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Four-Lump Kinetic Model for Fluid Catalytic Cracking Process

LIANG-SUN LEE", YU-WEN CHEN, and TSUNG-NIEN HUANG Department of Chemical Engineering, National Central University, Chungli, Taiwan 32054, R.O.C. WEN-YEN PAN Chinese Petroleum Corporation, Taipei, Taiwan 10033
In the fluid catalytic cracking reactor heavy gas oil is cracked into more valuable lighter hydrocarbon products. The reactor input is amixture of hydrocarbons which makes the reaction kinetics very complicated due to the involved reactions. In this paper, a four-lump model is proposed to describe the process. This model is different from others mainly in that the deposition rate of coke on catalyst can be predicted from gas oil conversion and isolated from the c144 gas yield. This is important since coke supplies heat required for endothermic reactions occurring in the reactor. By this model we can also conclude that the CI-C4 gas yield increases with increasing reactor temperature, while production of gasoline and coke decreases.

Dans un reacteur de craquage catalytique fluide, on obtient B partir du gazole lourd des produits hydrocarbures ldgers plus intbressants. L'alimentation du rkacteur est composee d'un melange d'hydrocarbures, ce qui complique beaucoup la cinetique de reaction en raison des rdactions presentes. On propose dans le present article un modtle B quatre groupes dans le but de decrire le procede. Ce modkle se distingue des autres en particulier parce qu'il permet de prkdire la vitesse de ddpBt du coke sur le catalyseur B partir de la conversion du gazole et de I'isoler du rendement en gaz C1 B C4 augmente avec la temperature du reacteur alors que la production de gazoline et de coke diminue. Keywords: FCC process, fluid catalytic cracking, catalytic cracking, four-lump kinetic model. h i d catalytic cracking (FCC) is a process which uses an acidic catalyst to decompose heavy oil, such as vacuum gas oil, into more valuable lighter hydrocarbons at temperatures of about 5 10C.Since this cracking reaction is endothermic, heat is usually supplied by the regenerator in which the deposited coke is burnt out to reactivate the catalyst. In the reaction section, the preheated gas oil at 340C is fed into the bottom of the riser, where it becomes tiny oil drops and contacts the reactivated catalyst. The reactions take place immediately in the riser and gas volume increases drastically. This gas phase containing reactant and product, and carrying catalyst particles flows upward to the top where the reactions are completed. The product gas and catalyst are than fed to the cyclone and separated. Catalyst is transported to the regenerator and then recycled back to the reactor. The makeup catalyst is added regularly due to the losses by friction and attrition of catalyst particles. In the FCC process, heat generated by burning deposited coke on the catalyst surface supplies heat required for gas oil vaporization and endothermic reactions. Therefore an accurate estimate of coke formation will provide also an accurate measure of heat generated for heat integration. One way to achieve this goal is to obtain coke formation independently from other constituents. In this paper a 4-lump model is proposed for reactor kinetics to examine coke formation with conversion and yield of gasoline. Before this new model is described in detail, other models frequently quoted are introduced.

Models for reaction kinetics


The earliest equation relating coke formation and gas oil conversion was proposed by Voorhies ( 1945). The equation he suggested was CJ= B f

. . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . (1)

where Cfis ratio of coke formed to feed in weight %, t is gas oil conversion %, and B and m are the parameters which depend on temperature, feed composition, and catalyst type. This equation is very simple but not of practical use, since it only relates coke formation and extent of conversion of gas oil. Because other products are not considered in this expression, further analysis from this model is limited. Weekman (1968) proposed a more realistic 3-lump model. He assumed that the catalytic cracking kinetics are second order, and lumped reactant and all products into three major groups : feed, coke plus C 1 4 4 hydrocarbons, and gasoline (Cs-21o'C). Wojciechowski ( 1968) used the same lumping consideration except that the reaction kinetics are considered to be a dependent variable of feed composition, so that this model has two more variables than the original 3-lump model of Weekman. It involved more complicated mathematics in some cases which limits its popular acceptance. However, these two 3-lump models have similar advantages compared to others: 1. simplicity 2. ease of set up and solution of kinetic, material, and energy equations. 3. ability to calculate gas oil conversion and gasoline yield simultaneously. However, the weak point of the 3-lump model is that the coke generated in the cracking reaction cannot be determined. Jacob et al. (1976) proposed a more complicated and detailed 10-lump model. Based on molecular structure, he lumped the reaction feed into concentrations of paraffins; napthenes; aromatic rings; and aromatic substituent groups in both the heavy (>343"C) and light fractions of the charge stock, and two + coke and gasoline of C5-221"C. product groups of C I - C ~ In this 10-lump model the reaction rate constant is considered to be independent of feed composition. Advantages of the model are that the gas oil conversion extent can be estimated, and that production rate of some specific products such as heavy fuel oil, light oil, and gasoline can be calculated also. The shortcomings of this model are: very complicated
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THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67, AUGUST, 1989

