Chem. Eng. Comm., 192: 310326, 2005 Copyright # Taylor & Francis Inc.

ISSN: 0098-6445 print=1563-5201 online DOI: 10.1080=00986440590473515

Simultaneous Reaction-Deactivation Kinetics in N-Octane and Methylcyclopentane Reforming Reactions on Platinum-Containing Catalysts
ALFRED A. SUSU HORACE M. NGOMO OLAOSEBIKAN A. OLAFADEHAN ELIZABETH D. TADOR
Department of Chemical Engineering, University of Lagos, Lagos, Nigeria
The deactivation data obtained from the multiple regeneration of platinumcontaining catalysts were utilized to explore the efficiency of reforming catalyst utilization. The data were collected in a CSTR at a total pressure of 101.325 kPa and W=F values up to 0.33 g min=cm3. The reactive system investigated was the re-forming and coking of n-octane and methylcyclopentane on the monometallic Pt=Al2O3 and the bimetallic Pt-Re=Al2O3 catalysts. The deactivation models combined the kinetic equation with the coking equation; both of these equations were derived from mechanistic models. The kinetic expressions were based on the models of Susu et al. for n-octane reaction and Dartingues et al. for methylcyclopentane reaction. The coking mechanism of Corella and Asua was used for the coking reaction. The coupling of the two models resulted in a dynamic expression, and the parameter estimates were carried out without decoupling the main reaction from the coking reaction. The model formulation affords the estimation of the level of residual activity by the incorporation of a factor, f, representing incomplete deactivation. A high value of f was obtained for all deactivation-kinetic data indicating high utilization efficiency for the catalysts for the two reactants, regardless of the large difference in the coking ability of the hydrocarbon species. Keywords: n-Octane; Methylcyclopentane; Platinum and platinum-rhenium catalysts; Deactivation models of residual activity

Introduction
The deactivation of industrial catalysts adversely affects the profitability of industrial catalytic plants, as the catalytic process may represent a major cost component of the plant. For example, a catalytic re-former processing 100,000 bpd crude oil may cost about $1 billion, and the platinum catalyst cost may be about $278 million (Somorjai and Davis, 1982), at todays price of about $600 per ounce of platinum.
Received 24 May 2002; in final form 26 July 2003. Address correspondence to Alfred A. Susu, Department of Chemical Engineering, University of Lagos, Lagos, Nigeria. E-mail: alfredasusu22@hotmail.com

