Reactor Engineering

Ken K. Robinson
Mega-Carbon Company, St. Charles, Illinois, U.S.A.

INTRODUCTION Reactor and reaction engineering play a vital role in petroleum and chemical processing. The aim of this article is to acquaint the reader with the interaction between reactor design=selection and the characteristics of the chemical reaction of interest. Reactor selection and design are the basis of economical and safe operation. Chemical reactions in petroleum rening include a huge spectrum of unique properties. This includes how the reactants are contacted, whether a catalyst is used, how much heat is evolved or absorbed, and how fast the reaction takes place. This article guides the reader in selecting and designing reactors that will best carry out the reactions of interest. The reactor types discussed focus on those in a petroleum renery, but many can be used in chemical processing as well. This article rst describes the ideal reactor types, namely batch, plug ow, and completely mixed reactors. Then, the petroleum reactors are discussed based on whether the reaction occurs in the vapor, liquid, or mixed vaporliquid phase. More specically, the naphtha-processing reactors are examined rst, then gradually moving to heavier hydrocarbons, like kerosene and distillate, that react partially in the liquid and gas phases, and nally ending with a discussion on reactors processing heavy hydrocarbons like petroleum residuum, which reacts completely in the liquid phase.

THE IMPORTANCE OF REACTOR ENGINEERING Commercial reneries represent huge investments in capital. Small errors in equipment sizing or yield translate to millions of dollars in unnecessary expense. Hence, it is extremely important to do the best job possible on sizing, modeling, and specifying reaction conditions for petroleum rening reactors. We need to have a clear understanding of reactors in the three stages of development. At the earliest stage, the laboratory reactors explore new reaction conditions, catalyst formulations, or feedstock types. Reaction kinetics may also be studied at this stage and reaction rate models developed, making sure that there are no
Encyclopedia of Chemical Processing DOI: 10.1081/E-ECHP-120040388 Copyright # 2006 by Taylor & Francis. All rights reserved.

confounding factors of the experimental test that will not scale appropriately to the commercial reactor. The second stage of development is typically aimed at mimicking commercial operations by employing recycle streams to achieve realistic simulations of the integrated process. Isothermal conditions are usually maintained in the reactor, but if heat release is a concern, such as residuum hydrotreating, then it is wise to run adiabatically so that the adiabatic reaction temperature can be established and also how much heat must be removed in the nal commercial design. Dening catalyst deactivation, yield patterns, and how various feed types inuence the process are typical aspects to explore. Finally, we move to commercial scale and adiabatic operation. We need to design the commercial reactor so that it is sized properly, can be started up and shut down safely, and can be operated condently under steady-state conditions. It is a formidable problem for reaction engineers, but if they are careful and rigorous, the end product will be a success. The ow diagram of a gasoline-orientated renery is shown in Fig. 1. Most important, we look at the numerous reactors, which can convert feedstocks, sometimes catalytically and at other times with thermal processing to more valuable products. The reactors are summarized in Table 1 with some of the general characteristics. The large spectrum of reactors is shown in Fig. 2 with the vertical axis showing the progression from the simplest types such as a delayed coker (a semibatch reactor) to the highly complex uid catalytic cracking (FCC) unit, which has both the reaction phase and the catalyst being transported through the reactor.

REACTOR TYPES/MODELS Ideal ReactorsA Brief Review Many types of reactors have entered the eld of petroleum rening, but they can be roughly divided into three types: 1) batch; 2) continuous stirred tank reactor (CSTR); and 3) continuous plug ow. In smallscale studies, the researcher may use a simple pipe reactor, which is operated batchwise. The CSTR reactor is used in small-scale studies for kinetic studies
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Reactor Engineering

Gases Lt Naphtha C5-C6 Isomerization

BenZene Saturation

Chemicals Isomerate Lt Naphtha Lt Reformate

Reformer Fd Fractionator

Naptha HDS

Cat Reformer

Reformate Fractionator

Hvy Reformate Jet Fuel Diesel/Furn Oil Lu Arom Diesel

Hvy Naphtha Hydrocracker Aromatics Saturation LCCO Cat Feed Hydrotreat Fluid Cat Cracker Slurry Oil Delayed Coker Coke Gas Recovery Butane C4 Isom Iso C4 C4 Dehy MeOH

Atm Crude Crude oil Still

Kero HDS Diesel HDS

Lt Hydrocrackate Hvy Hydrocrackate Cat Naphtha C3-Olefins Butylene Alkylate Alkylation Unit

VGO Vac Distillation H2 Plant Vac Bottoms

MTBE/ TAME Fuel Oil

MTBE/ TAME

Fig. 1 Flow diagram of a gasoline-oriented renery. (View this art in color at www.dekker.com.)

because the reaction rate is derived directly from the inlet and out concentrations, and it may simulate operation in a larger commercial reactor such as an ebullated bed where the high recycle rate approximates complete mixing. For continuous processing, almost any petroleum fraction may be fed over a xed bed of catalyst in a plug ow reactor, with vapor phase operation for naphthas and trickle phase for distillates and residuum. The reactor performance equations for these three ideal reactors are given later. A microbatch reactor (5 ml) such as the tubing bomb reactor is a common, inexpensive device to develop data. The reactants and, optionally, the catalyst are changed in the small reactor, sealed, and then pressured. To start the reaction, the tubing bomb is typically immersed in a heated uidized sand bath for a specied length of time with agitation. Shortly after immersion in the heated sand bath, the reactor pressure is increased to a nal level, close to commercial conditions. To stop the reaction, the microreactor is pulled out of the heated bath and rapidly quenched in a cooling uid. The dening equations are given in Eq. (1).

Batch reactor equations Z t CA o

o x

dx rA

NA o t W

Z
o

dx 0 rA

thermal where

catalytic

t time CAo feed concentration of A x fractional conversion of A rA reaction rate (mol/hr/volume of the reactor), 1 dNA V dt 0 rA reaction rate (mol/hr/weight of the catalyst); 1 dNA W dt W catalyst weight NAo molar feed rate of A: The CSTR operates continuously and is frequently a better tool to obtain kinetic data, if one can afford

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Table 1 Types of reactors in a petroleum renery Reactor(s) Naphtha hydrotreater Catalytic reformer Alkylation unit Distillate hydrotreating cat-feed hydrotreater Hydrocracker Fluid catalytic cracker unit Coker Residuum hydrotreater Type Vapor phase catalytic Vapor phase catalytic Catalytic liquid phase (H2SO4 or HF) Trickle phase catalytic Trickle phase catalytic Vapor phase catalytic Semibatch thermal Trickle phase catalytic=thermal Purpose Remove S and N from catalytic and virgin naphtha before catalytic reforming Convert parafns to higher-octane aromatics and isoparafns Combine isoparafns with olens to gasoline Remove S and N and saturate aromatics Convert gas oils, coker gas oil, and light catalytic cycle oil to lighter products Convert vacuum gas oil to catalytic naphtha Convert residuum to gas oil and coke Convert heavy residuum to lighter distillates, removing metals (Ni, V), S, and N

the time and expense of setting one up. The reaction rate can be derived directly from experimental data as pointed out by Mahoney.[1] The reactor has no concentration or temperature gradients, and conversion is controlled by changes in feed rate or reactor temperature. A unique aspect of petroleum rening, relative to chemical processing, is that the streams are mixtures of thousands of compounds. Thus, it is not easy to work with moles as is common for a simple feed. We must, therefore, frequently use mass rather than moles for the reactor design equations. A common convention is to replace space time (J reactor volume=

volumetric feed rate) with reciprocal space velocity, using 1=WHSV for mass of catalyst=time=mass of feed or 1=LHSV for volume of catalyst=time=volume of feed. The reactor performance equation for a CSTR is given in Eq. (2). CSTR reactor V CA o X W X 1 X t 0 000 Q rA FAo rA WHSV rA thermal catalytic 2

Simplest

Vapor
Naphtha HDS & Cat Reformer Packed Bed Reactor

Mid and Light Distillate

Delayed Coker Semi-Batch

Resid

Liquid Dist

Olefin Isobutane Alkylate Distillate Hydrotreater and Hydrocracker Trickle Bed Reactor

Hydrogen

Cascade Alkylation Unit Tank-In-Series

Naphtha vapors

Regenerator

Riser

Most

Resid Hydrotreater Ebullated Bed recycle Resid Hydrogen Complex

Vac Gas Oil Air Riser Cat Cracker, FCU Plug flow (reactor) mixed flow (regenerator)

Fig. 2 Petroleum rening reactors. (View this art in color at www.dekker.com.)

