UNIVERSITY OF KHATOUM FACULTY OF ENGINEERING CHEMICAL ENGINEERING DEPARTMENT PRODUCTION OF CUMENE A PROJECT SUBMITTED IN PARTIAL FULLFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF BS.C. (HONORS) IN CHEMICAL ENGINEERING BY: ISHAG HAROON MOHAMED ALAWAD 072013 AMR ABDALLA IBRAHIM ABDALLA 072032 MOHAMED ABDELAZIM OMER MIRGANI 072036 SUPERVISED BY: Dr. TAJ ALASFIA MUBARAK BARAKAT. SEPTEMPER 2012Dedications This project is dedicated to our families, teachers and to all of our colleagues and friends with love and respect. To all of people that we love and respect and helped us, we are very thankful to all the people who inspired us with their attitude and unlimited support.Acknowledgement We would like to offer our deep thanks to our supervisor Dr.Taj Alasfia Mubarak Barakat for his unlimited support, grateful efforts, guidance and continuous encouragement to present this research in this form.Abstract The objective of this project is to design plant to produce cumene from 20 % of locally produced propylene in 2011, with the rate of 30,973.84 ton per year. Cumene production process is gaining importance and so the process needs to be studied to reduce the production cost. The main use of cumene is as a feedstock for the production of phenol which is used for production of polycarbonate (PC) resins. The Q - Max process was used here for cumene production from propylene and benzene on Zeolite-beta catalyst. The main units of this process are two reactors and three distillation columns. Based on this process the materials, unit operations and processes involved are identified. Material and energy balances were sequentially carried out for each unit in the same order by which they appear in the rough flow sheet. Steady state simulation was done. The production rate of cumene was found to be 60,217.6 ton per year with purity of 99.56 %. Process equipment and ancillaries were designed with their corresponding control systems. Also economic viability of plant was studied and the plant found to be feasible. It has a positive net present value, payback period of four years and intemal rate of retums higher than the preveiling interest rate. HAZOP and environmental analysis were conducted and the plant found to be environmentally friendly. Plant location was selected in Khartoum north and site was laid out. Finally recommendations for future works were considered.List of contents: Content Page No. Dedication T ‘Acknowledgements Abstract it perce] 1 List of Contents Ne List of Figures xIV [seCeebee S|: Sah.) see aetieneneeer eres bavi Chapter I: Introduction and Literature Review T 1.1 Introduction a ait te 1 1.2 Literature Survey I 1.2.1 Physicel properties 3 ~~ 1.2.2 Chemical Properties S 12.3 Uses 3 12.4 Demand 6 "12.5 Market 7 1.2.6 Production processes 8 1.2.7 Current Industrial process 17 1.2.8 Production Target 7 | Chapter 2: Process Description einen 2.1 General Process Description 21 2.2 Deiailed Process Desorption D 2.2.1 Section 1: Alkylation and Transalkylation 224.45 Alkylation Reactor Pre-heater, E-101 @ 4.4.6 Alkylation Reactor, R-101 6 47 Depropanizer Columa Pre-cooler, E-201 A 4.4.8 Depropanizer Column, T-201 a 4.4.9 Pre-Transalkylation Reactor Mixer (7 44.10 Benzene and DIPB Pump, P-102 Th 44.11 Trasalkylation Reactor Pre-Heater, B-102 75 44.12 Transalkylation Reactor, R-102 76 44.13 Pre-benzene Column Mixer 77 44,14 Benzene Column Pre-Cooler. B-202 3 8 44.15 Benzene Column, T-202 B 44.16 Cumene Column, T-203 80 4.5 Process Simulation r= 81 45.1 introduction a1 45.2 Cumene Process Simulation 82 4,6 References af 84 Chapter 5: Equipment Design 85 3.1 Introduction 85 5.2 Reactor design 8 5.2.1 Alkylation Reactor a 86 5.2.2 Transalkylation Reacior 107 3.2.3 References of reactor design 4 3.3 Distillation Columns Design 15 533.1 Introduction 1s 3.3.2 Distillation column design r 16 122 5.3.3 Chemical design of T-202 vu6.54 Cumene Storage Tank, T-202 242 6.5.5 Propylene Feed storage Tank, T-102 243 6.5.6 Propane By-product storage Tank, T-201 243 | 66 Cooling Tower [24 6.6.1 Total Water Load anii2as: 6.6.2 Cooling Tower Sizing 245 67 Steam Load ib 248 6.8 References 249 | Chapter 7: Process Control 250 77.1 Introduction 7.2 Requirements of control 72.1 Safety 72.2 Product specifications 251 7.2.3 Environmental regulations 21 | 7.2.4 Operational constraints 251 72.5 Economic 251 9)| 73 process variables 252, 7d Hardware elements of a control system | 253 7.4.1 The chemical process 255" 7.42 The measuring instrument or