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Obviously, multiple regeneration and reuse of these catalysts is mandatory for the profitability of the refinery process. How long the catalyst lasts depends on how well the regeneration operations are carried out. It is therefore not surprising that the study of the deactivation of industrial catalysts is a fertile area of catalytic research. Understanding the coking process focuses on the structure of the various coke entities, their location on the catalyst surface (Barbier, 1987; Gallezot et al., 1989), whether the coke on the metal or on the support is responsible for the mortality of the catalyst, and whether the coke produced in the laboratory under an accelerated deactivation regime differs significantly from the coke produced under industrial re-forming conditions (Pieck and Perera, 1989). The focus on these issues has as the primary objective the fundamental understanding of the mechanism of the coking process and how that understanding could ultimately assist the prolongation of re-forming catalyst life (Ngomo and Susu, 1996). The modeling of deactivation kinetics is one of the methods used for understanding the deactivation process. The formulation of a reliable deactivation model that incorporates kinetic parameters for the reaction on the fresh catalyst surface is a daunting task because of the coupling of the kinetic expressions with the deactivation equations. This complexity is exacerbated by assumptions like the steady-state approximation and concepts of the rate-determining step and the most abundant intermediate. The decoupling is normally done universally through the assumption of separable kinetics whereby the deactivation expression is couched in terms of separate rate forms, involving factoring out the activity term. This approach of decoupling utilizes the extrapolation of the measured conversions to zero coke content or zero time. Modeling by nonseparability involves the coupling of the coking reaction with the main reaction(s) and the solution of the coupling equations for the decline in reaction rates. The nonseparability model of catalyst decline was first used by Forzatti and Ferratis (1982) to explain the deactivation mechanism of methanol oxidation on Fe2O3MoO3 catalyst. The kinetics for the fresh and deactivated catalyst was derived from the data of a chemical investigation carried out by Carbucicchio et al. (1979). Recently, we reported on the use of the nonseparability model to explain the deactivation kinetics of cyclohexane dehydrogenation on platinumalumina catalyst (Ngomo and Susu, 1996b). In that study, a residual activity term, f, was introduced into the analysis as a measure of catalyst utilization. Values of f of 0.918 and 0.948 were reported for h 1 and h 6 1, where h is the number of active sites involved in the coking reaction. This shows an unusually high efficiency for the catalyst utilization for cyclohexane dehydrogenation on Pt=Al2O3 catalyst. Also, the Langmuirian constants for the equilibrium and kinetic parameters were simultaneously determined by the model. It would therefore be instructive to apply the same technique to the more complex reactions of n-octane and methylcyclopentane on the platinum-containing catalysts; in addition, these two hydrocarbon reactants produce more coke on the catalyst surface than cyclohexane, which is a low coking reactant. The coking ability of the three hydrocarbon reactants proceeds according to the following sequence: methylcyclopentane > > n-octane > cyclohexane. It will therefore be instructive to see whether the values of f would be significantly dependent on the coking abilities of these hydrocarbon reactants. In this presentation, we report on our investigation on the application of the nonseparability model to the deactivation data of Onukwuli (1993) on n-octane and methylcyclopentane reaction on Pt=Al2O3 and Pt-Re=Al2O3 catalysts. Unlike in a previous presentation for the dehydrogenation of cyclohexane on Pt=Al2O3

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catalyst (Ngomo and Susu, 1996), the reversible conversion of the two hydrocarbon reactants was considered. The deactivation-kinetic data were collected in a continuous stirred tank reactor (CSTR) with N2 as carrier gas.

Derivation of Reaction-Deactivation Kinetic Models

n-Octane Susu and Ako (1986) proposed the reaction scheme shown in Figure 1 for the catalytic re-forming of n-octane (N) on Pt=Al2O3 catalyst to form ethylbenzene (EB), ortho- (OX), para- (PX), and meta-xylene (MX). A mechanism based on this scheme was developed by Onukwuli and Susu (2000), and they derived the following relationship for the re-forming of n-octane on the Pt=Al2O3 catalyst surface: ro where U KN CN K1 C1 KCP CCP KEB CEB KOX COX KH CH
2 KMX CMX KPX CPX 1=2

KA CN KB CEB CH 1U

1=2

In the presence of coke, the following relationship can be derived for the rate of reaction: ro kr KA CA kr0 KB CEB CH 1 c 1U
1=2

where c CC =Ct , the fraction of the catalyst surface that is deactivated from a single main reaction. The term (1 c) is the fraction of the catalyst surface that is clean, and it is commonly called the decay term. We need to develop an adequate expression for the decay term for an appropriate coking mechanism. The coking mechanism we have chosen is the d- mechanism that was proposed by Corella and Asua (1982). By this mechanism, M is the coke precursor and it is adsorbed on a site S: M S $ MS Km Cms Pm CS

Figure 1. Network of single reactions for n-octane reforming on Pt=A12O3 catalyst.

