,77-81. Hess, F. H. Ph.D. Dissertation, Texas A&M University, College Station, TX, 1977. Hess, F. H., C. D. Holland, R. McDaniel, and N. J. Tetiow. Solve More Distillation Problems: 7. Absorber-Type Pipestills. Hydroc. Proc, 56(5), 241.

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Holland, C. D. and Liapis A. I. Computer Methods for Solving Dynamic Separation Problems. McGraw-Hill Book Company, New York City, NY, 1983. Huq, I. and M. Morari. Modifications to Model IV Fluid Catalytic Cracking Units to Improve Dynamic Performance. AIChE Journal, Vol. 41, No. 6, 1481-1499. Jacob, S. M., B. Gross, S. E.Voltz, and V. W. Weekman Jr. A Lumping and Reaction Scheme for Catalytic Cracking. AIChE Journal, Vol. 22, No. 4, 701-713. Jones, J. Personal Communication, Lubbock, TX 1999. Lin, S. Petroleum Refining Engineering. Petroleum Industry Press, Beijing, P. R. China, 1988. Lin, T.D. V. FCC Advanced Control and Optimization. Hydroc Proc, 56(5), 107, 1993. Maxwell, J. B. Data Book on Hydrocarbons. D. Van Norstrand Company, Princeton, NJ, 1950. Marlin, T. E. Process Control: Designing Processes and Control Systems for Dynamic Performance. McGraw-Hill, Inc., New York City, NY, 1995. McFarlane, R. C , R. C. Reinemann, J. F. Bartere, and C. Georgakis. Dynamic Simulator for a Model IV Fluid Catalytic Cracking Unit. Comput. Chem. Eng., 17, 275-299, 1993. McKetta, J. J. Petroleum Processing Handbook. Marcel Dekker, Inc., New York City, NY, 1992. Mizoguchi, A., T. E. Marlin, and A. N. Hrymak. Operations Optimization and Control Design for a Petroleum Distillation Process. The Canadian Journal of Chemical Engineering. 73(6), 1995, 896-907. Morris, W. E. Optimum Blending Gives Best Pool Octane. Oil & Gas Journal, Jan. 20 1986,63-66. Morris, W. E. Gasoline Compositions in no-lead era. Oil & Gas Journal, Mar. 18 1985, 99-106. Morris, W. E., W. E. Smith, and D. D. Snee. Interaction blending equations enhance reformulated gasoline profitability. Oil & Gas Journal, 92(3), 1994, 54-58. Moran, M. J. and H. N. Shapiro. Fundamentals of Engineering Thermodynamics. John Wiley & Sons, Inc., New York City, NY, 1996. 205

Nelson, W. L. Petroleum Refinery Engineering. McGraw-Hill, Inc., New York City, NY, 1958. Palmer, F. H., A. M. Smith. The performance and specification of gasoline. E.G. Hancock (Ed.) Technology ofGasoline, Blackwell Scientific, London, 1985. Pelham, R. and C. Pharris. Refinery Operations and Control: a Future Vision. Hydroc. Proc, 75(7), 1996, S9-94. Pelham, R. Process optimization in the HPI. Hydroc Proc, July 1996, 89-94. Riazi, M. R. and T. E. Daubert, Simplify Property Predictions. Hydroc Proc, 59(3), 1980,115-116. Riggs, J. B. An Introduction to Numerical Methods for Chemical Engineers. Second Edition, Texas Tech University Press, Lubbock, TX, 1994. Riggs, J. B. Chemical Process Control. Ferret Publishing, Lubbock, TX, 1999. Sadeghbeigi, R. Fluid Catalytic Cracking Handbook. Gulf Publishing Company, Houston, TX, 1995. Schoen, W. F. and A. V. Mrstik. Calculating gasoline blend octane ratings. Ind. and Engr. Chem., 47(9), 1955, 1740-1742. Singh, A, J. F. Forbes, P. J. Vermeer, and S. S. Woo. Model-based real-time optimization of automotive gasoline blending operations. Journal of Process Control, 10, 2000, 43-58. Symonds, G. H. Linear Programming Solves Gasoline Refining and Blending Problems. Ind andEngr Chem.,4%{3), 394-401, 1956. Stewart, W. E. Predict RVP of Blends Accurately. Petroleum Refiner, 38(6), 1959, 231234. Stewart, W. E. Predict Octanes for Gasoline Blends. Petroleum Refiner, 38(12), 1959, 135-139. Taskar, U. Modeling and Optimization ofa Catalytic Naphtha Reformer. Ph.D. dissertation, Texas Tech University, 1996. Taskar, U. and J. B. Riggs. Modeling and Optimization ofa Semiregenerative Catalytic Naphtha Reformer, ^/C/z^Jowma/, 43(3), 1997, 740-753.