mathematical equations are involved, feed composition must be analyzed beforehand, more experimental data are needed, and coke formation still cannot be determined independently. As mentioned earlier, the endothermic heat needed in the reactor is supplied by burning coke which has deposited on the catalyst. Thus, the accurate prediction of coke formation will aid heat integration and reactor temperature control. However, the models developed so far have no advantage for this purpose, whereas the following 4-lump model is developed based on this consideration.

Proposed 4-lump model


This proposed 4-lump model, as shown in Figure 1, is similar to the 3-lump model of Weekman, the main difference being that coke is independently considered as a lump. Other lumps are feed, gasoline, and C 1 4 4gas. We assume that the vacuum gas oil is cracked into the most desired gasoline, and the by-products of Cl-C4 gas and coke. Since the FCC reactor is operating at high temperature, the secondary cracking reaction occurs for gasoline to form coke and C I - C gas. ~ There is no inter-reaction between coke and C I - C ~ gas. Several assumptions are imposed on this proposed 4-lump model: 1. Gas flow in the reactor is an ideal plug flow. 2. Axial dispersion in the reactor is negligible. 3. Gas oil cracking reaction is second order. 4. Gasoline cracking reaction is first order. 5. Both gas oil and gasoline have identical activity decay function $. 6. C1-Q gas does not produce coke, which is mainly produced from aromatic hydrocarbons. 7. Coke content in feed is very low. Based on the above assumptions and the depiction of the 4-lump model diagram (Figure l), the overall reactions can be expressed by Equations (2) to (6):

Figure I - Four-lump kinetic model.

H =

c/o* s * VR * PF .......................

(9)

The catalyst residence time is given by

The gas oil space time is given by


h. = H/GF = tc * C/O

.......................

( 1 1)

If catalyst in the riser is assume to be in plug flow, the differential equations can be solved for the system variables. The conversion of gas oil can be obtained directly from Equation (2):

yl =

Cllc

where ki Equation ( 2 ) ,we obtain

+ kit,, (1 - EXP(-at,) ) . . . . . . . . . . . . . (12) = ki2 + k 1 3 + ki4. If Equation (3) be divided by

arc

dY3 _ - k13@yl 2 dt,'


- = k14@YI

+ k23@y2 .....................
+ k24@y2 .....................
.............................

.... (13)
.(4)
.(5)

dY4

dti,

which has initial conditions y i = 1, y2 = 0. Here k2 = k23 + k24. This is the equation for the yield of gasoline. Solution of Equation (13) gives y2 in terms of y i :

@ = Exp (-arc)

.(6)

We also assume that the cracking reaction is almost completed in the riser. Since the velocities of gas and solid in the riser may be different, the ratio of these two velocities is defined as the slip factor

where ri = k i d k i , r2 = k d k i and

The catalyst hold-up can be expressed as H = CCR * s * VR * PF GF

Equation (4) divided by Equation ( 2 ) will give the yield of C 1 4 4gas in terms of yi andy2:

......................

.(8)

Let CCRIGF = C/O represent the circulation rate of catalyst per unit mass of feed. Then
616

for which y i = 1, y3 = 0.

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67, AUGUST, 1989

TABLE 1

Experimental Data (Wang, 1974) Temp. "C


482.2

CIO 4
4 4

tc-', hr-'

YI, wt.%

y3, wt.%

p, wt.%
-

y4, w t %

120 32 40
40

59.98 29.13 33.28 49.83 50.74 37.96 28.82 17.62 46.26 30.17 22.38 20.75 28.76 39.06

30.22 49.82
-

548.8

3 4 4 4
4

615.5

3 3 3
4

60 30 20 10 240 120 80 120 180 300

37.09 37.69 43.85 48.65 54.16 -

14.52 9.95 8.85 13.60 16.81 21.28 -

'

4 4

50.39 47.02 -

22.44 17.56 -

6.53 5.73 3.13 2.74 4.59 5.72 7.14 3.28 5.09 6.21 6.42 5.03 3.35

Equation (5) divided by Equation ( 2 )will give coke formation in terms of yi and y2:
dy4