sensor 253 7.43 Transducers 253 | 7.44 Transmission line is 253 7.4.5. The controller | 253° 7.4.6. The final control element 258° | | TAT Recordingelement 2 | 7.5 Classifications of control 2548.3.5 Handling and Storage Precautions: 288 | 8.3.6 Exposure Controls and Personal Protection 288 3.4 Propylene hazards identification 289 8.4.1 Flammability 289 8.4.2 Toxicity 289) 8.43 Health effects 789 8.4.4 First aid measures 290 8.4.5 Fire and explosion hazards 2 291 8.4.6 Firefighting instruction 291 8.4.7 Handling and storage 292 8.4.8 Engineering controls 392 | 8.4.9 Eyc/face protection 292 8.4.10 Skin protection D 292 8.5 Propane hazards identification [293 8.5.1 Toxicity 293 «| 8.5.2 Flammability 293 8.6 Di-isopropylbenzene hazards identification 294 8.6.1 Flammability 294 8.6.2 Health effects 294 | 863Pistadmeasres = 204 8.6.4 Handling 294 8.6.5 Storage | 294 8.7 Beazene hazards identification 295 1 Toxicity and health effects | 295 (7keamabiny | = gee, ceie = tae 295 8.7.3 Firefighting procedures 295 xt10.3 Site Layout 362 [104 PlantLayouw 364 10.5 Cumene Plant Site Selection and Leyout 367 10.6 References — 30 Conclusion 370 Recommendations 31 ‘Appendices 372 xuFigure 4.12: E-201 A [Figure 4.13: T-201 7 | Figure 4.14: Pre-transalkylation Reactor Mixer B [Figure 4.15: P-102 ii iF 7h “Feue 4.16: E-102 rE Figure 4.17. Transalkylation Reactor 76 Figure 4.18; Pre-benzene Column Mixer 7 ae 7 Figure 4.19: B-202 B Figure 4.20: T-202 B Figure 4.21: T-203 “al 80 Figure 4.22: Process Simulation Flow Diagram 82 Figure 5.1: Spatial structure of beta zeolite 6 Figure 5.2: Mole balance around differential volume clement — 90 Figure 5.3: I/-t, Vs. X, along the reactor 96 Figure 5.4: Hemispherical Head for the alkylation reactor 9 Figure 5.5: Temperature — conversion profile along the reactor 103 | Figure 5.6: Temperature — length profile of the reactor 105 Figure 5.7: Alkylation Reactor Dimensions 106 ‘Figure 5.8: Hemispherical Head for the transalkyletion reactor T10 Figure 5.9: Transalkylation Reactor Dimensions 113 Figure 5.10; Distillation column (a) Basic column (b) Multiple feeds and | 117 side streams Figure 5.11; Flooding velocity, sieve plates 133 Figure 5.12: Selection of liquid flow arrangement 139 Figure 5.13: Relation between downcomer area and weir length 140 Figure 5.14: Relation between hole area and pitch 142 xv[Figure 7.4: Reactor pressure control loop 262 “Higare 75: Reactor overall cortol i |262 Figure 7.6: Pre-cooler control loop 264 | Figure 7-7: Distillation column top pressure control loop Tek 266 Figure 7.8: Dram level control loop for distillation column 268 | Figure 7.9: Re-boiler level control loop 269 Figure 7.10: Distillation column overall control 270 Figure 9.1: Column plates cost. Time base mid-1998 317 Figure 9.2: Cost of vertical pressure vessels. Time base mid-1998 318 Figure 9.3: Cost of shell and tube heat exchanger. Time base mid-1998 | 321 Figure 94 The cost of the pump, Time base mid-1998 = 324 Figure 9.5: The cost of the cooling tower, Time base mid-1998 325 Figure 10.1 Plant layout 368Table 4.4; Mean heat capacities calculation using equations él Table 4.5: Mean critical temperature and pressure of the mixture calculation | 62 Table 4.6: Heats of formation i 70 Table 4.7; Latent heat constants 7 72 Table 5.1: Physical propertics of a zeolite catalyst [87 Table 5.2: Calculation of the mean specific heat capacity 92 “Table 5.3: The alkylation reactor feed component flow-rates. 93 Table 5.4: X, and -1 versus temperature within the reactor 95 Table 5.5: The variation of selectivity with feed temperature iol Table 5.6: Alkylation reactor final design specification 105 Table 5.7: The transalkylation reactor feed components molar rates 108 Table 5.8: Transalkylation reactor Final design specification 112 Table 5.9: The feed, top and distillatc flow rates and compositions | 122 composition of T-202 ‘Table 5.10: the constants for the vapor pressure calculations for T-202 123 Table 5.11: 126 Table 5.12: The liquid vi 127 Table 5.13: vapor density calculations with data obtained from Chemead for | 131 7-202 Table 5.14: Liquid density calculation with data obtained from Chemead for | 132 T-202 Table 5.15; Contribution to Sugdens’s parachor for organic compound 135 Table 5.16: Surface tension calculations for T-202 [136 | Table 5.17: The bottom liquid and vapor flow rates and compositions for T- | 137 202. Table 5.18; Provisional Plate Design Specification for 1-202 167 xxTable 6.6: Nominal Capacities of