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Taylor, D. L., and W. C. Edmister. Solutions for Distillation Processes Treating ?etroleum Fractions. AIChE Journal, 17(6), 1971, I324-I329. Turpin, L. E. Modeling of commercial reformers. Chemical Industries, 61, 1994, 437480. Twu, C. H. and J. E. Coon. Predict Octane Numbers Using a Generalized Interaction Method. Hydroc Proc, 75(2), 1996, 51-56. Twoi, C. H. and J. E. Coon. Estimate Octane Numbers Using an Enhanced Method. Hydroc Proc, 76(3), 1997, 65-68. Xu, J. S., personal communication, Houston, TX, 1998. Watkins, R. N. Petroleum Refinery Distillation. Second Edition, Gulf Publishing Company, Book Division, Houston, TX, 1979. Unzelman, G. H. Gasoline Volatility-Environmental Interactions With Blending and Processing. Fuel Technology & Management, May/June 1996, 39-44. Vazquez-Esparragoza, J. J., Iglesia-Silva G. A., Hlavinka M., and Bullin, J. A. How to Estimate Rvp of Blends, Hydroc Proc, 71(8), 1992, 135-138. Zahed, A. H., S. A. Mullah, and M. D. Bashir. Predict Octane Number for Gasoline Blends. Hydroc Proc, 72(5), 1993, 85-87.

207

APPENDIX CONSTANTS OF POLYNOMIAL EXPRESSON

Table A.l Constants of Polynomial Expression for the TBP Curve ofthe Mixed Cmde in Summer Mode, Calculating the Vol.% Given the Temperature in F. Order ofthe Polynomial Expression Polynomial Constant Name 5 Polynomial Constant Value 0.8957974413351622 -0.01372701021955436
<^2

0.0002952782429384016 -2.I49703441506334e-007 -3.854442121853092e-011 5.81465I604877458e-014

Table A.2 Constants of Polynomial Expression for the TBP Curve ofthe Mixed Cmde in Summer Mode, Calculating the Temperature in F Given the Vol.%. Order of the Polynomial Expression Polynomial Constant Name 5 Polynomial Constant Value 29.84428824723 25.62933368742233 -0.7922673091416073 0.01622221295752979 -0.0001531047698293264 5.656848165464662e-007

208

Table A.3 Constants of Polynomial Expression for the TBP Curve ofthe Cmde in Winter Mode, Calculating the Vol.% Given the Temperature in F. Order of the Polynomial Expression Polynomial Constant Name 5 Polynomial Constant Value 2.193431671505095 -0.0401I70I235776854 0.0003645596718904187 -1.94657827079503e-007 -I.66907967834I765e-0I0 1.25674218569036Ie-013

Table A.4 Constants of Polynomial Expression for the TBP Curve ofthe Cmde in Winter Mode, Calculating the Temperature in F Given the Vol.%. Order ofthe Polynomial Expression Polynomial Constant Name Polynomial Constant Value 53.61544856365072 24.49778891041933 -0.8004076310844539 0.0170606968280822 -0.0001706104416978604 6.7218355I2472907e-007

209

Table A.5 Constants of Polynomial Expression for the API Gravity Curve ofthe Mixed Crude in Summer Mode, Calculating the API Gravity Given the Vol.%. Order ofthe Polynomial Expression Polynomial Constant Name 7 Polynomial Constant Value 119.7573532466777 -13.51427730842261
<^2

1.155003649306309 -0.05227710492067672 0.00129277077527945 -1.763855119596425e-005 1.24550423408025e-007 -3.55I0902548I0048e-0I0

Table A.6 Constants of Polynomial Expression for the API Gravity Curve ofthe Mixed Cmde in Winter Mode, Calculating the API Gravity Given the Vol.%. Order ofthe Polynomial Expression Polynomial Constant Name 7 Polynomial Constant Value 115.3176682424892 -13.66362146845495 1.199745867594174 -0.05421826016288378 0.001324183745545327 -1.77568580195242e-005 1.2296309055042I6e-007 -3.43531951355496Ie-0I0

