Applied Catalysis A: General 213 (2001) 233237

The kinetics of methanol decomposition: a part of autothermal partial oxidation to produce hydrogen for fuel cells
Peter Mizsey1 , Esmond Newson , Than-binh Truong, Peter Hottinger
Paul Scherrer Institut, CH-5232 Villigen-PSI, Switzerland Received 26 June 2000; received in revised form 8 December 2000; accepted 8 December 2000

Abstract Methanol is considered as a renewable energy source for fuel processorfuel cell systems. The determination of the kinetics of methanol autothermal partial oxidation can be simplied if the problem is divided into subproblems. As a rst step, the kinetics of methanol decomposition (Me) are studied. To describe this subproblem, a reaction system consisting of four reactions is assumed. The reactions are: Me, dimethyl ether (DME) formation, steam reforming, and water gas shift (WGS) which are studied on a commercial copper containing catalyst (5 wt.% copper on alumina). The dehydration of methanol to DME is a second order reaction and essentially provides an excess of water over the whole reactor allowing rst order kinetic assumptions for steam reforming and WGS. The WGS reaction proves to be slow, compared to the other reactions, and equilibrium limited. The activation energies (kJ/mol) are estimated: Me 76 (4%), DME formation 117 (2%), steam reforming 81 (7%), WGS 50 (25%). Turnover frequencies for Me are estimated based on copper surface areas determined by the nitrous oxide pulse reduction method. At 220 C, values of 0.05 s1 are estimated compared to a literature value of 0.019 s1 at 200 C. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Methanol decomposition; Kinetics; Fixed bed reactor; Fuel cell

1. Introduction Fuel processorfuel cell systems offer a cleaner alternative to internal combustion engines for mobile systems based on well-to-wheel analysis but only the fuel reformerfuel cell power train using methanol has the advantage that the methanol could be derived from a renewable energy source (biomass). This case has the lowest environmental impact, is CO2 neutral, and offers a sustainable energy solution. The methanol can
Corresponding author. Tel.: +41-56-310-2640; fax: +41-56-310-2199. E-mail address: newson@psi.ch (E. Newson). 1 Present address: Department of Chemical Engineering, Technical University of Budapest, H-1521 Budapest, Hungary.

be catalytically converted to produce clean hydrogen for the fuel cell. The exothermic partial oxidation of methanol in a xed bed hot spot reactor has been already proposed [1]. Higher hydrogen production from methanol can be achieved if autothermal partial oxidation is applied:
1 4 CH3 OH + 3 H2 O + 2 O2 11 H2 +4 CO2

(1)

Developments in the kinetics of autothermal partial oxidation [2] and reactor start-up dynamics [3] have shown advantages over the endothermic steam reforming of methanol [4]. An analysis of full fuel cycle efciencies has shown [5] that the fuel processorfuel cell subsystem must reach an energy efciency of 40% so that the full fuel cycle efciency (24%) exceeds comparable values of 18% for internal combustion

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 6 - 8 6 0 X ( 0 0 ) 0 0 9 0 7 - 8

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P. Mizsey et al. / Applied Catalysis A: General 213 (2001) 233237

Nomenclature A DME E k Keq Me P r R SR T WGS x

0 HR

pre-exponential factor (mol/g cat s kPax ) symbol for dimethyl ether formation activation enthalpy (kJ/mol) reaction rate constant equilibrium coefcient symbol for the methanol decomposition reaction partial pressure rate of reaction (mol/g cat s) gas coefcient, 8.314 (J/mol K) symbol for the steam reforming reaction temperature symbol for the water gas shift reaction sum of the stoichiometric coefcients in the rate equation standard heat of reaction (kJ/mol)

using a commercial copper on alumina catalyst as part of more comprehensive kinetics for autothermal methanol partial oxidation. Preliminary work with the commercial catalyst on Me showed that four reactions are necessary to describe the reaction system (Table 1). The solution of the kinetics of the four-reactionsystem can be further simplied if the reactions could be studied individually. For such an individual study only the WGS reaction can be considered with the assumption that the presence of the other components, e.g. methanol, has negligible impact on the kinetics.

2. Experimental The experimental system consists of three major parts: feed, reactor, and analytical (Fig. 1). The system is fully computer controlled for continuous operation and safety features. Flows, pressure, and temperature parameters are controlled (FC, PC, TC). The methanol is vaporised and contacted in a static mixer with the diluent nitrogen according to requirements. The system allows the study of other cases, e.g. if oxygen and/or hydrogen are also used for experiments, methanol feed quality is analysis grade (99.8%) and gas purities are 99.995%. The feed mixture enters the microreactor, which has an internal diameter of 4 mm and a total length of 130 mm. The length of the isothermal catalyst bed is 14 mm, containing 100 mg of crushed, commercial catalyst in the particle size range of 0.250.5 mm. The catalyst, supplied by JohnsonMatthey plc, UK, under a condentiality agreement, contained 5 wt.% copper on alumina. Characterisation for copper surface area is made by using the nitrous oxide pulse reduction method. The product of the reactor is analysed by a GC (HP 6980) having three different columns and two different detectors (FID, TCD). The water content in the condenser is analysed by a 737KF Coulometer. The temperature ranges between 220 and 300 C, the weight hourly space velocities of methanol (WHSV) go up from 5 till 40 h1 , at 300 C even till 100 h1 . The pressure is constant at 3 bar. Thirty-seven independent isothermal points were measured and evaluated, the C, H, O balances were within 510%.