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By the d-1 mechanism, M the coke precursor is adsorbed in the main reaction in the following manner: nM hMS $ P1 Sh PSh coke precursor n 0; 1; h 1; 2 The coking sequence is given by: nM hMS $ P1 Sh $ P2 SH $ P3 Sh Step 2 in the above sequence is rate determining, and hence we have: dCP1 Sh h kd Pn m Cms dt Cms Km Pm Cs Hence, dCP1 Sh m h h kd Pn m Km Cs dt The site balance for strongly adsorbed products is given as follows:
2 CS Ct Cs KN CN CS K1 C1 CS KEB CEB CS KPX CPX 1=2

3 4

KMX CMX CS KOX COX CS KCP CCP CS KH CH CS hCP1 Sh Factorizing, we have: CS Ct hCP1 Sh 1U

Substituting Equation (7) into (5) yields:

nh h KA Ct hCP1 Sh h dCP1 Sh kd CA dt 1 Uh

In Equation (8), A has been substituted for M since the coke precursor, M, is the same as A. Integrating Equation (8) for h 1, we obtain, after suitable rearrangement, the equation for the decay term: 2 3 Zt n1 k C K 1 d A A c 1 exp4 dt5 9 Ct 1 U
0

Substitution of Equation (9) into (2) yields:   1=2 kr KA CA kr0 KB CEB CH Ct ro 2 0 1U 0 113 Zt n1 k C K 1 d A A dtAA5 41 f @1 exp@ Ct 1 U
0

10

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where f is the residual activity. It is a constant and is less than unity. For an mth site of the main reaction, Equation (10) becomes: h  m i 1=2 Ctm kr KA CA m kr0 KB CEB CH ro 1 Um 2 0 0 113 m Zt n 1 k C K 1 A d A AA5 41 f @1 exp@ Ct 1 U
0

11

The counterpart of Equation (11) for h 6 1 is given by: h  m i 1=2 kr KA CA m kr0 KB CEB CH Ctm ro 1 Um 93m 8 2 1 2 31 h> > Zt < nh h kd CA KA 5 =7 f h1 h 6 1 41 41 dt 5 > h> Ct 1 U h ; :
0

12

Methylcylopentane Figure 2 shows the reaction network for the kinetic conversion of methylcyclopentane on Pt=Al2O3 catalyst as reported by Dartingues et al. (1978). The mechanism for this network of reactions had been developed by Onukwuli and Susu (2000), and it was used to derive the following relationship for the rate of reaction with the dehydrogenation of adsorbed methylcyclopentane to adsorbed methylcyclopentene as the rate-determining step: ro KA CMCP KB CCH CH2 1U 13

Figure 2. Network of single reactions for methylcyclopentane on A12O3 catalyst.

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The equivalent of Equation (10) is given by the following relationship for methylcyclopentane for h 1: 0 kr KA CA kr KB CCH CH2 Ct ro 1U 2 0 0 113 Zt n 1 kd CA KA AA5 1 dt 14 41 f @1 exp@ Ct 1 U
0

For an mth site of the main reaction, Equation (14) becomes: 0 kr KA CA m kr KB CCH CH2 m Ct m ro 1 Um 2 0 0 113 m Zt n 1 kd CA KA CC7 1 6 B B dtAA5 41 f @1 exp@ Ct 1 U
0

15

The equivalent relationship to Equation (15) for h 6 1 is shown in Equation (16): 0 kr KA CA m kr KB CCH CH2 m Ct m ro 1 Um 93 m 8 2 1 2 3 1 h> > Zt < n h h f h 1 h k d C A K A 5 = 7 6 1 41 41 dt 16 5 > h> Ct ; :
0

Computational Experience
The estimated parameters were used as starting values in the general analysis scheme when all the parameters were estimated together in the models. The number of sites, m, involved in the main reaction is limited to one or two, as three or more sites for the main reaction are highly improbable. This limitation reduces the complexity of the highly nonlinear search routine of the program. The program was limited to m being unity, since the method used to determine m from an initial guess exhibited system instability and was found to be very sensitive to step changes. The model parameters in Equations (11), (12), (15), and (16) were estimated by minimizing DIFER (y), the residuals (objective function), which is the sum of squares of the difference between the experimental and predicted rates for i 1 to N: DIFER
N X i 1

rAi ^ rAi

where rAi is the predicted rate represented by the rate expressions in Equations (11), (12), (15), and (16) and b rA is the rate observed experimentally using the CSTR. For model parameter estimation, a nonlinear least square technique, the Flexible Polyhedron Simplex method for constrained optimization (David and Himmelblau, 1970; Himmelblau, 1982), was used to estimate the model parameters by minimization of the nonlinear objective function. This technique is an improvement of the regular Simplex technique, and it is very efficient and easy to implement on

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the computer. It is better than the direct search method because it requires less computer time to implement even though the convergence to termination is slower.