210

Table A.7 Constants of Polynomial Expression for the Sulfiir Curve ofthe Mixed Cmde in Summer Mode, Calculating the Sulftir Given the Vol.%.' Order of the Polynomial Expression Polynomial Constant Name 6 Polynomial Constant Value -5.210428584234705e-005 7.080959174388113e-005 -3.525307004426104e-006 -I.0I7925910437589e-007 9.0797230957798I3e-009 -I.487796790868834e-010 7.430537669733543e-013 'The sulfur content is in wt.%). Table A. 8 Constants of Polynomial Expression for the Sulfur Curve ofthe Mixed Cmde in Winter Mode, Calculating the Sulftir Given the Vol.%.' Order ofthe Polynomial Expression Polynomial Constant Name ~c Cj c c ^
''4

6 Polynomial Constant Value 0.00030I4440208000I24 -9.6I6598620532102e-005 1.523461 lI5826574e-005 -8.795002067220337e-007 2.239074678304I39e-008 -2.49238838646I639e-010 I.0I0096349284079e-012

^ r The sulftu- content is in wt.%).

211

Table A.9 Constants of Polynomial Expression for Converting ASTM End Point to TBP End Point. 1,2
Polynomial Constant Name Polynomial Constant Value -89.99134827 2.74798583 -0.01068849 3.17354667D-5 -4.87231402D-8 3.72814245D-11 -1.11569087D-14

' The ranges that the polynomial expression applies to are: ASTM 95% point, 230-800F; TBP end point, 250-850F. ^The polynomial expression is regressed from the curves in Figure 2.15 of Watkins (1979). Table A. 10 Constants of Polynomial Expression for Converting Gap (5-95) ASTM to Gap (0-100) TBP. 1,2
Polynomial Constant Name '0 Polynomial Constant Value, hd-AGO 84.0867095 -1.16113063 -5.0455864D-3 1.2298931 lD-4 C4 ^5 1.45938226D-7 -6.04374077D-8 Polynomial Constant Value, Id-hd 116.80769309 -3.34042753 0.18403357 -8.27984365D-3 1.6959039 lD-4 -1.33260699D-6 Polynomial Constant Value, Ln-hn, hn-ld 171.90777015 -5.6022091 0.16631373 -3.16940048D-3 1.97107064D-5 0

' The polynomial expression correlates data when Gap (0-100) TBP is between 0F and 100F, and Gap (5-95 ) ASTM is between -20F and 60F. ^The polynomial expression is regressed from the curves in Figure 2.16 of Watkins (1979).

212

Table A. 11 Constants of Polynomial Expression for Calculating the Molecular Weight of a Cmde Cut Given the Mean Average Boiling Point and API gravity, Characteristic Factor from 12.1 to 12.6.'"^ Order ofthe Polynomial Expression Polynomial Constant Name 5 Polynomial Constant Value -85.12057662010193 1.381740973796696
^^2

-0.003432246121519711 4.653977835999967e-006 -2.013575892828579e-009 2.29628573710579e-0I4

' The range of MeABP is from 200F to 900F. ^The polynomial expression is regressed from the curves in the figure on page 22 of Maxwell (1950). Table A. 12 Constants of Polynomial Expression for calculating the molecular weight of a Cmde Cut Given the Mean Average Boiling Point and API gravity. Characteristic Factor from 11.7 to 12.0.''^ Order ofthe Polynomial Expression Polynomial Constant Name Polynomial Constant Value -64.81157898902893 1.187273759860545 -0.002771734283669503 3.45I7646I6357878e-006 -9.924137883005058e-0I0 -2.998295810238759e-0I3 ' The range of MeABP is from 200F to 900F. ^The polynomial expression is regressed from the curves in the figure on page 22 of Maxwell (1950). 213

Table A. 13 Constants of Polynomial Expression for Calculating the Molecular Weight of a Cmde Cut Given the Mean Average Boiling Point and API gravity. Characteristic 1,2 Factor from 11.3 to 11.6. Order of the Polynomial Expression Polynomial Constant Name Polynomial Constant Value -52.26850727200508 1.051935468334705
^2

-0.002316809990588808 2.74I261329930467e-006 -5.501099888116645e-010 -3.779033623234492e-013