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Reactor Engineering

where t V =Q; volume of the reactor/volumetric flow rate FAo molar feed rate of A
000 rA g=hr=g catalyst WHSV weight hourly space velocity

Endothermic

Exothermic

Reforming

Distillate Hydrotreating

Alkylation

g total feed/hr/g catalyst). The plug ow reactor is probably the most commonly used reactor in catalyst evaluation because it is simply a tube lled with catalyst that reactants are fed into. However, for catalyst evaluation, it is difcult to measure the reaction rate because concentration changes along the axis, and there are frequently temperature gradients, too. Furthermore, because the uid velocity next to the catalyst is low, the chance for mass transfer limitations through the lm around the catalyst is high. Eq. (3) is the reactor performance equation for a plug ow reactor. Integral plug ow V t CA o Q or W FAo Z dx 0 rA Z dx rA thermal Z

Cat-Cracking

Residuum Hydrotreating/ Hydrocracking

To, feed temperature

Fig. 3 Heat effects.

where Cp molar heat capacity of stream BTU/lb/mol/ F DT temperature difference, outlet minus inlet DHr heat of reaction BTU/lb/mol: Endothermic Reactions (Cat-Cracking, Reforming, Coking). In Fig. 3, we see that the uid cracking unit (FCU) requires heat input to maintain the reaction temperature in the cracking zone and is shown on the far right in the endothermic region. Burning coke off the catalyst in the regenerator provides this heat and the recirculating catalyst transfers that energy to the cracking reaction in the riser of the FCU. Catcracking involves bond breakage and may be classied as endothermic. The second reaction that is highly endothermic is catalytic reforming. The dehydrogenation reaction is very endothermic and requires a reactor system of three to four reactors in series, with interstage heating between the reactors because the reaction temperature drop in each stage must be increased so that the reaction rate does not slow down too much. Thermally Neutral (Isomerization). Isomerization, represented by the vertical line in the diagram, involves skeletal rearrangement of molecules but no change in the molecular weight. Thus, the reaction does not cause any cooling or heating of the feed stream. Exothermic (Hydrotreating, Hydrocracking, Alkylation). Many of the petroleum rening reactions are exothermic. Hydrocracking is very exothermic

1 WHSV

dx 000 rA

catalyst 3

Commercial Reactor Design and Scale-up The design of larger commercial reactors provides a signicant challenge because heat effects are typically substantial and vary with the endothermic cat-cracking or reforming reactions to the highly exothermic hydrotreating and hydrocracking reactions; the ow regime deviates from the ideals of plug ow and perfect mixing. We examine commercial reactors in increasing order of complexity.

Heat Aspects An energy balance is given below in Eq. (4) and is shown graphically in Fig. 3 for the various types of rening reactions, with the graph developed by Levenspiel.[2] Energy balance for reactor Cp DT X DHr 4

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owing to aromatic saturation reactions. Although the molecular weight is reduced by the cracking reaction, this is preceded by hydrogenation (HDN) reactions, for example, aromatic ring saturation, which is necessary before the ring opening can occur. Alkylation is also quite exothermic because higher molecular weight compounds are formed from isobutane and olens. Distillate and naphtha hydrotreating also release heat when organo-sulfur and nitrogen compounds (i.e., dibenzothiophene and pyridine) are converted to hydrogen sulde and ammonia, respectively.

Naphtha=light hydrocarbon processing Catalytic Reforming of Naphtha. Catalytic reformers may be differentiated as to mechanical design. Those that do not employ on-stream regeneration of the catalyst are xed-bed processes and are called semiregenerative. The regenerative or cyclic processes include the original hydroforming process (Exxon), ultraforming (Amoco), and power forming (Exxon); they are characterized by a swing reactor in the multiple reactor train that is substituted for the reactor, which is off-line during regeneration (see Fig. 4).[3,4] The uid hydroforming employs uidized bed and the thermofor and hyperforming processes employ moving beds of catalyst. Universal Oil Products has developed a unique reforming process, called CCR for continuous catalyst regeneration, which integrates the reactor with the regeneration process in a stacked reactor concept. It makes use of a radial ow reactor with a moving bed of catalyst. The CCR platforming process (see Fig. 5) utilizes naphtha boiling in the range of 180400  F to produce high-octane gasoline or petrochemical precursors. This technology is one of the worlds leading reforming processes, with many units operating currently. The platforming process provides reners with proven, ultra-low-pressure

(50 psig reactor pressure) operation and the highest reforming yields. In gasoline applications, the platforming process produces high-octane reformate for unleaded gasoline blending. In reformulated gasoline applications, the low-pressure, low-severity platforming process restores a renerys hydrogen balance by maximizing the yield of hydrogen, even at the required low-octane severities. With appropriate prefractionation, the process produces the low-benzene, lowvapor-pressure material mandated by reformulated gasoline. The principal problem in the design of catalytic reformers is heat balance, with many of the reactions that produce aromatics being very endothermic. Cyclic mode is preferred for high aromatics production, while semiregenerative for moderate to high severity. Low-octane naphtha is converted to high-octane reformate by dehydrogenation and dehydrocyclization of parafns to make an aromatic-rich product. Fig. 4 shows cyclic reforming where any reactor can be isolated, regenerated, and placed back on-stream. Typical yields and process conditions for these two processes are listed in Tables 2 and 3. Catalysts Reforming catalyst was developed essentially for the production of high-octane blending components from low-octane naphthas. Hydrogenationdehydrogenation and acidic catalytic components are required for the various reactions that produce high-octane materials. These components are supported on a suitable base. Reforming catalyst has generally used platinum for the HDNdehydrogenation function and chloride active sites for the acidic function, both supported on gamma alumina. The desirable reactions for octane production are listed below: 1. Dehydrogenation of cyclohexanes to aromatics. 2. Dehydroisomerization of cyclopentanes to aromatics.

(Swing Rctr)

Heavy Virgin Naphtha or Lt Hydrocrackate

Recycle Gas Reformate Product

Fig. 4 Catalytic reforming unit (semiregenerative or cyclic).

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REACTORS RECYCLE GAS COMPRESSOR

Reactor Engineering

REGENERATED CATALYST

NETT HYDROGEN

LIGHT ENDS TO RECOVERY

STABILIZER

REGENERATION SYSTEM

HEATERS

LOW PRESSURE HIGH PRESSURE SEPARATOR SEPARATOR

SPENT CATALYST

FEED

RECYCLE HYDROGEN PLATFORMATE

Fig. 5 CCR reforming process.

3. Dehydrocyclization of parafns to aromatics. 4. Isomerization of n-parafns to isoparafns. 5. Hydrocracking of low-octane, long-chain parafns. Reformer reactor variables Temperature. Normally, inlet temperatures range between 850 and 1000  F. The temperature at which the catalyst beds are held is the primary variable available to the rener to control product quality. Very high temperatures, above 1000  F, can cause thermal reactions that will decrease reformate yields and increase catalyst deactivation from coke formation.