Standard Vertical Cylindrical Tanks 241 Table 6.7: Cooling water requirement 245 Table 6.8: steam requirement — 248 Table 7.1: The kinds of controllers suitable for the common variables 254 Table 7.2: Control Loop elements Identification 255 ir fiaok Foam op iy i mn ote 101 temperature control Table 7.4: Elements of control loop for the Alkylation reactor R-101 | 259 temperature control Table 7.5: Elements of control loop for alleylation reactor R-101 temperature | 261 control Table 7.6: Elements of control loop for the heat exchanger E-102|263 | temperature control Table 7.7: Elements of control loop for distillation column 1-201 pressure | 265 Table 7.8: Control loop elements for drum level control for T-201 267 | Table 7.9: Control loop elements for Re-boiler liquid level control 269 Fable 7.10: Elements of control loop for the heat exchanger B-102| 271 temperature control Table 711: Elements of control loop for the transalkylation reactor R-102 | 272 ‘temperature control Table 7.12: Elements of control loop for the Alkylation reactor pressure | 273 control Table 7.13: Elements of control loop for the Heat Exchanger E-104 | 274 temperature control Table 714 Elements of control loop for Benzene distillation column T-202 | 275 | top section pressure xTable 9.10: Flectrical components cost 332 Table 9.11: Yard improvements costs of the plant 334 Table 9:12: costs of service facilities 335 Table 9.13: Enginesting and supervision costs 337 Table 9.14: Typical variations in construction expenses 338 | Table 9.15: Depreciation of items calculation 342 Table 9.16: Depreciation of the plant through 20 years period calculation | 343 Table 9.17: Predetermined utilities amount for the plant (346, Table 9.18: Net profit calculation : 351 Table 9.19; Present value calculations for each year 353 Table 9.20: Sensitivity analysis 356 xtChapter 1 Introduction and literature | reviewChepter 1: Introduction 1 Introduction Tsopropyl benzene popularly known as cumene is an important intermediate in the chemical and polymer industries. During World War Il, cumene was used to make ‘a high-octane blending component for military aviation gasoline, whereas today cumene is no longer used as a fucl, but it has grown in importance as a feedstock for the production of phenol ""). Besides being the principal chemical used in the production of phenol and its co- product acctone on an industrial scale; cumene is elso the starting material in the production of Acetophenone, methyl styrene, di isopropyl benzene and di-Cumyl peroxide. Minor uses of cumene include gs a thinner for paints, enamels, and lacquers, as a constituent of some petroleum-based solvents such 2s naphtha, It is also a good solvent for fais and resins and has been suggested as a replacement for benzene in many ofits industrial applications. ‘The majority of all cumene manufactured in the world today is used for the production of phenol. Tae demand for pheno! for the manufacture of Bisphenol-A and subsequently polycarbonates is accelerating, owing the broadening applications of polycarbonates in the electronic, healthcare and automobile industry. A shift in the phenol derivatives market has taken place in receat years, with Bisphenol-A overtaking phenolic resins 2s the major driver for phenol growth. Consequently, pressure has increased for product improvements in both phenol and acctone, in turn creating demand for higher quality Cumene produced upsircam. By Cumene is currently produced by the allylation of benzene with propylene over an acid catalyst such as Aluminum Chloride, Boron tri-Fluoride, Phosphoric Acid, Hydrogen Fluoride, supported Phosphoric Acid (SPA) etc. The alkylation reaction is indicated by the following chemical equation:Chapter 1: Introduction 1.2 Literature Survey 1.2.1 Physical properties Cumene (CAS no. 98-82-8) with a chemical formula of CyHi2 is also known as 2-phenylpropane, isopropylbenzene and 1-methylethyl-benzenc. It is a volatile, colorless liquid at room temperature with a characteristic sharp, penetrating, aromatic odor, is nearly insoluble in water but is soluble in alechol and many other organic solvents. It is combustible and not compatible with oxidizers, nitric acid and Sulphuric Acid. Structurally, cumene is a member of the alky! aromatic family of Hydrocarbons, which also includes Toluene (methylbenzene) and Ethylbenzene. Its structural diagram is given below in Figure 1.1 and some relevant physical and thermodynamic properties of cumene are listed