C-,

' The range of MeABP is from 200F to 900F. ^The polynomial expression is regressed from the curves in the figure on page 22 of Maxwell (1950). Table A. 14 Constants of Polynomial Expression for Calculating the Enthalpy ofa Cmde 1,2 Cut from Its API Gravity, Temperature and Phase. Phase API Order ofthe Polynomial Expression Polynomial Constant Name Polynomial Constant Value 58.86276904234546 0.350323675930667 3.154147293926712E-4 -2.422868286555691E-7 2.670881203784828E-10 -9.569643092979734E-14 Polynomial Constant Value 63.49363322873251 0.374694305181038 2.455940050722916E-4 1.791162849984485E-8 -6.447463588954254E-I2 -2.499495895424942E-15 Liquid 0 5 Liquid 10 5

214

Table A. 14 Continued. Phase API Order ofthe Polynomial Expression Polynomial Constant Name Polynomial Constant Value 67.71119381915196 0.407442995888232 1.365238904540433E-4 3.40132834300566IE-7 -3.63881982759582E-10 1.372545297683309E-13 Phase API Order ofthe Polynomial Expression Polynomial Constant Name
^0 ^1 C2

Liquid
20 5

Liquid 30 5

Polynomial Constant Value 70.58775514527224 0.445968287169308 -6.67553647062391lE-5 1.094693139080949E-6 -1.397221644590038E-9 6.189472668211555E-13 Liquid 50 6

Liquid 40 5

Polynomial Constant Vali 73.53287428134354 0.487630852423536 -4.193622I423I0005E-4 2.815101644570994E-6 -4.582843798569582E-9 2.585350426563243E-12

7.852145754557569E+I 0.2332I2633516814E 3.992606531028287E-3 -2.54298013011578E-5 8.03349052350I33E-8 -1.174861450157626E-10 6.44705865814373E-14

Ci C^
n

215

Table A. 14 Continued. Phase API Order ofthe Polynomial Expression Polynomial Constant Name Polynomial Constant Value 79.85688170857611 0.361148813299224 1.71I36428I39107E-3 -9.349315025275473E-6 3.02I385889742656E-8 -4.69397245I398978E-11 2.835893371433551E-14 Phase API Order ofthe Polynomial Expression Polynomial Constant Name
Co
C^ Ci Ci
^4

Liquid 60 6

Liquid
70 3

Polynomial Constant Value 81.30727554178702 0.460461386308936 2.079979360163353E-4 4.238046095624004E-7

Liquid 80 7

Vapor 10 5

Polynomial Constant Valu 84.04810924726189 0.290888623800129 8.617715997388586E-3 -I.55I777304769075E-4 1.423607972839136E-6 -6.656375318991881E-9 1.532741903504612E-11 -1.376303736593522E-I4
185.5089059815509 0.3I06I1488926043 2.78I889429286366D-4 3.2I0699037192732D-8 -8.566150055727608D-1I 3.49229007131788D-14

^5
Ce
r

216

Table A. 14 Continued. Phase API Order ofthe Polynomial Expression Polynomial Constant Name
Co

Vapor 20 5

Vapor 30 6

Polynomial Constant Value 206.0313633410842 0.263410338567155 5.549406963822889E-4 -6.I89165425302123E-7 6.05569I909972712E-10 -2.3688445303691 lE-13
-

Polynomial Constant Value 219.8464761304203 0.343124140861619 -1.409107793506337E-4 I.841500715915601E-6 -3.701660586125782E-9 3.545420054274547E-I2 -I.354470866I46257E-I5 Vapor 50 5

c,
C2 Ci

c,
^5
Ce

Phase API Order ofthe Polynomial Expression Polynomial Constant Name

Vapor 40 5

Polynomial Constant Value

233.9651934063586 0.292765165784658 3.028I93795628908E-4 1.581314566512226E-7 -3.90264I490I37124E-10

Polynomial Constant Value

244.699721654586 0.301180828185352 2.330962857755026E-4 3.511663374533569E-7 -6.03663435I300283E-I0 2.9780138812054I6E-13

^5 Ce
C-,

2.14459I979966532E-13

217

Table A. 14 Continued. Phase API Order of the Expression Polynomial Constant Name Vapor 60 5 Polynomial Constant Value 251.8660791841976 0.306490229043447 2.448736920257488E-4 1.660I99941688756E-7 -2.37550436I9027IE-I0 9.481283506091226E-14 Vapor 70 5 Polynomial Constant Value 261.3058801981097 0.302175899050781 2.705655244454874E-4 1.169952889013004E-7 -2.028500223696939E-10 8.5602828I6441859E-14