Analysis of Experimental Data

The data used for the validation of the deactivation models were gathered by Onukwuli (1993) in a CSTR with variable partial pressures of n-octane and methylcyclopentane at different temperatures. The initial concentration, CAo, is obtained from the initial partial, PAo, of n-octane and methylcyclopentane, CAo PAo=RT, and the rate equation is calculated from the equation: rA 1=W dNA=dt CAo VX=W. The concentration at any time, t, is calculated from CA CAo(1 XA). Using this formula for the conversion of n-octane to iso-octane, hydrogen, EB, O, P and MX, we have CN CAo(1 XN), as one mole of n-octane yields one mole each of the designated products. Since four moles of hydrogen were produced for every mole of reactant consumed, the concentration of hydrogen, CH2, is given by CH2 4(CAoCN). The value of experimental W=F 0.11 g=cm3. The above equations were used to calculate the rates and concentrations from experimental data and the results are displayed in Table I for n-octane conversion for Pt=Al2O3 catalyst, Table II for several process variables for methylcyclopentane conversion on Pt=Al2O3 catalyst, and Table III for methylcyclopentane conversion on Pt-Re=Al2O3.

Table I Experimental rates and concentrations for n-octane conversion on Pt=Al2O3 catalyst at PN 1.37 10 3 atm, CAO 0.2334 kg=m3, and temperature 713 K Rate 10 (kg=m=s) 2.3807 1.9092 0.8753 0.1400
3

Conversion (XA) 0.3300 0.2400 0.1600 0.1650

Concentration (kg=m3) CN 0.1564 0.1774 0.1961 0.1949 CEB 0.0770 0.0560 0.0373 0.0385 CPX 0.0770 0.0560 0.0373 0.0385 CMX 0.0770 0.0560 0.0373 0.0385 COX 0.0770 0.0560 0.0373 0.0385 CH2 0.3080 0.2240 0.1492 0.1540 CCP 0.0770 0.0560 0.0373 0.0385

Table II(a) Experimental rates and concentrations for methylcyclopentane conversion on Pt=Al2O3 catalyst at PMCP 0.092 atm, PH2 0.5 atm, CAo 1.686 kg=m3, and temperature 633 K Rate 10 (kg=m3=s) 1.794 1.204 6.25 0 0
4

Conversion (XA) 0.200 0.1500 0.2200 0.1000 0.1000

Concentration (kg=m3) CMCP 1.3488 1.4331 1.3150 1.5174 1.5174 CBZ 1.2363 0.2529 0.3710 0.6186 0.1686 CCH 1.2363 0.2529 0.3710 0.1686 0.1686 CN 1.2363 0.2529 0.3710 0.1686 0.1686 CH2 3.7089 0.7587 1.1130 0.5058 0.5058

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Table II(b) Experimental rates and concentrations for methylcyclopentane conversion on Pt=Al2O3 catalyst at PMCP 0.092 atm, CAo 1.686 kg=m3, PH2 0.33 atm, and temperature 663 K Rate 10 (kg=m3=s) 3.123 7.390 2.650 0
5

Conversion (XA) 0.1300 0.0825 0.0575 0.0500

Concentration (kg=m3) CMCP 1.4670 1.5511 1.5890 1.6017 CBZ 0.2190 0.1349 0.0970 0.0843 CCH 0.2190 0.1349 0.0970 0.0843 CN 0.2190 0.1349 0.0970 0.0843 CH2 0.6570 0.4047 0.2910 0.2529