engines in mobile systems. With a 50% efciency for the polymer electrolyte fuel cell, an 80% efciency of the fuel processor is required which is determined by the catalyst kinetics and reaction engineering of the subsystem. The understanding of the kinetics of the methanol autothermal partial oxidation can be simplied if the reaction system is studied following a step-by-step methodology. As a rst step, the kinetics of Me is studied and the data obtained will be used later for the determination of the kinetics of autothermal partial oxidation [2]. In addition, Me is one possible reaction which produces carbon monoxide to which low temperature fuel cells are extremely sensitive. Recent literature on the comprehensive kinetics of methanol-steam reforming over a commercial shift catalyst [68] suggested that the rate determining step for both steam reforming and decomposition was the dissociation of formate species to hydrogen and carbon dioxide, the formate derived from adsorbed methoxy species on active copper metal sites. To include reactions containing carbon monoxide, water gas shift (WGS) was considered non-negligible in contrast to earlier work [9]. The purpose of this paper is to determine the applied kinetics for methanol decomposition (Me)

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Reaction 4: Steam reforming (SR) Keq,SR = 1.849E+10 exp 56087 RT (5)

Fig. 1. Experimental apparatus for methanol decomposition.

The kinetics are signicantly inuenced by the WGS equilibrium, less so for DME and Me, and insignicant for SR, that is the production of methanol in the reverse reactions can be practically excluded. The kinetics of the WGS reaction can be studied individually. In separate experiments a reformate gas mixture (2% CO, 10% CO2 , 20% H2 , 68% N2 ) was used to determine the kinetics of the WGS reaction. The measurements at different temperatures, water compositions (water contents: 4.2, 20, and 30% of the total mixture), and conversion rates show that the rate of reaction of WGS depends both on the water (PH2 O ) and the carbon monoxide composition (PCO ) and can be described by the following equation: rWGS = 2.25E 3 exp 50000 RT EqWGS (mol/g cat s) PCO2 PH2 Keq,WGS PCO PH2 O PCO PH2 O (6)

3. Results and discussion For the kinetic model, each reaction is rst studied to determine if equilibrium limitation is signicant. Based on Gibbs free energies, the equilibrium coefcients (Keq ) are determined. Reaction 1: Dimethyl ether formation (DME) Keq,DME 21858 = 0.106 exp RT (2)

where the partial pressures are in kPa, and EqWGS is EqWGS = 1 (7)

Reaction 2: Methanol decomposition (Me) Keq,Me = 1.718E+14 exp 95418 RT (3)

Reaction 3: Water gas shift (WGS) Keq,WGS = 9.543E 3 exp 39876 RT (4)

In these separate experiments, the WGS reaction has a rst order dependence on the partial pressure of water but in the global evaluation of the four reactions, due to water rapidly produced from the DME reaction, zero order dependence on the partial pressure of water is assumed. During the evaluation of the experimental data for the whole four-reaction-system, it is found that the WGS reaction rate is one to three orders of magnitude less than those of the other reactions, and therefore, this reaction can be neglected at the conditions studied

Table 1 The four reactions considered to describe the methanol decomposition system Name DME formation MeOH decomposition Water gas shift (WGS) Steam reforming (SR) Reaction 2CH3 OH CH3 OCH3 + H2 O CH3 OH CO + 2H2 CO + H2 O CO2 + H2 CH3 OH + H2 O CO2 + 3H2
0 HR (kJ/mol)

21 +91 41 +50

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Table 2 Pre-exponential factors and activation energies for methanol decomposition Reaction DME MeOH decomposition (Me) WGS (individually determined) SR Activation energy (kJ/mol) 117 76 50 81 (2%) (4%) (25%) (7%) Pre-exponential factor (mol/g cat s kPax ) 2040 (15%) 1.12 (12%) 0.0023 (32%) 6.75 (34%)

and only a three-reaction-system (DME, Me, SR reactions) is to be solved for the kinetic model of Me. The measured isothermal data points are evaluated with the SIMUSOLV software package [10]. Arrhenius temperature dependence is assumed during the evaluation, the activation energies and the pre-exponential factors are determined by the multidimensional optimisation method of gradient type, part of the SIMUSOLV program. The results of the evaluation of the measured data show that the second-order dehydration of methanol to dimethyl ether (DME) can be described with a second order mechanism. This reaction proves to be much faster than the others and essentially provides an excess of water over the whole reactor allowing rst order kinetic assumptions for Me, and steam reforming. The rates of reactions can be written in the following form: 1. DME formation
2 r1 = k1 PMeOH EqDME