Phase API Order ofthe Expression Polynomial Constant Name

Vapor 80 5 Polynomial Constant Value 275.80426423467 0.299026886717911 3.42965375921267E-4 -I.56378III4599649E-7 I.8I222870965312E-I0 -9.784376469162197E-14

Vapor 90 5 Polynomial Constant Value 299.5719446004368 0.30523I3I3810509 2.9157460I0856424E-4 2.7813798764I5357E-8 -8.450989602939215E-11 3.1I26I7977833836E-14

'The polynomial expressions correlate the data in the temperature range of 0F to I200F. The basis is liquid at -200F. The unit of enthalpy is Btu/lb. ^The polynomial expression is regressed from the curves in Graph 1 in Appendix 2 of Watkins (1979).

218

Table A. 15 Constants of Polynomial Expression for Calculating the Enthalpy ofa Cmde Cut in Saturated Vapor Phase from Its API Gravity and Temperature. '^ Phase API Order of the Expression Polynomial Constant Name Vapor 40 6 Polynomial Constant Value 233.4883816781221 c,
C2 Ci
CA

Vapor
50 6 Polynomial Constant Value 243.9527180031873

0.3285I8587I42753 -I.808624958812288E-4 2.632468991237147E-6 -6.258886072613157E-9 6.897744067547659E-12 -3.070086345068816E-15 Liquid 60 6 Polynomial ConstEuit Value 251.8582088107942
0.338170381568489 -9.376740388233884E-4 1.340003429817216E-5 -6.I00737995340388E-8 1.2145I1902912453E-10 -8.96174754299945IE-14

0.403622100740904 -1.852045328405438E-3 1.56524139338643E-5 -5.057826952398203E-8 7.465319567696318E-11 -4.157782127940892E-I4 Liquid 70 7 Polynomial Constant Value 262.0953662637621
0.217428358620964 2.309650226379745E-3 -2.73092370264294E-5 2.319865486377637E-7 -1.094177708507726E-9 2.487165117448216E-12 -2.138475785738538E-15

^5
Ce

Phase API Order ofthe Expression Polynomial Constant Name

r.

219

Table A. 15 Continued. Phase "API Order of the Expression Polynomial Constant Name Co c, c, C3 c c,
^^5

Vapor 80 7 Polynomial Constant Value 276.035738839535 0.279704957385547 2.320989198778989E-3 -6.030673040413603E-5 7.08380111014I508E-7 -4.129376077188773E-9 1.I56369803785671E-11 -I.246418830627948E-14

Vapor '~

Polynomial Constant Value

c c

'The polynomial expressions correlate the data in the temperature range of 0F to 1200F. The basis is liquid at -200F. The unh of enthalpy is Btu/lb. ^The polynomial expression is regressed from the curves in Graph 1 in Appendix 2 of Watkins (1979).

220

Table A. 16 Constants of Polynomial Expression for Calculating the Steam-free Delta T Given the Value ofthe Percent Stripout of Cmde Cuts. ''^ Constant
Order 0.04486391365208 1.876074961444829 0.070454820517625 6.651550673268503E-3 3.945026107317062E-4 1.150802438765197E-5 1.367411382319217E-7 0.047805972615606 1.472885452181799 0.047401526691829 -5.117099429298833E-3 3.396233130956716E-4 -1.063810533707965E-5 1.270384760859722E-7 -0.05627695162184 1.388574574821178 -0.0155528174116392 2.29546409696013 lE-3 -9.220926313879829E-5 1.397773963740523E-6

Light Naphtha, Heavy Naphtha

Light Distillate

Heavy Distillate, AGO, VGO

The polynomial expressions correlate the data in the percent stripout range of 10% to 30%. The unit of steam-free Delta T is F. ^The polynomial expression is regressed from the curves in Figure 2.20 of Watkins (1979).