Space Velocity. Space velocity is dened as volume of naphtha processed per hour per volume of catalyst (or weight of naphtha per hour per weight of catalyst). It determines the limits of product quality (i.e., octane number). The greater the space velocity, the lower the limit, or maximum octane possible. For highly naphthenic feedstocks, high space velocity can be used. For more parafnic feedstocks, lower space velocity is required to achieve the desired octane number in the product. Pressure. Pressure affects dehydrogenation and hydrocracking reactions. Increasing the pressure will increase hydrocracking but adversely affect equilibrium aromatic

Table 2 Yields for semiregenerative and cyclic reforming Yield 57 30 57 53 API naphtha vol% cycloparafns vol% parafns Research octane No. (RON)


Semiregenerative 2.3

Cyclic 2.6

H2 (%)

C1C4 (%) C5 (%) RON

13.1 78.5 99

11.2 79.1 101

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Table 3 Process conditions for semiregenerative and cyclic reforming Process variable Pressure (psig) Temperature ( F) Feed rate, WHSV Catalyst Octane, (R M)=2


Semiregenerative mode 150 (low severity) 960 5.5 Pt=Re (0.4=0.4%) 93

Cyclic mode 350 960 5.5 Pt=Re (0.4=0.4%) 98

formation. Higher pressure reduces carbon deposition on the catalyst and slows down deactivation. Reformer reactor design aspects The principal problem in the design of catalytic reformers is heat balance. Reactions that produce aromatics are very endothermic, being partially offset by exothermic hydrocracking reactions. Large amounts of heat must be supplied to the reaction zone to keep the temperature high enough. In xed-bed units the heat is supplied by reactors in series with intermediate reheating. The largest temperature drop is in the rst reactor. Reactor models The plug ow model is frequently used to describe catalytic reformers. Referring to Eq. (5), we see that one way to calculate the amount of catalyst needed for a specied conversion level and naphtha feed rate is to graphically integrate the expression on the right-hand side of the equation. We do this by plotting 1=rate vs. the fractional conversion, and then compute the area. This area yields a value for 1=WHSV, the ratio of the catalyst charge to the oil ow rate. For a multiplestage reactor, with an endothermic reaction, we have the plots shown in Fig. 6 for three reactors in series. As the temperature decreases in the reactor, the rate is correspondingly lowered and causes the 1=rate curves to increase as conversion, x, increases. The interstage heaters, between each reactor, bring the naphtha temperature up for the next reactor stage, so that the reaction rate is maintained high enough. The size of each stage can be computed from the area and the total area representing either W=Fao or 1=WHSV (reciprocal space velocity). Reactor performance equations for a plug ow reactor dx dx 0 00 rA or rA dW=Fao d1=WHSV Z Z dx dx W=Fao or 1=WHSV 0 00 rA rA

where x fractional conversion W catalyst charge lb Fao molar feed rate mol/hr WHSV weight hourly space velocity lb oil/hr/lb catalyst
0 rA reaction rate mol/hr/lb catalyst 00 rA reaction rate lb/hr/lb catalyst:

The energy balance equations for a plug ow reactor are given below in Eq. (6) and relate temperature change to either reactor length, z, or reciprocal space velocity, 1=WHSV. Energy balance equations for plug ow reactor P r DHr i ri dT b dz GCP P P dT DHr ri ai dx d1=WHSV d1=WHSV CP

Fig. 6 Plug ow reactors in series.

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Reactor Engineering

where T temperature (F) z reactor length (ft) rb bulk density of catalyst G mass velocity of feed lb/hr/ft2 Cp heat capacity of feed stream BTU/lb DHr heat of reaction BTU/lb/mol ri reaction rate of species i WHSV space velocity lb naphtha/hr/lb catalyst ai adiabatic temperature rise for reaction i x fractional conversion of species i: If the ow regime in the reactor has some mixing and=or dispersion and deviates slightly from plug ow conditions, then the mass balance can account for this with an axial dispersion model, a one-parameter model.[5] The material balance is shown below in Eq. (7). Dispersion model for small amounts of mixing
0 trb rA D d2 x dx 0 x 0 at Z 0 uL dZ2 dZ CA o 0 rf rA D d2 x dx 0 uL dZ2 dZ WHSV CAo dx 0 at Z 1 dZ

The second-order differential equation is solved with a numerical differential equation solver. The dispersion number is estimated by rst predicting the particle Peclet number, Pe0 , from the equation above. Then, the value of the reactor Peclet number, Pe, is predicted from the particle Peclet number Pe0 by multiplying by the ratio of the particle diameter, dp, to the reactor length, L. Pe is the only parameter required to solve the dispersion model equation. Alkylation In sulfuric acid alkylation, olens and isobutane react to form a gasoline blending component at around 45  F.[6] This reaction only occurs in the acid phase. Olens are extremely soluble in sulfuric acid; isobutane is only slightly soluble. Olens will polymerize in the absence of isobutane. The polymerization reaction competes with the alkylation reaction: Olefin olefin polymer Olefin isobutene alkylate A simplied sketch of an alkylation unit is given in Fig. 7. Olen and isobutane are charged to a refrigerated stirred reactor. Acid in the reactor efuent is removed in a settler and recycled to the reactor. The most commonly used reactor in sulfuric acid alkylation is the Stratco contactor.[7] The principal advantage of the Stratco contactor is the high isobutane concentration in the reactor efuent. This is achieved by operating the contactor at a pressure sufcient to suppress vaporization of the isobutane refrigerant recycle. The heat of the alkylation reaction is removed indirectly by partially vaporizing the settler efuent through the tube bundle shown in Fig. 8. The Kellogg cascade autorefrigeration unit, shown in Fig. 9, differs from the Stratco process in that the refrigeration is provided in situ by allowing a proportion of the reactants to vaporize within the reaction zone. In the cascade system, dilute olen concentrations are obtained by splitting the olen feed into a number of parallel streams, each of which is fed to a separate reaction compartment containing its own mixer. Isobutane passes through all of the compartments in series, but the olen-containing feed is divided among the several components. The Kellogg cascade alkylation unit can be approximated by a tank-inseries reactor model. Any olen-containing hydrocarbon stream may be used to alkylate isobutane. Butenes are the usual alkylating agents, but propylene is also used, and ethylene and pentenes are employed to a limited extent.

where xA conversion Z axial position in reactor; z=L dimensionless u superficial velocity, Q=A L reactor length D=uL dispersion number, 1/Peclet (reactor) Peclet Pe0 dp =L dp catalyst particle diameter Pe0 particle Peclet 20=Re=Schmidt 1=2 rf fluid density rb bulk density of catalyst
0 rA reaction rate of A mol/hr/ft3 reactor t space time hr

CAo feed concentration z G=rb WHSVft G mass velocity, rf u lb/hr/ft2 :

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Product*

Settler Chilled feed*

Emulsion recycle

Refrigerant Recycle acid * Includes recycle isobutane

Fig. 7 Simplied sketch of an alkylation unit.

The chief sources of olens are cracking operations, especially catalytic cracking. However, olens can be produced by the dehydrogenation of parafns; butanes are dehydrogenated commercially to provide feeds to alkylation. Isobutane is obtained from crude oils, cracking operations, catalytic reformers, and natural gas. To supplement these sources, n-butane is sometimes isomerized. Only small concentrations of diolens are permissible in feeds to alkylation, particularly for sulfuric acid catalyst. Diolens increase the consumption of acid. Although the majority of early alkylation units used sulfuric acid as a catalyst, there has been a trend over recent years in favor of the hydrouoric (HF) process. Today, the installed capacity of each process is roughly the same. The HF alkylation process is offered by two licensors, Universal Oil Products and Phillips Petroleum. The reaction is carried out at temperatures between 75 and 115  F, which is considerably higher than the sulfuric acid process.