4. Steam reforming (SR) r4 = k4 PMeOH EqSR (11)

(8)

2. MeOH decomposition r2 = k2 PMeOH EqMe 3. Water gas shift (WGS), neglected

0 r3 = k3 PCO PH2 O EqWGS

(9)

(10)

The pre-exponential factors and activation energies are summarised in Table 2. The standard deviations are also indicated in percentages of the actual values. The condence of the parameter estimation completed for the three-reaction-system is also tested. The correlation matrix is shown in Table 3. The correlation matrix shows that there is a strong correlation between the pre-exponential factor and the activation energy of each individual reaction but intercorrelations of kinetic constants are insignicant. Turnover frequencies for Me for the commercial copper containing catalyst are determined based on copper surface areas. A copper surface area value of 5.2 m2 /g catalyst was measured by pulsing nitrous oxide over the sample at 80 C. Turnover frequencies for Me at 220 C were estimated at 0.05 s1 compared to literature values of 0.019 s1 at 200 C for a 15 wt.% Pd/ZrO2 catalyst [11]. The accuracy of the kinetic model is tested, by comparison of the predicted and observed rate of reaction for the Me (Fig. 2). The agreement is within 10% which is the error expected from the mass balances and the standard deviations of the kinetic constants

Table 3 Correlation matrix of the three-reaction-system for methanol decompositiona ADME ADME EDME AMe EMe ASR ESR
a

EDME 1.000 8.4791E02 8.3176E02 0.2067 0.2110

AMe

EMe

ASR

ESR

1.000 0.9988 9.2138E02 9.1063E02 0.2013 0.2041

1.000 0.9966 0.5884 0.5788

1.000 0.5834 0.5745

1.000 0.9972

1.000

A: pre-exponential factor; E: activation energy.

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determined. Four reactions were considered, DME formation, steam reforming and WGS, in addition to Me, which produces carbon monoxide and hydrogen. Auxiliary experiments show that the WGS reaction is negligible with this catalyst. The activation energies for DME formation, reforming and decomposition (117/81/76 kJ/mol, respectively) are comparable to literature values. Turnover frequencies (0.05 s1 ) are similar to a Pd/ZrO2 catalyst (0.019 s1 ) from literature. References
[1] J.W. Jenkins, E. Shutt, Platinum Met. Rev. 33 (3) 1989 118. [2] E. Newson, P. Mizsey, T. Truong, P. Hottinger, in: A. Corma, F.V. Melo, S. Mendioroz, J.L.G. Fierro (Eds.), Studies in Surface Science and Catalysis, Vol. 130, Elsevier, Amsterdam, 2000, p. 695. [3] S. Golunski, Platinum Met. Rev. 42 (1) (1998) 2. [4] B. Hhlein, M. Boe, J. Bogild-Hansen, P. Brckerhoff, G. Colsman, B. Emonts, R. Menzer, E. Riedel, J. Power Sources 61 (1996) 143. [5] B. Hhlein, in: Proceedings of the 2nd IEA Advanced Fuel Cell Workshop, Wislikofen, Switzerland, 1997, p. 43. [6] B.A. Peppley, J.C. Amphlett, L.M. Kearns, R.F. Mann, Appl. Catal. A 179 (1999) 21. [7] B.A. Peppley, J.C. Amphlett, L.M. Kearns, R.F. Mann, Appl. Catal. A 179 (1999) 31. [8] S.P. Asprey, B.W. Wojciechowski, B.A. Peppley, Appl. Catal. A 179 (1999) 51. [9] C.J. Jiang, D.L. Trimm, M.S. Wainwright, N.W. Cant, Appl. Catal. A 97 (1993) 145. [10] SIMUSOLV Version 3.0-150, Dow Chemical Company, 1993. [11] Y. Usami, K. Kagawa, M. Kawazoe, Y. Matsumura, H. Sakurai, M. Haruta, Appl. Catal. A 171 (1998) 123. [12] M. Wittman, Ph.D. Thesis, Technical University Mnchen, Germany, 1991.

Fig. 2. Comparison of observed (robs ) and predicted rates of reaction (rpred ) for Me (mol CH3 OH/g cat s).

and shows that the kinetic model can be used for the description of Me. The activation energy for DME formation is similar to the value obtained for -Al2 O3 [12], and consistent with the high alumina content (94%) of the catalyst used in this study. Using non-isothermal temperature scanning methods with a commercial low temperature shift catalyst, activation energies of 70/102/81 kJ/mol were obtained by Peppley et al. [68], for Me, steam reforming and WGS, respectively. Corresponding values from this work (Table 2) are comparable especially for decomposition and steam reforming. 4. Conclusions The kinetics of the Me reaction system with a commercial copper on alumina catalyst are