Table II(c) Experimental rates and concentrations for methylcyclopentane conversion on Pt=Al2O3 catalyst at PMCP 0.092 atm, CAo 1.686 kg=m3, PH2 0.778 atm, and temperature 663 K Rate 10 (kg=m3=s) 1.2940 1.2650 0 0
5

Conversion ( XA) 0.2575 0.2000 0.1875 0.3450

Concentration (kg=m3) CMCP 1.2520 1.3488 1.3699 1.1043 CBZ 0.4340 0.3372 0.3161 1.1043 CCH 0.4340 0.3372 0.3161 0.5817 CN 0.4340 0.3372 0.3161 0.5817 CH2 1.3020 1.0116 0.9483 1.7451

Table II(d) Experimental rates and concentrations for methylcyclopentane conversion on Pt=Al2O3 catalyst at PMCP 0.092 atm, CAo 1.686 kg=m3, PH2 0.111 atm, and temperature 663 K Concentration (kg=m3) Rate 10 (kg=m3=s) 12.940 0 35.91 39.190 9.7265 0
5

Conversion (XA) 0.300 0.3375 0.3250 0.0825 0.0175 0.0075

CMCP 1.1802 1.1170 1.1381 1.5469 1.6565 1.6734

CBZ 0.5058 0.5690 0.5479 0.1391 0.0295 0.0126

CCH 0.5058 0.5690 0.5479 0.1391 0.0295 0.0126

CN 0.5058 0.5690 0.5479 0.1391 0.0295 0.0126

CH2 1.5174 1.7070 1.6437 0.4173 0.0885 0.0378

Results and Discussion

The general procedure in kinetic data procurement is to obtain conversion data on a fresh catalyst at different flow rates when the catalyst surface is free of coke or carbonaceous deposits. Modeling equations are then tested on these data, and the appropriate model parameters are determined on the basis of goodness of fit and

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Table III(a) Calculated rates and concentrations for methylcyclopentane conversion on Pt-Re=Al2O3 catalyst at PMCP 0.1447 atm, PH2 0.5 atm, CAo 8.8933 kg=m3, and temperature 683 K Rate 10 (kg=m3=s) 8.979 8.225 5.679 0
4

Conversion (XA) 0.200 0.1363 0.0825 0.0396

Concentration (kg=m3) CMCP 7.1146 7.6811 8.1596 8.5411 CBZ 1.7787 1.2122 0.7337 0.3522 CCH 1.7787 1.2122 0.7337 0.3522 CN 1.7787 1.2121 0.7337 0.3522 CH2 5.3361 3.6366 2.2011 1.0566

Table III(b) Experimental rates and concentrations for methylcyclopentane conversions on Pt-Re=Al2O3 catalyst at PMCP 0.092 atm, CAo 8.8933 kg=m3, PH2 0.5 atm, and temperature 683 K Concentration (kg=m3) Rate 10 (kg=m3) 23.807 19.092 8.7530 1.4004
4