Rate Models for Alkylation. The rate model to describe alkylation of isobutane with olens is complicated by the presence of two phases, sulfuric acid and hydrocarbon, and the transfer of reactants between these two phases. As mentioned earlier, the alkylation reaction takes place in the acid phase, with olens highly soluble in the acid and isobutane only moderately soluble. The isobutane is fed in large excess to compensate for the lower solubility and the olen concentration must be kept low or it will polymerize and form red oil, consuming the sulfuric acid catalyst. In Fig. 10, we have shown the lm model, with olens in the bulk gas phase, transferring rst through the gas lm, then dissolving in the acid, transferring through the liquid lm, and nally entering the main body of the bulk liquid acid phase. The rate expression must account for the mass transport across both the gas and the liquid lms as well as the alkylation reaction in the acid phase.

Fig. 8 Stratco contactor for alkylation.

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Reactor Engineering

Vapors to compressor

Isobutane recycle and refrigerant

Recycle acid

Olefin feed

Spent & recycle acid

Fig. 9 The Kellogg cascade autorefrigeration unit for alkylation.

Reactor effluent

Levenspiel has presented a thorough analysis of the many situations involving multiphase kinetics and the equation that applies to alkylation is given below:[8]
000 ro

1=kog a Ho =kol

Po $ aE Ho =k Ciso fl 8

where
000 ro reaction rate mol/hr/ft3 reactor

Stratco unit with the single mixer on one end is approximated by a single mixed tank, as shown in the upper part of the gure. However, the Kellogg cascade unit has a series of compartments with mixers and olen is sparged into each compartment to keep the concentration low so that it reacts with the isobutane rather than polymerizing. The tank-in-series model may be used to model this type of unit and this is shown in the lower part of the gure. A mass balance can be made for a stirred tank reactor readily because the composition is the same everywhere in the vessel.

Po olefin partial pressure atm kog mass transfer coefficient for gas film mol/ft/hr/atm a superficial area ft2 =ft3 reactor Ho Henrys law constant atm/ft3 =mol kol liquid film mass transfer coefficient E liquid film enhancement factor, rate of transfer with chemical reaction rate for straight mass transfer k reaction rate constant ft3 liquid/mol/hr Ciso liquid concentration mol/ft3 fl fraction of liquid phase in the reactor: Reactor design equations The contacting pattern in two types of alkylation units is shown in Fig. 11. More specically, we see that the
Co Ciso gas film ro = liquid film Po 1/(kog a) + Ho/(kol a E) + Ho/(k Ciso f) poi po Rate expression ro = k Co Ciso f f = liq vol/rctr vol interface

Ciso Co main body of liquid

Fig. 10 Transfer of olen into acid phase, and then reaction with I-C4. (View this art in color at www.dekker.com.)

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IC4 Olefin Stratco Unit Alkylate

calculated separately and then the individual tank volumes are summed up to yield the total volume.

DISTILLATE PROCESSING
Alkylate

IC4 Olefin Kellogg Cascade Unit

Hydrotreating Hydrodesulfurization (HDS), HDN, and HDN of petroleum distillates (i.e., light cycle oil, kerosene, and light gas oil) can be accomplished in a down-ow trickle bed reactor, lled with cobaltmolybdenum (CoMo) or nickelmolybdenum (NiMo) catalyst. Hydrocarbon feed and hydrogen-rich gas are mixed, heated, and contacted with the catalyst. The outlet stream is cooled and separated, with hydrogen-rich gas recycled and additional makeup hydrogen blended into the feed stream; the liquid is stripped to remove dissolved hydrogen sulde and ammonia and then sent to storage. The process ow is shown in Fig. 12 for a distillate hydrotreating unit. In Table 4 are shown the reactor conditions for three streams varying in boiling point (i.e., naphtha, light catalytic cycle oil, and vacuum gas oil) and impurity content. In petroleum hydrotreating, both vapor phase and trickle bed reactors are used for catalytic hydrotreating of petroleum fractions. Under normal processing conditions, naphthas are completely in the vapor phase while higher boiling fractions are hydrotreated in a mixed-phase trickle bed reactor. These two types of catalytic reactors are discussed extensively. Fixed-bed catalytic reactors are widely applied to reaction systems in which the reactants are present in a single vapor phase. The scale-up and performance of commercial reactors can be predicted from experiments in small-scale reactors. On the other hand, the mixed-phase trickle bed reactor is considerably more complex to analyze and scale up. The performance of trickle bed reactors is inuenced by many factors associated with mixed-phase (gasliquidsolid) processing. Some of

Fig. 11 Contacting patterns for alkylation. (View this art in color at www.dekker.com.)

For the case of mass transfer and reaction in an agitated tank contactor, the balance is simply olen lost by gas disappearance of olen by reaction. Thus, the equation below is the reactor performance equation for a single stirred tank. Reactor performance for single stirred tank Fg 000 Q Po in Po out ro jat exit Vr where Fg molar flow rate of the gas Y total pressure Po in partial pressure of olefin into reactor Po out partial pressure of olefin leaving reactor 000 ro overall rate of conversion of olefinto alkylate Vr total volume of reactor: To estimate the reactor volume, Vr, the solution is 000 direct. Evaluate the overall rate, ro, from known stream compositions. Then, solve for the reactor volume. For several tanks in series, each tank is 9

H 2S Recycle H2

Lt Components

H2

Trickle Bed Reactor 1

3 2

HC Feed

Hydrotreated Product

Fig. 12 Distillate hydrotreating.

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Reactor Engineering

Table 4 Types of hydrotreaters Type of reactor Vapor phase Purpose Feed Gravity ( API)a Boiling range ( F) Sulfur (%) Nitrogen (ppm) Bromine (No.) H2 consumption (SCFB)b Temperature ( F) Pressure (psig) WHSV (lb=hr=lb catalyst) Catalyst Recycle gas rate (SCFB)
a b

Trickle bed Distillate HDS Light cycle oil, diesel 26 310660 1.4 400 30 350 625 400 4 CoMo=alumina 700 Kerosene 45 302490 0.5 10 150 600 350 4 400 Cat-feed hydrotreat Vacuum gas oil 17 6501000 1.4 6000 700 700 1000 1 NiMo=alumina 1500

Reformer feed treating Virgin=cracked naphtha 62 175360 0.001=0.1 4 0=19 80 550 500 6 500

Specic gravity 141.5=( API 131.5). SCFB Std. ft3 per barrel

these include gasliquid distribution, catalyst contacting, and mass transport resistances in the gas and liquid phases. To appreciate the complexity of this type of reactor, a step-by-step description of the reaction process follows: 1. Gasliquid distribution: Oil and hydrogen are fed into the top of the reactor and distributed uniformly over the catalyst bed. Further, down the catalyst bed, ow maldistribution (i.e., channeling, wall ow) may take place owing to nonuniform bed properties. 2. Catalyst contacting: Catalyst particles must be actively contacted with fresh reactant to effectively utilize the catalyst. Stagnant regions on the catalyst particles impair overall reactor performance. 3. Transport of reactants to catalyst: To supply the catalyst with fresh reactant, several mass transfer steps are involved. The hydrogen must rst transfer through the gasliquid interface before it is in the bulk liquid phase. Then, dissolved hydrogen and oil reactant (sulfur, nitrogen, aromatics) in the bulk phase transfer through the liquid lm around the catalyst to its outer surface. Finally, the reactants diffuse into the catalyst pores. 4. Catalytic reaction: The reactant molecules chemisorb on the active sites of the catalyst surface, react, and then desorb off the active site.