221

Table A. 17 Constants of Polynomial Expression for Calculating Stripout from Steam Rate 1,2 Constant Light Naphtha, Heavy Naphtha Light Distillate 32.79539154772647 -140.9899756833911 673.3640444278717 -2.076813027858734E3 3.610560988426209E3 -3.2039297351837I6E3 1.1I5012320518494E3 Reduced Cmde 36.73691331990995 -276.1504411064088 1.645269501239061E3 -6.296468217134476E3 1.382960I08709335E4 -1.533274863910675E4 6.3985597968I0I5E3

c^ '0 ' c^ c^
^2 ^

26.14695580938133 -142.7715174853802 983.3651920557022 -4.343146883010864E3 1.035283389568329E4 -1.197023190975189E4 5.10I304268360138E3

Heavy Distillate, AGO, VGO 42.21995899023023 -182.3823599107564 914.8338382840157 -3.330140159606934E3 7.333609569549561E3 -8.285482303619385E3 3.52004I457176209E3

^3 c,4 ' ' c^ c

Constant c^ c,
''I

^0

c^ c^ c c

''5

' The range of steam rate that the correlations apply is from 0 to 60 pounds of steam/barrel of stripped liquid. The unit of stripout is vol.%. ^The polynomial expression is regressed from the curves in Figure 2.13 Watkins (1979).

222

Table A. 18 Constants of Polynomial Expression for Calculating the Steam-free DT Minus Actual DT(F) from the Temperature (F) Difference between Feed and Stripping Steam and Percent Stripout. ''^ Percent Stripout Order
0.033722314836866 -1.065916488052709E-3 1.403707231880618E-6 -3.384139080733591E-8 -6.43010240533469E-12 1.4733666746051lE-13 4.334365325077462E-3 -7.77647455743441E-3 -7.249742002063996E-7 -2.896324521711872E-8 5.159958720330243E-12 -1.587679606245378E-15 0.025291736127647 -0.056599241882988 -3.732436294355723E-6 -9.642573628642823E-8 2.897515281416171E-11 -9.097404143844305E-14

10%

20%

30%

'The polynomial expressions correlate the data in the range of-400F to 400F for the difference between feed temperature and stripping steam temperature. The unit of Steam-free DT is F. The polynomial expression is regressed from the curves in Figure 2.21 of Watkins (1979).

Table A. 19 Constants of Polynomial Expression for Calculating the Enthalpy of Steam from Temperature. 1,2 Order ofthe Polynomial Expression Polynomial Constant Name Polynomial Constant Value 4.070E+0 -0.616E-3 I.281E-6 -0.508E-9 0.0769E-I2 'The polynomial expressions correlate the data in the temperature range of 540R to 1800R. The unit of enthalpy is Btu/lb. ^The polynomial expression constants are from Table A-21E of Moran and Shapiro (1996). 223

Table A.20 Constants of Polynomial Expression for Calculating the Enthalpy of Air from Temperature. 1,2 Order of the Polynomial Expression Polynomial Constant Name Polynomial Constant Value -1.705163359642029 0.248415488749743 -I.90835I259771735D-5 1.393I9320524578D-8 5.89I37245932I254D-13 -1.166776I32260656D-15 'The polynomial expressions correlate the data in the temperature range of 500R to 1320R. The unit of enthalpy is Btu/lb. ^The polynomial expression is regressed from the data in Table A-22E of Moran and Shapiro (1996).

Table A.21 Constants of Polynomial Expression for Calculating the Enthalpy of Water from Temperature. 1,2 Order ofthe Polynomial Expression Polynomial Constant Name Polynomial Constant Value -31.808 0.9984 'The polynomial expressions correlate the data in the temperature of I IOF to 150F. The unit of enthalpy is Btu/lb. ^The polynomial expression is regressed from the data in Table A-2E of Moran and Shapiro (1996).

224

Table A.22 Constants of Polynomial Expression for Calculating the Slope of Flash Reference Line from Corresponding Distillation Reference Line.'
Order ofthe Polynomial Expression Polynomial Constant Name 5 Polynomial Constant Value 1.281878608097031 E-3

0.143415450581415
C2 Ci

0.085872677521365

-2.583246I7I070641E-3 -2.19426I556383026E-4
1.534796214297529E-5

c,

'The polynomial expression is regressed from the curve in the top fiugre on page 228 of Moran and Shapiro (1996). Table A.23 Constants of Polynomial Expression for Calculating the Ratio of DT(flash)/DT(TBP) from Volumetric Percent Distillated. 1,2
Order ofthe Polynomial Expression Polynomial Constant Name Polynomial Constant Value

0.206045789459949 0.098090319869243 -0.021268318498414 2.577717061399198E-3

-1.856466131933132E-4

7.70299445962408E-6 -I.685715965774048E-7
1.50049388647662E-9

'The volumetric percent distillated is in the range of 0% to 100%. The unit of temperature isF. ^The polynomial expression is regressed from the curve in the top figure on page 229 of Maxwell (1950).