in Table 1.1 Figure 1.1 structural diagram for cumene “!Chapter 1: Introduction Table 1.1 Physical & thermodynamic properties of Cumene, cont, 41 Property value | Melting point, °C ity at 20°C, eCm" | Thermal conductivity at 25°C, WinK 1.2.2 Chemical Properties ™ > Cumene undergoes oxidation to give cumene hydro peroxide by means of air or oxygen: CoHCH(CH:), + O}————+ C By the catalytic action of dilute Sulphuric acid, cumene hydro peroxide is split into phenol and Acetone: CoHsC(CH;,00H —————» C,H;OH + CH;COCH cumene hydro peroxide phenol acetone 1.2.3 Uses ‘Around 98% of cumene produced is used to produce phenol and its co-product acetone. However, the requirement of cumene is largely dependent on the use of phenol’s derivatives which have resulted in increasing requirement rates for cumene. The largest phenol derivative is bisphenol-A (BPA) which supplies the polycarbonate (PC) sector. PC resins are consumed in automotive applications in place of traditional materials such as glass and metals. Glazing and sheet uses, such as architectural, scourity and glazing outlets, are also important PC applications. ‘The third largest use for PC is optical media such as compact dises (CDs) and digital versatile discs (DVDs)."!Chapter J: Introduction 1.2.5 Market Demand for cumene is strongly tied to the phenol market. Trade in cumene accounts for only 4% of world production. The biggest exporters of cumene are the United States (to Germany) and Japan (to the Republic of Korea). Taiwan also imports large amounts of cumene for phenol production. As of carly 2011, the U.S. cumene market was tight primarily as @ result of a shortage of feedsiock propylene. Scheduled plant maintenance by several large cumene manufacturers wes also planned for early to mid-2011. Because of the cumene shortages, phenol and acetone plant operating rates have been reduced significantly, which in turn has restricted phenol exports to Europe and higher-domand regions such as Asia and South America." Tnereased demand for Bisphenol-A and phenolic resins will result in strong demand for phenol, particularly in Asia (excluding Japan). As a result, consumption of cumene for phenol production is forecasted to grow at approximately 8% per year in the region. China alone is expected to add over a million metric tons of cumene capacity during 2011-2015 (with most capacity coming on-stream in 2013) to supply its phenol/acetone plants that are expected fo come on-stream during that period. Overall, worldwide cumene consumption for the production of phenoV/acetone is forecasted to grow at an average annual rate of about 4.5% during 2010-2015. Some of the biggest cumene manufacturers in the world are: Continental Chemical USA, Flint Hills Resourees, INEOS, Georgia Gulf Corporation, Chicago Bridge & Company N.V.'Chepter 1: Introduction purification column, The laiter column separates overhead Cumene product from a stream containing the heavy polyallkylates."! The main limitations of the SPA technology are related to product purity and yield, as well as operational and environmental issues. Phosphoric acid is not sufficiently active to promote the transalkylation of PIPB back to Cumene. PIPB and other heavy components must be removed in the bottoms of the lest distillation column, resulting in yield losses. To minimize the formation of PIPB, as well as of propylene oligomers, the process typically employs a high benzene/propylene (B/P) feed ratio of the reaction system that reaches 8:1. Because of the high operating temperatures in the SPA-based reactor, the catalyst is subjected 10 dehydration and requires the controlied addition of water for proper performance. If excessive water is introduced, the SPA pellets tend to agglomerate, resulting in shorter catalyst life and difficultics in ualoading the reactor. The catalyst is not regencrable and must be disposed of after 6 to 18 months of continuous operation." ‘The Aluminum Chloride Based Process AICls has long been used as a catalyst in liquid-phase alkylation processes, particularly in the production of ethylbenzene from benzene and ethylene, In the 1970s, Monsanto and Lummus introduced a modified version of the technology, using smell concentrations of AICI in a homogeneous liquid-phase reactor. During the 1980s, three Cumene producers in the United States, France, and Finland retrofitted their SPA-based plants into single-phase AIC)s-hased processes. This technology, currently licensed by Kellogg, was also employed