5. Transport of reactants from catalyst: Reaction products diffuse out of the catalyst pores, then through the lm around the catalyst to the bulk phase, and nally the gaseous product (H2S, NH3, or H2O) transfers through the gasliquid interface into the bulk gas phase. Heat transfer is also an important consideration in a commercial operation, because reactors are operated adiabatically. The heat release from desulfurization, polyaromatic saturation, etc., produces a temperature gradient along the catalyst bed, the magnitude directly proportional to hydrogen consumption. Temperature control in a multibed commercial reactor frequently employs cold-shot cooling between the beds with hydrogen to limit the maximum temperature rise. Other cooling means such as interreactor heat exchangers are also used. On the catalyst particle scale, heat transport considerations are usually not important. Interphase (lm) and intraparticle temperature gradients are not large because the liquid phase effectively transfers heat from the particle.

General Kinetic Rate Model for Mixed-Phase Catalytic Systems In general, the rate equation for heterogeneous reactions accounts for more than one rate process. This leads one to ask how processes involving both physical transport and reaction steps can be incorporated into one overall

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rate expression. We can make an analogy with conductive heat transfer, in which a combination of different resistances is applied to chemical systems. In Fig. 13, we see that when catalyst particles are immersed in a liquid, there are two lm resistances, one at the gas liquid interface and the other on the catalyst surface, that must be accounted for plus the catalytic surface reaction, which can be inuenced by pore diffusion. Thus, we can write the following equation to account for all of these physical transport and reaction steps. H2 D ! Products rH 2 where PH2 hydrogen pressure H Henrys law constant atm/ft3 =mol kl liquid film mass transfer coefficient a interfacial area between gas and liquid as catalyst external area k0 catalyst film mass transfer coefficient E catalyst effectiveness factor for pore diffusion effects k rate constant for catalytic reaction CD concentration of D in liquid phase: PH2 H=kl a H=k0 as H=EkCD 10

for partial vaporization of the liquid hydrocarbon as it enters the reactor; a plug ow model is used.[9] Some of the hydrocarbon travels downward through the liquid phase, while the portion that is vaporized travels with the hydrogen-rich phase. The reactor model is given below in Eq. (11) and the energy balance equation follows it. Rate equation dx1 reaction rate of species i d1=WHSV Pio a H=O Pv 1 a P where Pio feed partial pressure of i atm a fractional vaporization of liquid feed xi fractional conversion of i H mol gas/barrel of oil O mol oil/barrel of oil Pv vapor pressure of oil P total pressure ri reaction rate of i lb/mol/hr/lb catalyst WHSV space velocity lb oil/hr/lb catalyst: Energy balance equation P dT ai dxi d1=WHSV d1=WHSV where ai adiabatic temperature rise per unit of conversion of i. Hydrodesulfurization Kinetics Reactions for removing sulfur, nitrogen, and oxygen, which are present as organic compounds, are characterized by replacement of the nonhydrocarbon component with hydrogen. The nonhydrocarbon component is hydrogenated (to H2S, NH3, and H2O) and subsequently removed by stripping and fractionation. The desulfurization reaction for single compounds (i.e., benzothiophene and dibenzothiophene) can be modelled with the FreyMosby relationship, which has a LangmuirHinshelwood form and accounts for inhibition by hydrogen sulde and aromatics.[10] This works well for single-sulfur compounds, but it should be pointed out that overall desulfurization kinetics, which includes compounds with a large range in reactivity, often behaves more like second order [see Eq. (12)]: Rate expression 11

Plug Flow Reactor Model for Mixed-Phase Reactor The general reactor model for a trickle bed reactor was derived by Frey and Mosby and appropriately accounts
gas-liquid interface

catolyst surface

pH2

CD

liquid film

main body of liquid

film

Fig. 13 Multiphase resistances in distillate hydrotreating. (View this art in color at www.dekker.com.)

rs

ks ActPs PH2 1 KHS PHS KAR PAR 2

12

2570

Reactor Engineering

Performance equation for plug ow reactor ln 1 ks Act PH2 1 x WHSV 1 a a H=O Pv P 1 KHS PHS KAR PAR 2

where DGo free energy of formation at To DHR heat of reaction is exothermic, is endothermic) To temperature under standard conditions T reaction temperature Psat saturated aromatic pressure PA aromatic pressure kA rate constant of reaction Act catalyst activity for aromatic saturation R gas constant K equilibrium constant:   1 ln 1 X=Xe n kA ActM 1PH2 WHSVM Xe 1 a a H=O Pv P where M ratio of saturates/aromatics in the feed stream and Xe equilibrium conversion value: Hydrogen Consumption Estimates for Hydrotreating The hydrogen used in hydrotreating can be predicted from the set of equations given in Table 5, which are based on stoichiometry of model reactions. The formulas correspond to 1, 3, and 5 mol of hydrogen per mole of olen, sulfur, and nitrogen, respectively.

where Act catalyst activity. Denitrogenation Rate Equation Nitrogen removal is generally more difcult than desulfurization, for several reasons, for instance: 1) side reactions yield nitrogen compounds more difcult to remove than the original ones (indole ) quinoline and carbazole derivatives) and 2) heterocyclic, nitrogen-containing rings must saturate during the hydrogenolysis, and the presence of large side groups on the ring appears to hinder the reaction sterically. Ho has a comprehensive review on hydrodenitrogenation catalysis that covers many topics.[11] The rate of denitrogenation is frequently described as being rst order in nitrogen and hydrogen, as discussed by Sattereld and Yang, and the rate equation is given below as Eq. (13):[12] rN KN Act PN PH2 where rN rate of denitrogenation Act catalyst activity PN partial pressure of nitrogen compounds PH2 partial pressure of hydrogen: Nitrogen becomes increasingly harder to remove as the number of aromatic rings increase. More specically, as we go from single-ring heterocyclic compounds such as pyridine to multiring compounds like quinoline, nitrogen removal is signicantly more difcult. Aromatic Saturation Rate Equation (Equilibrium Limited) 13

DISTILLATE HYDROCRACKING The aromatic saturation rate equation is similar in form to denitrogenation with the exception that it is strongly inuenced by chemical equilibrium, instead of the irreversible form. Levenspiel has developed an integrated expression for reversible reactions and this is provided in Eq. (14):[2]
n rA kA ActPA PH2 1=KPsat kA Ko eDGo =RTo ksat ! DHR 1 1 lnK=Ko T To R

14

Since the mid-1960s, hydrocracking has become a major rening process. It is one of the most versatile of modern petroleum processes. Flexibility of operation, with respect to both feedstock and product, has been reported. This exibility in operation may be related to the development of specic families of the catalyst, the design of processing schemes that allow the catalysts to function efciently, and the optimum rening relationships between hydrocracking and other rening processes. Whereas the commercial feedstocks range from naphtha to residua, there is a wide choice for the product of a hydrocracker.

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2571

Table 5 Calculation of hydrogen consumption Feed density (lb=gal) lb=gal lb=gal lb=gal Hydrogen consumed (SCFB = SCFB1 + SCFB2 + SCFB3) SCFB1 SCFB2 SCFB3

Reaction Desulfurization Denitrogenation Olen saturation

Constant 0.15 0.57 0.10

Feed impurity %S %N Bromine number

Conversion % Desulfurization % Denitrogenation % Saturation

SCFB Std. ft3 per barrel

The hydrocracking catalyst is dual functional: 1) cracking of high molecular weight hydrocarbons and 2) HDN of the unsaturates either formed during the cracking step or otherwise present in the feedstock. A typical cracking catalyst is silicaalumina and a base or noble metal serves as a hydrogenating catalyst. In a way, HDN helps cracking. The metal HDN sites keep the acid sites of the cracking catalyst clean and active by HDN of the coke precursors. During the past several years, interest in zeolite catalyst has been relatively high. Zeolites X and Y, and mordenite have been the center of attraction. [13] Zeolite, being a superior cracking catalyst compared to amorphous silicaalumina, permits a decrease in reaction temperature for the same level of conversion. The major HDN components are platinum, nickel, palladium, molybdenum, cobalt, etc. These may be altered by promotion with another metal. Inorganic salts, water, metals, and organic compounds of sulfur, nitrogen, or oxygen in petroleum act as poisons for the hydrocracking catalysts. Sulfur compounds inhibit the HDN component while nitrogen compounds inhibit the cracking component of the catalyst. Metal contaminants are deposited on the catalyst to deactivate it. These deposits, when in the active state, promote various dehydrogenation reactions and increase coke-producing tendency.