225

Table A.24 Constants of Polynomial Expression for Calculating the Temperature Difference between the Distillation and Flash Reference Curves from the Slope of Distillation Reference Curve.''^ Case Order ofthe Polynomial Expression Polynomial Constant Name T50 (Distillation Reference Curve) < 300 F
10

T50 (Distillation Reference Curve) > 300 F 10 Polynomial Constant Value 7.510650799842551 5.426912218332291 -19.98555105924606 26.42150974273682 -18.22189289331436 7.298733577132225 -1.746701300144196 0.253036742098629 -0.021768757607788 1.024311339278938E-3 -2.0320097I7822803E-5

Polynomial Constant Value 0.046535948757082 -4.02163065969944 12.65744310617447 -12.82720935344696 5.004324972629547 -0.43010459802977 -0.194861501455307 0.060458100866526 -7.29041948216036E-3

Co

4.I90444597043097E-4 -9.5I13I7557553412E-6

'10

'The slope is in the range of 1 to 12. The unit of temperature is F. ^The polynomial expression is regressed from the curve in the middle figure on page 228 of Maxwell (1950).

226

Table A.25 Constants of Polynomial Expression for Calculating the T50 of Flash Curve under Vacuum from the Pressure and T50 ofthe Flash Curve under Atmospheric Pressure.
1,2

Pressure Order ofthe Expression Polynomial Constant Ntime

5 mmHg

lOmmHg

Polynomial Constant Value -1422.40771484375 47.98374176025391 -0.601449653506279 0.00387019373010844 -1.40265651680238Ie-005 2.897231166087977e-008 -3.1809I3909009431e-01I 1.440629782690204e-0I4

Polynomial Constant Value 993.2503967285156 -26.02331018447876 0.2790574356913567 -0.001563787373015657 5.065428638317826e-006 -9.480977780640387e-009 9.524453057838112e-0I2 -3.975758540364488e-015 50 mmHg 5 Polynomial Constant Value -147.5445291846991 2.970037258812226 -0.0I730I7894876466 6.152585774188424e-005 -9.930441327229977e-008 6.058668425965486e-011

Pressure Order ofthe Expression Polynomial Constant 'Name

25 mmHg 7 Polynomial Constant Value -39.01131057739258 -1.205847382545471 0.03788168542087078 -0.0003145772279822268 1.342447035312944e-006 -3.07732755944201 le-009 3.6129467202283I3e-012 -1.705918532418649e-015

227

Table A.25 Continued Pressure Order ofthe Expression Polynomial Constant Name Polynomial Constant Value -39.28636805340648
"-1

100 mmHg

200 mmHg

Polynomial Constant Value -38.44197991769761 1.383079235354671 -0.005222666145073163 2.I29300323439054e-005 -3.68I46I7920I2786e-008 2.341769013081753e-011 400 m m H g 5

1.059575435821898 -0.002797604639908968 l.I7I939102029285e-005 -I.94886755414I254e-008 209850868949959e-0Il

c,
c.

Pressure Order ofthe Expression Polynomial Constant Name

300 mmHg 5
Polynomial Constant Value -46.21546807419509 1.752744925528532 -0.00828888484647905 3.486289179832625e-005 -6.448200663179693e-008 4.374364872I323I4e-0Il

Polynomial Constant Value -29.64459969289601 1.454257622928708 -0.005063669466494503 2.092687345367494e-005 -3.797053613197043e-008 2.536417829122271e-01I

228

Table A.25 Continued Pressure Order of the Expression Polynomial Constant Name 500 mmHg 5 Polynomial Constant Value -15.75690979277715
"1
C-,

600 mmHg 5 Polynomial Constant Value -19.58084477111697 1.597486192593351 -0.008274154270111467 4.942406480523687e-005 -I.46668I26477234e-007 2.125436487237804e-010 -1.201000766633333e-0I3

1.200692083148169 -0.002377156030320293 9.557379709423941e-006 -1.668142990407517e-008 1.0758158373411Ie-011

Ci

c,

' The range of T50 that the correlations apply is from 50 to 500C. ^The polynomial expression is regressed from the curves in Figure II-1-24 in Lin (1988).

229