Case study
A FCC process obtained from the literature of Wang (1974) is selected to be analyzed by the proposed 4-lump model. For this real process, some considerations must be made: 1. The catalyst is highly active, so that the cracking reaction is almost completed in the riser. 2. The catalyst particle is small, and the vaporized gas oil or products carrying the catalyst particles flow at high velocity in the riser, so that the slip factor can be assumed unity. 3. The conversion is defined as: (100-weight percentage of products with B.P >204"C). Through the analysis of this 4-lump model, the reaction rate constants, the activation energies, and the frequency factors at different temperatures are calculated and given in Table 2. Figures 2 to 7 show the conversion of gas oil, gasoline yield, and coke formation obtained by this model and also the experimental values. It is obvious that the calculated results match the experiment very well. This shows that this 4-lump model is reasonable and reliable to predict FCC reaction kinetics. Also, some characteristics of FCC reaction kinetics are worth mentioning: I. The cracking reaction of gas oil is second order, while for the gasoline the cracking reaction is first order. Both 3-lump and 4-lump models have this identical assumption, which has been proved by Weekman's experiments (1979). 2. Cracking reactions of gas oil and gasoline take place on the acidic sites of catalyst, so that an identical decay function @ for both cracking reactions is reasonable. 3. Gasoline yield increases with conversion of gas oil, but there exists a maximum, beyond which the gasoline yield decreases due to cracking. The assumption of identical catalyst activity decay function will give both gasoline yield and coke formation as a function of conversion only. The reaction kinetics of the FCC reactor depend on process variables and parameters such as temperature, space velocity, ratio of catalyst circulation rate to oil mass flow rate, regenerator temperature, gas oil preheat temperature, physical properties of the gas oil and properties of the catalyst. Usually, feed and catalyst conditions do not change frequently. Thus, they are not considered to be variable in this study. Among all possible variables, the most important one is the reactor temperature. Figure 2 shows the effect of space velocity on gas oil conversion at different temperatures. It is found that the higher reactor temperature, the greater the conversion of gas oil and production of C I - C ~ gas, since the reaction is
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k14

k24 1'2
~

.....................

(16)

d Y 1

ki

k i yr2

withyi = l,y4=O.Equation(lS)andEquation (16)arehighly nonlinear and an analytical solution is not possible. Thus, a numeiical method for solving nonlinear differential equation must be employed here. Before the equations are solved, some reaction rate constants or parameters must be determined. The following section shows how these constants and parameters are evaluated with experimental data.
1) kl and a

With Equation ( 1 2 ) , which gives the conversion extent of gas oil, and a set of experimental data (rv, tc,yi), an objective function min. C(y1exp-ylcalc.)2 is defined for regression. The minimum objective function will give the best values of kl and a.

2 ) k12 and k2 With gasoline yield by Equation (13) and a set of experimental data (yl,y2), re ression analysis can be used to minimize Z(y2exp-~2calc.) .This will give the best values of k12/kI and k2/k1. The desired rate constants k12 and k2 are obtained by the known value of k'.

3) k 1 4 and k24 With Equation (16), which gives coke formation, and a set of experimental data 011,y4), regression analysis can be used to minimize Z(y4exp -y4caic.) 2. This will give the best values of k14/ki and k24/ki. The desired rate constants k 1 4and k24 are obtained by the known value of k l .
4) k 1 3 and k23 Reaction rate constant k 1 3 can be obtained by the equation
k13 = kl - k12

k14

.......................

(17)

and rate constant k23 can be obtained by


k23 = k2

k24

.............................

(18)

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67. AUGUST, 1989

TABLE 2 Reaction Rate Constants and Activation Energy Temperature, 'C

482.2
U
k12 ki k13 k14 k2 k23 k24

548.8 16.140 39.364 52.415 9.749 3.302 3.123 1.730 0.393

615.5 31.102 79.408 113.440 28.020 6.012 3.854 2.470 1.364 3.017 * 10' 7.978. lo5 1.937. lo6 4.549. lo6 3.765 lo4 4.308. lo3 3.255 . lo3 7.957. 10 117.7050 68.2495 72.2526 89.2164 64.5750 5 1.6726 52.7184 115.4580

1.944 15.644 20.264 3.323 1.297 1.122 0.711 0.411

* k (or a)= ko exp (-EJRT)


100 C/0=4

Temp: 548.8.C c/o : 4

01 0

10

20

30

40

50

60

70

80

35b

10

20

30

Space vel ocit y, h Ti


Figure 2 -Effect of space velocity on gas oil conversion.

Space vel oc it y, h r-'


Figure 3 -Effect of space velocity on gasoline yield.