entry. The various distillate-hydrocracking processes include Unicracking, Isocracking, Houdry-Gulf, Isomax, Ultracracking, and BASF-IFP. They can be operated in either a single- or a two-stage process and the product slate can be adjusted by catalyst selection, reaction temperature, and staging. Most of these processes recycle the unconverted higher boiling product to extinction. Unicracking is characterized by the use of a molecular sieve catalyst but many of these other processes are converting to this sieve catalyst technology. Typical conditions for distillate hydrocracking include:  Pressure: 10003000 psig  Temperature: 575825  F  Liquid space velocity: 0.32.0 volume of feed= volume of catalyst=hr  Recycle gas rate: 3000 std ft3 per barrel. A typical single-stage process is shown in Fig. 14 with the hydrocracking reactor in the middle and a pretreating section on the far left to convert sulfur, nitrogen, and oxygen compounds to hydrogen sulde, ammonia, and water. The efuent then ows directly to the hydrocracking reactor. Interstage quenching of recycle gas between catalyst beds controls heat release and maintains temperature control. A diagram of a ve-bed hydrocracker is shown in Fig. 15. The dimensions of this particular commercial reactor were 10 ft diameter with 8 in.-thick walls. The design of hydrocracking reactors must be carefully considered on account of the severe operating conditions to which they are subjected, namely:  High total pressure and hydrogen partial pressure.  High hydrogen sulde and ammonia partial pressure from the HDS and HDN reactions.  High operating temperatures.  High exothermic heat of reaction. The heat of reaction is a function of the amount of hydrogen consumed and is normally in the range

Types of Hydrocracking Depending on the feedstock used, two types of hydrocracking are practiced industrially. If the feedstock is a heavy distillate obtained from a straight-run rening or cracking operation, it is called distillate hydrocracking. Residual hydrocracking is the name given to the process if the feedstock happens to be the residue of straight-run rening. The residues are usually lower in API gravity and higher in carbon residues and carbon=hydrogen ratio as compared to distillates. Galbreath and Van Driesen have shown that residual hydrocracking is clearly a different process from distillate hydrocracking; a different type of catalyst is used at a relatively high temperature.[14] We will discuss residual hydrocracking in a later section of this

2572

Reactor Engineering

HYDROTREATING REACTOR

HYDROCRACKING REACTOR

RECYCLE COMPRESSOR

TAIL GAS C4 AND LIGHTER LIGHT NAPHTHA HEAVY NAPHTHA KEROSINE

HEATER

FEED

HYDROGEN MAKE-UP

SEPARATORS

FRACTIONATOR

Fig. 14 Hydrocracking process with recycle.

of 490630 kcal=m3 of hydrogen. To control the temperature in the reactor, the catalyst charge is split into a number of separate beds with means of cooling the efuent from each bed. This is normally achieved by injection of cold recycle gas between beds or injection of cold recycle liquid between the catalyst beds. Gas injection, the rst alternative, is the most favored. The reactor design equations, given for the trickle bed reactor in the previous section on hydrotreating, should be referred to for design of the hydrocracker. Unfortunately, we are not able to provide rate equations to describe the cracking reaction as this information is highly proprietary and is specic to the catalyst and feedstock used.

HEAVY GAS OIL CONVERSION Fluid Cat Cracking Fluid catalytic cracking is a process for the conversion of straight-run atmospheric gas oil, vacuum gas oil, and some atmospheric residues and heavy stocks into high-octane gasoline, light fuel oils, and olen-rich light gases. Basically, the cracking reactions are carried out in a vertical reactor vessel in which vaporized oil rises and carries along with it,

in intimate contact, small uidized catalyst particles (see Fig. 16). The reactions are very rapid and only a few seconds of contact time is necessary for most applications. Simultaneously, with the desired reactions, a carbonaceous material with low H=C ratio, coke deposits on the catalyst and deactivates it. The spent catalyst and the converted oils are separated and the catalyst passed down-ow to a separate chamber, the regenerator, where the coke is combusted, reactivating the catalyst. The regenerated catalyst is then conveyed down-ow to the bottom of the reactor riser, where the cycle begins again. Control of the regenerator temperature is based on coke made in the reactor. A major breakthrough in catalyst technology occurred in the mid-1960s with the development of zeolitic catalysts. These sieve catalysts demonstrated superior activity, gasoline selectivity, and stability characteristics compared to silicaalumina catalysts, then in use. The continuing advances in both activity and process design resulted in the advanced design concept of riser cracking in which all of the cracking reaction occurs in the dilute phase in the riser. The key to all-riser cracking is the design of a quenching system that stops the cracking reaction at the optimum yield of desired products. Operating conditions for a typical FCU are shown in Table 6 and how it might be altered is as follows.

Reactor Engineering

2573

Quench

23 m Dia. 3

Thermowells

1020 cm Wall

REACTOR EFFLUENT

Fig. 15 Five-bed hydrocracker.

Every FCC complex contains the following sections: 1. Reactor and regenerator: Reactor cracks feed to light hydrocarbons, gasoline, middle distillates, coke, hydrogen, and hydrogen sulde. In the regenerator, the circulating catalyst is reactivated by burning off the coke at high temperatures, releasing CO2, CO, water, and SO2. 2. Main fractionation column: Reactor efuent is separated into various products. The overhead includes gasoline and lighter material. The heavy liquid products, heavier naphtha, and cycle oils are separated as side cuts and slurry oil is separated as a bottom product. 3. Gas concentration unit: Unstable gasoline and lighter products from the main fractionation overhead are separated into fuel gas, C1C4 for alkylation, and debutanized gasoline.

New concepts for FCC Quick-Quench Cracking. Dilute phase cracking in the riser offers signicant advantages over dense-bed cracking. As much as 90% of the feed conversion takes place in the short-contact-time condition in the riser, while the remaining 10% conversion in the dense-bed reactor is accompanied by overcracking of the desirable products. The introduction of the high-activity zeolitic catalysts demonstrated the need for short-contact-time cracking. UOP modied the design of the riserreactor system. The rise was extended axially well into the reactor shell. The catalysthydrocarbon mixture exiting the reactor was directed through a simple device to disengage the hot catalyst from the products. In addition, the catalyst in the dense bed was also reduced. This quenched the cracking reactions at the riser outlet.

2574

Reactor Engineering

To Fractionator

Flue Gas

Reactor Open Riser Regenerator 2 Stripping Steam

Vacuum Gas Oil Feed

1 Air Diluent
Fig. 16 Fluid cat-cracking unit.

CO Combustion. Complete or partial CO combustion will often benet FCU operation. In conventional operation, the carbon from the spent catalyst is converted to equimolar quantities of carbon oxides. If the remaining CO is converted to carbon dioxide, the potential heat can be increased by 4050%. This combustion can be promoted by adding very small amounts of platinum to the cracking catalyst. Complete CO combustion results in the regenerator ue gas containing less than 500 ppm CO, eliminating the need for a CO boiler. The increased heat release produces a higher regenerated catalyst temperature. Therefore, less catalyst recirculation is required to satisfy the reactor heat demand. Coke yield is also decreased and correspondingly is matched on a weightfor-weight basis with an increase in FCC products.

Types of FCU Designs Model II down-ow The Model II down-ow design (Fig. 17) was the rst improvement to the Model I up-ow unit. The principal features of Model II include a reactor vessel near ground level with the catalyst regenerator offset and above it. A rather short transfer line carries both catalyst and hydrocarbon vapor to a dense-bed reactor. Double slide valves are used at various points in the unit, and the long regenerated-catalyst standpipe causes major operating problems. Commercial evidence indicated that although conversions were relatively low (4055 vol%), a large portion of the cracking took place in the short transfer line.