in a grassroots cumene plant in Taiwan that came on stream in 1995." In the Monsanto-Kellogg process, the catalyst is a mixture of anhydrous AICls and hydrogen chloride, which is completely dissolved in the liquid hydrocarbon phase. Benzene alkylation takes place below 135°C (275°F), and at sufficient pressure to 8Chapter 1: Introduction ‘An additional drawback of the use of AICI; and hydrogen chloride is that they are highly corrosive. Special materials of construction must be used in the reaction and catalyst separation systems.”) ‘The Zeolite-Based Process Zeolite catelysts have been commercially employed in ethylbenzene processes since 1980. Their use for eumene production, however, required additional years of research, In 1992, Dow added a zeolite transalkylation reactor to its SPA-based cumene plant at Tereuzen in Netherlands. In the next few years, cumene processes based completely on zeolite technology slarted to be offered for license. Examples include the processes developed by Mobil-Badger, UOP, and CDTech (a partnership between ABB Lummus Global and Chemical Research & Licensing). Between 1996 and 1998, several cumene expansions employing zeolite technology were completed worldwide. In the United States, 7 cumene plants were retrofitted from SPA to zeolite technology, with 4 using the Mobil- Badger process and 3 using UOP technology. The CDTech process will be used in a grassroots plant planned for construction in Taiwan by 2000. EniChem also developed its own zeolite technology, which was employed to revamp its SPA-based facilities at Porto Torres, Italy." Except for the CDTech process, which combines catalytic reaction and distillation ina single column, all zeolite-based processes consist of essentially the same flow sheet configuration. The alkylation reaction is carried out in fixed-bed reactors at temperatures below those used in SPA-based processes. When refinery-grade propylene is used as a feedstock, the effluent from alkylation is sent to a depropanizer column that removes propane overhead, A separate transalkylation reactor converts recycled PIPB and benzene to additional cumene. The bottoms of the depropanizer are then mixed with the transatkylation reactor effluent and fed to a series of three distillation columns. Benzene, product cumene, and PIPB are unChapter 1: Introduction Technical Developments of Zeolites-Based Process Zeolites are porous erysialline materials composed of a three-dimensional framework of SiO4 and AO, tetrahedra, each with a silicon or aluminum atom in the center. These tetrahedra are cross-linked by the sharing of adjacent oxygen atoms, forming ring structures thet are characteristic of each type of zeolitic material, The number of tetrahedra in the rings determines the size of the pores and channels within the zeolite famework. High reaction selectivities can be obtained with zeolite catalysts, partly because of the molecular sieving effect of the zeolites.) Medium-pore zeolites (such as Mobil's ZSM-5) are well-known alkylation catalysis, particularly in the vapor-phase production of ethylbeazene. These catalysis normally require the use of high reaction temperatures to achieve acceptable rates of benzene diffusion. For cumene production, however, high ‘temperatures lead to excessive formation of n-propylbenzene (NPB) and propylene oligomers, as well as fast catalyst deactivation. Thus, most recent research has focused on the use of wide-pore zeolites, such as zeolite Y (faujasite-type), modernite, and zeolite beta. The main challenge has been to develop a 7eolite combining high activity, selectivity. and stability for cumene production." Zeolites are frequently prepared in a sodium form and subsequently treated by ion exchange with acids or ammonium salts, In the case of the ammonium-exchanged zeolite, the acidic form is normslly obtained by an additional heating step that releases ammonia, Rare earths, alkaline metals, or other metal components can also be added to the zeolite by ion exchange or impregnation. To increase the physical strength and attrition resistance of the catalyst, the zeolite crystals are often mixed with a binder material such as clay, silica, or a metal oxide," Important factors to be controlled in a zeolite include surface area, pore size distribution, crystal size, and SVAl molar ratio, By increasing the Si/A1 ratio of the 8Chapter 1: Introduction propylene conversion in the distillation reactor is limited to about 90%, which requires the use of