Conversion (XA) 0.3300 0.2400 0.1600 0.1650

CN 0.1564 0.1774 0.1961 0.1949

C1 0.0770 0.0560 0.0373 0.0385

CEB 0.0770 0.0560 0.0373 0.0385

CPX 0.0770 0.0560 0.0373 0.0385

CMX 0.0770 0.0560 0.0373 0.0385

COX 0.0770 0.0560 0.0373 0.0385

CH2 0.3080 0.2240 0.1492 0.1540

CCP 0.0770 0.0560 0.0373 0.0385

the positivity of the parameters; an additional requirement is that the residual activity, f, must be less or equal to unity. The modeling is done without decoupling the main reaction from the coking reaction. The deactivation kinetic rate model developed here for the re-forming of n-octane and methylcyclopentane is a dynamic one that requires experimental temporal deactivation data for validation and parameter procurement. The modified Nelder-Mead (1965) Flexible Polygon Simplex Method was used to estimate the parameters. The deactivation data on Pt=Al2O3 catalyst for n-octane conversion at a partial pressure of 0.0137 atm and a temperature of 713 K and also for methylcyclopentane reaction at varying temperatures and partial pressures on Pt=Al2O3 and Pt-Re=Al2O3 catalysts were used for the modeling. The predicted profiles are shown against experimental data for n-octane conversion on Pt=Al2O3 catalyst (PN 0.0137 atm, PH2 0.5 atm, and T 713K) in Figure 3; that for MCP conversion on Pt=Al2O3 catalyst (PMCP 0.092 atm, PH2 0.5 atm, and T 633 K) is shown in Figure 4; that for MCP conversion (PMCP 0.092, PH2 0.33 atm, and T 633 K) is shown in Figure 5; that for MCP conversion (PMCP 0.092 atm, PH2 0.778, and T 633 K) is shown in Figure 6; that for MCP conversion (PMCP 0.092 atm, PH2 0.111 atm, and T 633 K) is shown in Figure 7; that for MCP conversion on Pt-Re=Al2O3 catalyst (PMCP 0.1447 atm, PH2 0.5 atm, and T 683 K) is shown in Figure 8; and that for MCP conversion (PMCP 0.092 atm) is shown in Figure 9. In all cases, the prediction is good.

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Figure 3. Model prediction of experimental data for n-octane conversion on Pt=A12O3 catalyst at PN 0.0137 atm, PH2 0.5 atm, T 713 K.

Figure 4. Model prediction of experimental data for MCP conversion on Pt=A12O3 catalyst at PMCP 0.092 atm, PH2 0.5 atm, T 633 K.

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Figure 5. Model prediction of experimental data for MCP conversion on Pt=A12O3 catalyst at PMCP 0.092 atm, PH2 0.33 atm, T 663 K.

Figure 6. Model prediction of experimental data for MCP conversion on Pt=A12O3 catalyst at PMCP 0.092 atm, PH2 0.778 atm, T 663 K.

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Figure 7. Model prediction of experimental data for MCP conversion on Pt=A12O3 catalyst at PMCP 0.092 atm, PH2 0.111 atm, T 633 K.

Figure 8. Model prediction of experimental data for MCP conversion on Pt-Re=A12O3 catalyst at PMCP 0.1447 atm, PH2 0.5 atm, T 683 K.

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Figure 9. Model prediction of experimental data for MCP conversion on Pt-Re=A12O3 catalyst at PMCP 0.092 atm, PH2 0.5 atm, T 683 K.

The final estimates of the parameters for the deactivation of n-octane on Pt=Al2O3 catalyst were: For h 1 at a temperature of 713 K and PN 0.0137 atm, kr 58.4109, kr0 11.6281, KA 250.6612, KB 9.5343, Ct 8.7757, KN 16.8843, K1 18.1351, KCP 25.6885, KEB 31.5787, KMX 52.1811, KPX 6.0458, KOX 10.5976, KH 30.1407, kd 30.1497, and f 0.9999. The value of the objective function 5.3490 10 6. The first observation about these computed parameters is that the forward rate constant is five times the value of the reverse rate constant. The value of KA is the largest by far of all the Ks (250.662) and should normally be indicative of very strong adsorption of A on the catalyst surface. However, KA k11K4KI, a composite of other rate and equilibrium constants, and no such inference can therefore be drawn. Of the remaining Ks, the dominant one is KMX (52.1811), indicating that metaxylene is the strongest held surface species on the catalyst surface. By the same argument, para-xylene is the least held of the three xylene species. The value of f is practically unity, indicating an efficient utilization of the catalyst. This confirms the earlier result for cyclohexane dehydrogenation on platinum catalyst. Equation (11) can now be fully written as follows: ro 25558:8242CA 4887:2491CEB CH 2 0 0 1 13 Zt 2 1 7551 : 3300 C A A A5 exp@ 41 0:9999@1 8:7757 1 U
0 1=2