Table 6 Process conditions for FCC Operating variable Pressure (psig) Reactor temperature ( F) Regenerator temperature ( F) Catalyst=oil Conversion (%) Coke yield (%) Catalyst makeup (lb=barrel) Catalyst type


Current 2030 925 1200 12 80 5 0.15 Ultrastable Y sieve 2030 1025 1200 14 85 4 0.15

Future

ZSM-5 additive for light olens desulfurization additive to capture S as H2S rather than SO2

Reactor Engineering

2575

FLUE GAS WASTEHEAT BOILER

MULTICYCLONES REGENERATOR TO FRACTIONATION

COTTRELL PRECIPITATOR

REACTOR

STEAM TO STRIPPING SECTION

OIL FEED

AIR

COLUMN BOTTOMS
Fig. 17 Model II down-ow catalytic cracker.

UOP stacked FCU Following the war, the stacked FCU design (Fig. 18), which featured a low-pressure reactor stacked directly above a high-pressure regenerator, was commercialized. The design was a major step toward shifting the cracking reaction from the dense phase of the catalyst to the dilute phase. UOP side-by-side FCU

assumptions are made regarding the catalyst deactivation rate model and the cracking conversion model. However, this allows us to clearly address the coupling of these two processing units and more elegant kinetics can be used for the cracking reactions to upgrade this model, as shown in Eq. 15: Performance equations for the simplest kinetics reactor (plug ow)regenerator (mixed ow) AR

In the mid-1950s, the straight riser or side-by-side design (Fig. 19) was introduced. The regenerator was now near ground level with the reactor to the side in an elevated position. Regenerated catalyst, fresh feed, and recycle were directed to the reactor by means of a long, straight riser located directly below the reactor; product yields and selectivity were substantially improved.

Cracking reaction (first order) : 0 rA k0 aCA and R k0 t0 Deactivation (first order) : da kd a and Rd kd ts1 dt Catalyst regeneration : da kr 1 a and dt

15

Reactor Performance Equations for the ReactorRegenerator System If the catalyst deactivates rapidly, such as in the FCU, and it is circulated between a regenerator and a reactor, we need to properly account for the catalyst age in the reaction kinetic expression. Some simplifying

Rr kr ts2

Solids in reactor :  a1 Rr 1 eRd Rd 1 Rr eRd

2576

Reactor Engineering

PRESSURE-REDUCING CHAMBER GAS CYCLONE REACTOR CATALYST STRIPPER STRIPPING STEAM CLARIFIED OIL REGENERATOR SLURRY SETTLER MAIN AIR BLOWER STEAM TREATED WATER STEAM GENERATOR GAS AND GASOLINE TO CONCENTRATION UNIT MAIN COLUMN LIGHT CYCLE OIL HEAVY CYCLE OIL

RAW-OIL CHARGE RECYCLE

Fig. 18 The stacked FCU design.

Solids in regenerator : ln

a2 R r
Rd

1 Rr eRd

1 RRr 1 e 1 X Rd 1 Rr eRd

where X fractional conversion of A a catalyst activity k0 rate constant t0 space time in reactor WCAo =FAo kd deactivation rate constant ts1 W1 =Fs and ts2 W2 =Fs W1 and W2 catalyst in reactor and regenerator Fs solids circulation rate: The nomenclature for the above set of equations is given for the reactorregenerator system in Fig. 20.

specically, a bimodal pore size distribution is frequently used with large macrofeeder (GT. 1000 A ) pores along with smaller mesopores.[15] Because residuum frequently has high levels of vanadium and nickel in it, the catalyst activity may actually increase initially and then slowly decrease as the promotional effects of the metals adsorbed on the hydrocracking catalyst are counterbalanced by deactivation because of coking. The resid hydroconversion reactors may be either trickle bed or moving bed. Because of the high rates of catalyst coking, most moving bed residuum conversion reactors have a capability for fresh catalyst addition and spent catalyst withdrawal while the reactor is operating. Typical conditions used for the hydroconversion of residuum include:  Pressure: 20002500 psig  Temperature: 725800  F  Space velocity: 0.40.8 volume of oil=hr=volume of catalyst. Process Kinetic Models

RESIDUUM PROCESSING Residuum Hydroconversion Residuum hydroconversion is a special case of hydrocracking. Compared to distillate hydrocracking, a signicantly different catalyst is used, frequently low metal loading with Mo, with a special pore size distribution less subject to pore plugging by coke. More S. J. Khang and J. F. Mosby (personal communication) have presented process models to describe the removal of sulfur, vanadium, and nickel in residuum hydroprocessing. The kinetic models are given below in Eq. (16): Desulfurization rate, second order; 1000 F inhibited rs aks 1 CA =CAo m S2

Reactor Engineering

2577

FLUE GAS TO CO BOILER GAS AND GASOLINE TO GASCONCENTRATION PLANT PRESSUREREDUCING CHAMBER REACTOR CATALYST STRIPPER STEAM FRACTIONATOR LIGHT-CYCLE GAS OIL

HEAVY-CYCLE GAS OIL CLARIFIED OIL SLURRY SETTLER

REGENERATOR

AIR CHARGE

Fig. 19 The straight riser or side-by-side FCU design.

Devanadation rate, first order, 1000 F inhibited rv akv 1 CA =CAo

n

Denickelation rate, first order, 1000 F inhibited rN akN 1 CA =CAo q N 16

where m, n, and q are the orders indicating the degree of inhibition by 1000 F materials.

Ebullated Bed Reactor for Resid Hydroconversion Two moving bed processes are available for license, and include the H-Oil process developed by Hydrocarbon Research Inc. and the LC-Fining process developed by Cities Service and C-E Lummus. The H-Oil reactor (Fig. 21) is rather unique and is called an ebullated bed catalytic reactor.[16,17] A recycle pump, located either internally or externally, circulates the reactor uids down through a central downcomer and then upward through a distributor plate and into the ebullated catalyst bed. The reactor is usually well insulated and operated adiabatically. Frequently, the reactor-mixing pattern is dened as backmixed, but this is not strictly true. A better description of the ow pattern is dispersed plug ow with recycle. Thus, the reactor equations for the axial dispersion model are modied appropriately to account for recycle conditions.

The schematic in Fig. 22 shows the key elements of recycling a portion of the exit stream with the feed stream and how that affects the feed concentration(s). The recycle increases the supercial velocity, u, and changes the feed concentration owing to dilution with the product stream. Although the H-Oil reactor is loaded with catalyst, not all of the reactions are catalyzed; some are thermal reactions, like thermal cracking, which depend on liquid holdup and not on how much catalyst is present. Thus, the material balance equations need to be divided into two categories, one set for the noncatalytic thermal reactions and another set for the catalytic reactions. A convenient parameter to use is the thermal volume=catalytic volume ratio, T=C, which is the ratio of liquid holdup to catalyst volume. In a commercial ebullated bed, this ratio is close to 1.0 under ebullation conditions. Consequently, the material balance equations for the catalytic reactions with no recycle are given in Eq. (17):

Dispersion model with no recycling catalytic reactiononly material balance ! 0 trA rB D d2 CA dCA 2 uL dz dz T=C &C C ; z 0 A Ao 0 z 1 C A CA f ;

17

2578

Reactor Engineering

Caf

a2,Fs

ts1 = W1/Fs tau' = W Cao Fao 1 mixed flow plug flow ts2 = W2/Fs W2 2

W1 Reactor

Regenerator

Cao, Fao

a1,Fs

Fig. 20 Reactorregenerator system. (View this art in color at www.dekker.com.)