8.0

Temp: 548.8.C

Conclusion In this paper a 4-lump model for FCC reactor analysis is proposed. Using this model, the reaction kinetics of FCC reactor are analyzed. The experimental data of Wang (1974) are used to estimate reaction rate constants and other parameters. Results obtained by this model show that the calculated values of gas oil conversion and gasoline production are very consistent with experiment. The main advantage of this proposed model is its ability to predict coke information, which other models are unable to do. This is important for heat integrationconsiderations. Acknowledgement The authors acknowledge the financial support for this research by the Chinese Petroleum Corporation. Nomenclature
CCR

' 0 10 20 30 40 50 60 70 80 90 100

Conversion, wt.%
Figure 4 -Coke yield vs. conversion at different temperatures.

endothermic. But higher temperature does not favour gasoline production, this can be observed from Table 1 or Figure 5. There must be an optimum point to consider gas oil conversion and gasoline production simultaneously.The next important variable might be the space velocity of reactant. The smaller space velocity will increase the contact time and favour gas oil conversion and also gasoline yield. Another important factor is the ratio of catalyst circulation to gas oil mass flow rate. This ratio also relates to the number of active sites availablefor gas oil cracking. The larger this ratio is, the more gas oil conversion is expected.

c/o

GF H
kij ko

El2

4
R
S

T
618

= rate of cycling catalyst, kg/hr = cycling catalyst rate/feedstock mass f l o w rate = activationenergy, kJ/mol = feedstock mass flow rate, kg/hr = catalyst hold-up, kg = reaction rate constant for reaction of lump i to lumpj = frequency factor i n Arrhenius Equation, hr = lumpnumber = universal gas constant = 0.00831 kJ/(mol.K) = slip factor = absolute temperature, K

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67, AUGUST, 1989

1001

-t
70
3

80

c/o=4 5 4 8 . 8 ~ A : c/o=3 54a.a.c : C/0=4 61 5.5'C


0 :

- 60

/ !
Con version, w t . %

1001

90

a0 70 -

Temp: 548.8.C 0 :c/o= 4 . .-In


7

2 0
gasoline

10

0 0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

Figure 5 - Gasoline yield vs. gas oil conversion at different catalyst residence time, hr gas oil space time, hr volume of riser, m3 catalyst flow velocity, m/hr gas oil weight percentage, wt% gasoline weight percentage, wt% C 1 4 4gas weight percentage, wt% coke weight percentage, wt%

Con version, w t. % Figure 6 -Different product yields vs. gas oil conversion.
Paraskos, J.A., Y.T. Shah, J.D. Mckinney and N.L. Cam, "A Kinematic Model for Catalytic Cracking in A Transfer Line Reactor", Ind. Eng. Chem. Proc. Des. Dev. 15, 165-169 (1976). Pohlenz, J.B., "How Operational Variables Affect Fluid Catalytic Cracking", Oil Gas J., April 1, 124-143 (1963). Voorhies, A., "Carbon Formation in Catalytic Cracking", Ind. Eng. Chem. 37,318-322 (1945). Wang, I., "High Temperature Catalytic Cracking", Ph. D. Dissertation, Fuels Eng. Department. Univ of Utah, Salt Lake City, Utah ( 1974). Weekman, V.W., "A Model of Catalytic Cracking Conversion in Fixed, Moving, and Fluid-Bed Reactors", Ind. Eng. Chem. Proc. Des. Dev. 7,90-95 (1968) Weekman, V.W., "Lumps, Models, and Kinetics in Practice", AIChE Monograph Series No. 11,75,3-29 (1 979). White, P.J., "How Cracker Feed Influences Yields", Hydrocarbon Processing 47, 103-108 (1968). Wojciechowski, B.W., "A Theoretical Treatment of Catalyst Decay", Can. J. Chem. Eng. 46,48-52 (1968).

catalyst decay parameter density of gas oil feed catalyst activity decay function defined in quation (6)

Blanding, F.H., "Reaction Rates in Catalytic Cracking of Petroleum", Ind. Eng. Chem. 45, 1186-1 197 (1953). Jacob, S.M.. B. Gross. S.E. Voltz and V.W. Weekman. "A Lumuine and Reaction Scheme for Catalytic Cracking", AIChE J.' 22: 701-713 (1976). Pachovbki, R.A. and B.W. Wojciechowski, "Theoretical Interpretation of Gas Oil Conversion Data on An X-Sieve Catalyst", Can. J. Chem. Eng. 49,365-369 (1971).

Manuscript received September 28, 1987; revised manuscript received November 28, 1988; accepted for publication January 10, 1989.

THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 67, AUGUST, 1989

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