an additional fixed-bed polishing reactor"! Acidic zeolites are sufficiently active to transalkylate poly sopropylbenzenes: (PIPB) back to cumene, Transallylation is typically carried out at 130-220°C (266-428°F) and 300-600 psi, with a benzene/PIPB molar ratio range of 4 to 10. ‘Although alkylation and transalirylation can occur simultaneously, two separate fixed-bed reactors are normally employed." In a typical zeolite-based process, the separation section includes a depropanizer, a recycle benzene column, a cumene rectifier, and a column for separating recyclable PIPB from small amounts of heavy residue, A portion of the benzene recycle stream is mixed with PIPB and sent to the transalkylation reactor, An additional reactor can also be used to convert diphenylalkanes into lighter aromatics. In the catalytic distillation process, the alkylation effluent strcam is essentially free from benzene, and a separate benzene recycle column is not needed. However, CDTech has disclosed the use of a depropanizer for further fractionation of the distillation reactor overhead. Compared with alkylation catalyzed by SPA, the zeolite-based alkylation generates a higher amount of diisopropylbenzone (DIPB). However, these by-products can be recycled to extinction in a separate transalkylation reactor, where they are converted to additional cumene, Because only small amounts of heavy compounds are generated, the zeolite-based process can achieve overall cumene yields above 99.5% and product purities as high as 99.97%. In UOP's process, product impurities are claimed to derive primarily from impurities in the feedstocks. A. particular advantage of the zeolite catalysts is their regenerability, waich allows use for several cycles and results in significantly less waste disposal than required with SPA and AICI3 catalysts, Zeolite regeneration can be carried out by thermal asChopter 1: Introduction, 1.2.7 Current Industrial process The rapid growth of Cumeno, phenol and Bisphenol-A production, however, has caused some concerns related to the imbalance of the acetone byproduct produced by the phenol plant. Acctone and phenol are produced at an approximately 1:1 molar ratio from cumene but are used at an approximately 1:2 molar ratio in the downstream bisphencl-A production process. The excess acetone that is not used in the production of bisphenol-A has caused some concem from phenol producers in that it may create supply-demand imbalance and disrupt the economics of phenol production business.“ In today’s olefin’s market, there is also a supply demand imbalance in the supply of propylene produced from conventional sources such as cthylene plants due to the availability of feedstock that generally favor the production of propylene. This imbalance has forced phenol producers to build their plants closer to feedstock supplies rather than to product outlets. Numerous sescarch cfforts has been directed at solving the acctone imbalance and propylene issues described above by recycling the excess acetone produced in the phenol plant to produce cumene. An alkylation process is created in which benzene is reacted with acetone in the presence of hydrogen and zink chloride cotalyst and another process is used to produce cumene from benzene & isopropanol in the presence of a pyrophosphate from a metal selected from group IB in the periodic table"! 1.2.8 Production Target The main objective of our project is to design a cumene plant that satisfies the local demand of cumene and a part of the world demand to achieve good economical revenues. This depends on raw materials availability (benzene and propylene) and world demand. The world demand for cumene is in increasing as indicated previously and the local produetion of benzene was 1,490,652 metric tons by year- end 2010£% Tn Sudan the imported cumene in 2007 was 43.44 metric tons, which v7: Introduction Chapter } Regenerable catalyst for less solid waste and lower disposal cost. > Longer catalyst eyeles for fewer turnarounds. > Non-corrosive system for lower maintenance costs. ‘Threc-fourths of all cumene units are integrated with a downstream phenol unit Combining the Q-Max process with the Allied/UOP Phenol process results in higher phenol yiclds, improved product quality, and lower overall utility consumption. The first Q-Max process unit came on stream at JLM Chemicals in August 1996 (see figure 2.2). The JLM project was @ revamp of an existing UOP Catalytic Condensation (SPA catalysi) unil, Revamp