where T=C thermal volume to catalytic volume CA concentration z axial position in reactor, l=L dimensionless D diffusivity u superficial velocity, Q=A L reactor length D=uL dispersion number 0 rA reaction rate of A mol/hr/weight of catalyst t space time; L=u rB bulk density of catalyst: The nal set of equations for the H-Oil reactor can now be written to account for the recycle situation, and thermal reactions in concert with catalytic reactions. The model for the H-Oil reactor introduces two complications beyond the axial dispersion model. First, the boundary conditions are modied to account for the recycle and second, the catalyst in the reactor means that both thermal and catalytic reactions are occurring simultaneously. The set of equations given in Eq. (18) are solved numerically with a differential equation solver. This allows the reactor size to be

determined by integrating along dimensionless distance z until concentration CA equals the desired nal concentration CAf. Dispersion model with recycling catalytic and thermal reaction material balance ! ! D d2 CA dCA r0 r t rA A B 0 uL dz2 dz T=C 8 < C CAo RCAf ; z 0 A1 1 R : CA C A f ; z 1

18

Energy balance dT 0 0 rA DHR rA DHR dz T To at z 0

ruCP

Two- or More-Stage Residuum Hydroconversion A two-stage residuum hydrocracker represents one additional level of complexity beyond the single-stage

Reactor Engineering

2579

Vapor outlet

Catalyst inlet Solid/liquid level Downcomer Catalyst level

Distributor

Plenum chamber Catalyst withdrawal Hydrogen Slurry feed

Ebullating pump

Fig. 21 Ebullated bed reactor.

H-Oil reactor. Now the exit stream from the rst reactor becomes the feed stream for the second reactor. The reactor system may be visualized as shown in Fig. 23. The approach to solving the above reactor system is to rst develop the exit values for Reactor 1 and then to use these outlet variables as input for Reactor 2. The reactors will usually be operated at different temperature levels with stage 2 cooler than stage 1 so that the equilibrium for aromatic saturation reactions is favorably shifted. The interstage cooler is shown in the diagram for this reason. Furthermore, the secondstage catalyst may be different.

DELAYED COKING Delayed coking is a semicontinuous process that is applied to the conversion of most types of residuum. Delayed coking is an endothermic process with the furnace supplying the necessary heat to complete the coking reaction in the coke drum. A diagram of the delayed coking process is given in Fig. 24, showing two coke drums, one active and the other off-line with the coke being cut out of it with high-pressure water nozzles. Hot fresh liquid feed is charged to the fractionator two to four trays from the bottom vapor zone. Any lighter material is stripped from the fresh feed

CA0

CA1 Reactor

I+R CAF R
Fig. 22 Recycle reactor.

2580

Reactor Engineering

CA2

CAF

CA1 CA0

C A3

Stage 1 Recycle ratio, R1 Temperature T1 Catalyst A

Stage 2 Recycle ratio, R2 Temperature T2 Catalyst B

Fig. 23 Two stage residuum hydrocracker.

and then combined with the unconverted residuum to be fed through a heater and into the active coke drum. Steam is usually introduced in the heater tubes of the furnace to control velocities and prevent coke deposition in the heater tubes. The unvaporized portion of the heater outlet settles out in the coke drum where the combined effect of retention time and temperature causes the formation of coke. The exact mechanism of delayed coking is complex and it is not possible to determine the reaction steps involved; however, three distinct steps take place:  Partial vaporization and mild cracking of the feed as it passes through the furnace.  Cracking of the vapor as it passes through the coke drum.  Successive cracking and polymerization of the heavy liquid trapped in the drum until it is converted to vapor and coke. Three basic operating variables contribute to the quality and yields of delayed coking products. They are temperature, pressure, and recycle ratio:  Heater outlet temperature: 875975  F  Top coke drum pressure: 15150 psig  Recycle ratio, volume of recycle=volume of fresh feed: 0.052. Temperature is used to control the volatile combustible material content of the coke product. The current

trend is to produce coke with volatile matter between 6% and 8%. Pressure tends to retain more of the heavy hydrocarbons in the coke drum. This increases the coke yield and slightly increases the gas yield while decreasing pentane and heavier liquid product yield. Recycle ratio has the same general effect as pressure. As the recycle ratio is increased, the coke and gas yields increase and pentane, etc. decrease. The recycle ratio is primarily used to control the end point of the coker gas oil. A typical coking cycle is as follows:

 Fill the drum with coke while it is in the active cycle24 hr.  Switch from active drum to inactive drum and steam out8 hr.  Cool with water and ll the entire coke drum3 hr.  Drain water from drum2 hr.  Unhead and decoke by drilling a 4 ft pilot hole and cutting5 hr.  Replace heads and test with steam2 hr.  Heat up by backing vapors from active drum to top of inactive drum7 hr.  Spare time for slippage of other steps2 hr.  Total48 hr (24 hr cycle).

Yields for Delayed Coking If the Conradson Carbon (Con Carbon) is known, the equations in Table 7 may be used.[18]

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2581

Table 7 Delayed coking yield equations Coke (wt%) Gas (C4) (wt%) Gasoline (wt%) Gas oil (wt%) Gasoline (vol%) Gas oil (vol%) 1.6 wt% Con Carbon 7.8 0.144 wt% Con Carbon 11.29 0.343 wt% Con Carbon 100 wt% coke wt% gas wt% gasoline 186.5=(131.5  API) gasoline wt% 155.5=(131.5  API) gas oil wt%

Reaction Model for Residuum Coking Levenspiel has developed an analysis for reactions where the phase changes from a liquid to a solid.[19] It is an adaptation of the ProutTompkins model and assumes that all coke nuclei are present at the start and no new ones are formed later.[20] Product grows from the nuclei along fracture places. The model is characterized by conversion rst being slow because the boundaries between the reactant and product are very small. Growth then speeds up and eventually slows down as advancing product fronts meet. Please refer to Fig. 25 for the model description. This sounds strikingly similar to the situation in a delayed coker and thus it is proposed for use in the delayed coking process. Because little kinetic analysis has been done

on this brute force process, it seems that some type of model is denitely needed for one to be able to predict performance and make logical judgments on process improvements. The reaction model takes the following form in Eq. (19):   XR ln Mt N 19 1 XR where XR residuum conversion M characteristic slope t time N intersection point of plot where ti N =M:

800F Vapor valves 280F O Combination tower 100F Wet gas

Compressor

Pumparound Inactive Coke drums Active Heat sink

Top reflux

Wild gasoline to VRU

400F Vapor line

Light coker gas oil to furnace oil desulfurizer

O 920F Coking heater

Bottom reflux 700F

530F

Heavy coker gas oil to FCCU

Resid feed

Fig. 24 Delayed coking process.

2582

Reactor Engineering

time

Product grows from nuclei In[XR/(1-XR)]

XR

slope = M

Point of inflection ti = N/m time,t

time,t

Fig. 25 Phase change model for coking. (View this art in color at www.dekker.com.)

In summary, a basic model can be used to interpret the coking data and establish how the coke is being formed as a function of cycle time in the coke drum. CONCLUSIONS The various reactors used in petroleum rening have been described along with the dening reactor performance equations and, occasionally, energy balances. The sizing of these reactors can be accomplished with these equations but, of course, for the detailed reactor design for materials of construction, process control, start-up=shut-down, we need to dig much deeper. Still, the methodology presented is the basic starting point to the nal design and gives the engineer the tools to begin the design process. For catalytic reactions, this means how much catalyst is needed, and for noncatalytic reactions, it establishes the reactor size given the feed ow rate to the conversion unit. Although the focus has been on petroleum rening reactors, it should be noted that many of the reactors in chemical processing are very similar, where one has a welldened feed composition rather than a mixture of many different hydrocarbons.

REFERENCES 1. Mahoney, J.A.; Robinson, K.; Meyers, E. Catalyst evaluation with the gradientless reactor. CHEMTECH 1978, Dec, 758.

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