17

Table IV Estimates of rate and equilibrium parameters for methylcyclopentane re-forming on Pt=Al2O3 and Pt-Re=Al2O3 catalysts at various process conditions Pt=Al203 PH2 0.5 atm; PMCP 0.09 atm T 663 K Pt-Re PH2 0.5 atm; PMCP 0.092 atm T 683 K 58.5174 12.0280 249.9365 10.8067 1.569 10 4 16.3515 18.6822 26.0804 30.0030 0.9959 8.3260 1.579 10 6 0.0801 57.4359 11.7239 249.0404 10.2558 4.735 10 6 16.5031 18.5800 25.8358 30.0146 0.9379 6.2627 4.151 10 8 0.1048 58.1659 11.1491 248.4652 11.4928 2.10 10 4 16.0367 18.4062 26.4988 31.4877 0.9977 8.4776 1.622 10 10 0.1101 Pt=Al2O3 PH2 0.778 atm; PMCP 0.09 atm T 663 K Pt-Re PH2 0.5 atm; PMCP 0.1447 atm T 683 K 56.8386 11.6551 248.8316 9.9793 1.240 10 5 16.4165 18.5455 25.6143 30.4538 0.8756 9.2389 1.738 10 5 0.1017

Pt=Al2O3 PH2 0.11 atm; Reaction PMCP 0.092 atm parameters T 663 K 59.3228 11.5187 250.9264 12.2765 3.426 10 5 18.4576 17.3486 27.0719 29.0909 0.9986 8.9866 5.244 10 0.09433

Pt=Al2O3 PH2 0.33 atm; PMCP 0.092 atm T 663 K

kr kr0 KA KB KMCP KC6 KCH KBZ kd F Ct y (OF)a r(rA)

58.7211 12.7211 249.7718 10.6502 7.942 10 5 16.3515 18.3935 25.8940 31.1067 0.9996 8.4450 3.009 10 5 0.08116

OF objective function.

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For h 6 1, the conditionality of positivity for the kinetic (kr and kr0 ) and the equilibrium (the Kis) parameters was satisfied, but the value of the deactivation term, f, was greater than unity (2.0003), thus violating the criterion that f, an efficiency parameter, must be less than 1. This was the case for all the models and therefore, the results for h 6 1 for all models will not be recorded. The average standard deviation for the re-forming of n-octane conversion on Pt=Al2O3 catalyst is given by: rrA 0:0841 Table IV shows the final estimates of the parameters of the model for the re-forming of methylcyclopentane on Pt=Al2O3 and Pt-Re=Al2O3 catalysts as functions of the process variables. The equilibrium and kinetic constants are relatively insensitive to variation in process conditions. The fact that KMCP is small (of the order of 10 5 to 10 6) is an indication of the very good adsorption of methylcyclopentane on the platinum-containing catalyst surface. Although the value of KA is about 250, it is difficult to ascribe it to strong adsorption because KA is a composite constant (k3KI). Benzene is the strongest held product species on the catalyst surface, reflective of the value of KBZ being about 26. As reported for n-octane, cyclohexane (Ngomo and Susu, 1996), and iso-octane (Essang, 1998), the values of the residual activity, f, can all be approximated to unity, which indicate very efficient utilization of the mono- and bimetallic platinum catalysts. Since the values of the equilibrium and kinetic parameters are quite comparable, we can as well report a single rate equation for methylcyclopentane reaction on Pt=Al2O3 and Pt-Re=Al2O3 catalysts incorporating one of the parameters indicated in Table IV. Equation (15) can now be fully written as: ro 23484:3369 5667:1828CCH CH2 1U 2 0 0 113 Zt 2 1 7823:5977CA AA5 exp@ dt 41 0:9997@1 8:4776 1 U
0