objectives wore: increased capacity, improved cumene yield, improved alphamethylstyrene quality from the phenol unit, lower catalyst cost, longer catalyst cycle length, and less equipment corrosion. ‘The QeMax unit at JLM met all performance guarantees and continues to satisfy ILM’s objectives. The unit continues to operate with the original catalyst loadings, adding 1o what is already the longest commercial zeolitic cumene catalyst run"! Figure 1.2: First -Max Unit: JLM Chemicals, Blue Island, IL, USA") 19CHAPTER 2 PROCESS DESCRIPTIONChapter 2: Process Description 2. Process Description 2.1 General Process Deseription Q-Max process is used in this project to design cumene plant. The process is divided into two sections which are alkylation/ transalkylation section and cumene recovery section as shown in figure 2.1. Propylene feed, a mixture of fresh and recycle benzene and recycle di-isopropylbenzene (DIPB) are charged to the alkylation and transalkylation section, where the propylene and DIPB react with benzene to form mainly cumene. Effluent from this cection is sent to the cumene recovery section, which removes the propane that entered the unit with the propylene feed, collects benzene and DIPB and reeyeles them to the alkylation & transalkylation section and recovers ‘cumene product and a small stream of heavy aromatic by-products.” Recydled Benzene Recycled DIPB Figure 2.1: Block Flow Diagram for the production of Cumene 21Chapter 2: Process Description additional cumene. The transalkylation reactor is operated at 160 °C and 35 bar, the benzene to DIPB ratio is 11 and the reaction is nearly isothermal. The effluent from the transalkylation reactor is then mixed with effluent from T-201 and sent to the benzene column T-202.! oo prsdoueons ssrenmoe of OD vor vara? cine unos aeateyg aa sooo zene as aoe oe = ‘wpresmat enone: eases i eogo lg 23Chapter 2: Process Description tom, iw ava raeaiee amutbisin —aatylon se Reverie” Roc ese pate eed adie = Ce (anaeet ‘To seetion | Flgure2. Process Flow Diagram for section 2 2sChapter 2: Provess Description 2.3 Process Chemistry The major reactions taking place are alkylation and trans-alkylation reactions. The other reactions involved include isomerisation and dis- proportionation. The reaction can proceed with or without carbonium ion intermediate. The alkylation of aromatic hydrocarbons belongs to a general class of electrophilic reactions known as Friedel-Crafts reactions. Propylene acts as the alkylating agent as shown in cquation (3.1). CHy—CH—CHy Acid + CH) =CH—CH3 ~ Benzene Propylene Cumene (2.1)8! ‘The reaction is exothermic (with heat of reaction equal to -23.4 kcal/mole at 250°C) ", rapid, and irreversible. Propylene conversions near 100% are usually obtained @. During alkylation, 2 small portion of cumene reacts further with propylene to form higher alkylated products as shown in equation (3.2)"!; Bene oy cH CH, —PH—CH, Bs Oo “Oe a, bs (22) The proportion of ortho, meta, and para configurations of diisopropylbenzene (DIPB) is affeeted by the type of catalyst used. The 2Chapter 2: Process Deseription 2.3.2 Other Side Reactions In addition to DIPB and TIPB, several minor by-producis are involved in the chemistry of cumene synthesis. Propylene can oligomerize to form hexenes, nonenes, or even heavier olefins. These by-products affect the Bromine Index, which is a measurement of olefins content in the final product. In addition, the olefin oligomers tend to react with aromatics fo form heavier alkylbenzenes, such as hexyl- and nonyl-benzene. Propylene oligomerization can be minimized by increasing the molar ratio of benzene to propylene in the reactor feed. However, larger amounts of benzene in the reaction system result in increased downstream separation costs"), Cracking reactions lead to the formation of ethylbenzene, butylbenzenes and diphenyl compounds. These reactions may involve cither the cracking of a higher alkylbenzene or the cracking of a propylene oligomer followed by benzene alkylation with the lower molecular weight olefins. Some a- methylstyrene may also be produced by cumene dehydrogenation ®), ‘The mechenism of cumene synthesis involves the protonation of propylene to form an isopropyl carbocation, which attacks the benzene ring by electrophilic substitution as illustrated by equation 3.5. An undesirable side reaction, known as “hydride transfer,” occurs when carbocation abstracts anbydride ion (H1) from the side chain of an alkylated aromatic as illustrated ty equation 3.6. Cumene, for instance, may be attacked by the isopropyl carbocation to form a cumylcarbonium ion. This intermediate may then react with a molecule of benzene and generate di-phenylpropane. A variety of bi- aromatic compounds can be formed, depending on which alkylated aromatic and which specific carbon is attacked by the carbocation. The hydride transfer reactions also Icad to the co-production of alkanes, such as propane and isomers of hexane ”!, 29Chapter 2: Process Description However, propane is inet during alkylation and is usually recovered in the cumene process as fuel or liquefied petroleum gas. Minor propylene impurities include ethylene, butylene, and cyclopropane, which by benzene alkylation may form ethylbenzene, butylbenzenes, and n-propylbenzenc respectively, Small amounts of methanol and ethanol are occasionally added to the propylene feed to prevent hydrate freezing in pipelines. During alkylation, these contaminants mey respectively form toluene and ethylbenzene. ‘Toluene, which is also an impurity in the benzene feed, can lead to the formation of cymenes (isopropylioluenes). Finally, commercial benzene may contain sulfur compounds like thiophene, which can be readily alkylated to isopropylthiophene™. 31Chapter 2: Process Description ‘Table 2.3: Heat exchanger F-101 stream table: Inputs outputs Se S “Temperature (°C) NA 160 Pressure(Bar) | 35—Stt~*«*@ 35 Component Flow rates (kmol/hr) | Benzene 444.44 444 ad Propylene 63.492 63.492, Propane 27.210 27.210 Cumene 0 0 DPB 0 0 “Total flow (kmollhr)| 935.143] 535.143 Table 2.4: Reactor R-101 stream table: ip Inputs ‘outputs S; Ss Temperature °C) “160 NIA Pressure (Bar) ~ 35 A 35 ‘Component Flow rates (Kmol/hr) ~~ Benzene 444.44 NA Propylene 63.492 NA Propane 22M 27211 Cumene 0 NIA DIPB 6 NIA | Toial flow (kmol/hr) 535.143 NIA 33Chapter 2: Process Description Table 2.7: Pump P-102 Stream table: Inputs outputs Sig Sis Temperature (°C) NA NA Pressure (Bar) NA 35 Component Flow rates (kmol/hr) ‘Benzene NA Al NA Propylene NA NA ‘Propane NA NWA Cumene NA NA DIPB NIA NA Total flow (kmol/hr) NIA N/A Table 2.8: Heat exchanger E-102 stream table: Inputs Outputs TS. § | Sis Temperature (°C) NA 160 Pressure (Bar) 35 es 35 Component Flow rales (mol) Benzene NA NA Propylene NA N/A Propane NIA N/A Cumene NIA N/A DIPB | NA N/A Total flow (kmol/hr) NA N/A 35Chapter Process Desc ‘Table 2.11: Benzene columnT-202 stream table: inputs, ouipuis Sis Sao Sa Temperature (C) NIA WA NA Pressure (Bar) NA Wa T 1 Component Flow rates (kmol/hr) Benzene NA NA NA Propylene NIA NA NIA Propane NA NIA NIA Cumene NA vA N/A DIPB NIA N/A N/A Total How (mols) | NIA WA NA Table 2,12: Cumene T-203 stream table: = i inputs outputs Sat Sx Sas ‘Temperature °C) N/A NA NIA Pressure (Bar) 2 NA NIA ‘Component Flow rales (kmol/hr) Benzene NIA NA NA Propylene NIA NA NIA Propane NIA NIA NA Cumene NIA NA NIA DIPB NA NA NIA NA NA NA Total flow (kmol/hr)CHAPTER 3 MATERIAL BALANCEChapter 3: Material Balance 3.1 Introduction In chemical processes, chemical engineers are interested in many of the physical parameters associated with each process such as flow rate of material that enters and leaves a piece of equipment, as well as several other parameters including the temperature of the of the material, and the pressure exerted by material. The material balance is basic work for designing any chemical or physical process units that used in any chemical industry. The material balance is the calculation of the material quantity of any stream enters or leaves a unit. This helps to achieve the best utilization of energy, equipment, process controlling and safety. ‘The best way to tackle a material balance problem will depend on the information given, the information required from the balance, and the constraints that arise from the nature of the problem. 3.2 Conservation of Mass Material balance is nothing more than the application of conservation aw for mass “Material is neither created nor destroyed". ‘Material balance is the arithmetic procedure which equilibrates the rates and exiting the process. It depends on the conservation law of materials which can be written as follows: Input + Generation = Output + Accumulation + Consumption en For steady state operation there is no accumulation, thus the conservation law becomes: Input + Generation = Output + Consumption (3.2) For steady state operation and without chemical reaction there is no disappearance or generation, thus the conservation law becomes: 39