18

We now need to comment on the high value of f reported here for n-octane and methylcyclopentane; similar high values had been reported elsewhere for cyclohexane (Ngomo and Susu, 1996) and iso-octane (Essang, 1998). The value of f is greater than 0.9 for both n-octane and methylcyclopentane. The value of f for iso-octane has been reported to be 0.810 on Pt=Al2O3 catalyst (Essang, 1998). Ngomo and Susu (1996) have also reported the value of f to be 0.9180.948 for the dehydrogenation of cyclohexane on Pt=Al2O3 catalyst. The fact that f exhibits a very high value for these hydrocarbon reactants with widely varying coking abilities can be ascribed to the existence of a predominant coke type for all the reactants. This predominant coke type is oxidizable coke, which is removable by an oxygen-containing gas. This coke is obviously nontoxic to the re-forming reactions, as regeneration restores the catalyst activity. Although it has been reported that toxic cokes are produced simultaneously from oxidizable coke at the coke-catalyst surface interface (Osaheni et al., 2000), the magnitude of the oxidizable coke is a thousand-fold higher than the deleterious coke types. Since the catalyst activity is still high after regeneration, we can conclude that oxidizable coke is still predominant during the catalysis reported

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here. It is probable that the values of f would be reduced if the deleterious coke types predominate. This will occur only towards the latter part of the catalyst life when the catalyst surface must have been covered by irreversibly deposited toxic coke. Coking on the bifunctional Pt=Al2O3 catalyst occurs on the metal and later spreads to the areas ( % 20 nm) around the metal (Galkzot et al., 1989). The coke on the support is more polymeric than that on the metal. It is conceivable that the spread of this polymeric coke in all directions would lead to the total deactivation of the catalyst. One could then envisage the residual activity approaching zero. However, even in this case, the templates of coke spread need to coalesce to leave no patches of clean surface sites on the surface. Thus, no matter how extensive the surface coverage of coke on the catalyst surface, there would still be clean patches remaining on the catalyst surface, as zero activity will mean complete enveloping of the catalyst surface by the enlarging template. So, as far as the industrial life of the catalyst is concerned, this study would suggest that the efficiency of catalyst utilization would be high for as long as oxidizable coke predominates on the catalyst surface.

Conclusions
The major conclusions derivable from this work are the following: 1. The predictions of experimental deactivation data for n-octane conversion on Pt=Al2O3 catalyst and for methylcyclopentane conversion on Pt=Al2O3 and Pt-Re=Al2O3 catalysts were found to be good for coupled nonseparable mechanistic models of the kinetic and coking reactions. 2. In all cases reported, the predicted rate constants for the forward reaction were about five times higher than those for the reverse reaction. 3. The residual activity, f, was found be practically unity for n-octane and methylcyclopentane conversion, indicative of efficient utilization of the Pt=Al2O3 and Pt-Re=Al2O3 catalysts.

Nomenclature
n-Octane CA concentration of reactant (n-octane) CP cracked products EB ethylbenzene I iso-octane MX para-xylene N n-octane OX ortho-xylene PH partial pressure of hydrogen PN partial pressure of n-octane PX para-xylene P1 coke precursor P2, P3 other forms of coke KA k11K4KI KB k12 =K8 K10 KI 1=K 5

326 KCP KEB KOX K11 KMX KN KPX kd 1=K3 1=K8 1=K9 1=K10 1=K11 K1 1=K12 deactivation constant

A. A. Susu et al.

Methylcyclopentane BZ benzene CA concentration of reactant (methylcyclopentane) CH cyclohexane CH= cyclohexene MCP methylcyclopentane MCP= methylcyclopentene P1 coke precursor P2, P3 other forms of coke RC6 hydrogenolysis products RC6 olefinic hydrogenolysis products KB k 4 =K 3 K 7 K 8 KMCP K1 KC 5 1=K11 1 1=K4 K6 KCH 1=K8 1=K7 CH2 KBZ 1=K10 KA k3K1 kd deactivation constant

References
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