International Journal of Hydrogen Energy 32 (2007) 1806 1810 www.elsevier.

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Reactor concept for improved heat integration in autothermal methanol reforming

T.J. Schildhauer , K. Geissler1
Laboratory for Energy and Materials Cycles, Paul Scherrer Institut, CH-5232 Villigen PSI, Switzerland Received 27 August 2006; accepted 27 August 2006 Available online 10 October 2006

Abstract With regard to mobile applications, the autothermal methanol reforming process as hydrogen source for PEM-fuel cells has advantages compared to the externally heated steam reforming reaction in terms of control and transient behaviour. However, thermal (hot-spot) control of the autothermal process turns out to be the key issue for scale-up in order to ensure selectivity, catalyst stability and process safety. Therefore, a novel reactor concept based on ow redirection around catalytically coated plates has been developed. It shows a low pressure drop, improves heat integration and solves the scale-up problem of autothermal processes like autothermal methanol reforming. These improvements have been shown in experiments using Cu/Zn/Al2 O3 as catalyst. 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
Keywords: Autothermal reactor; Methanol; Reformer; Catalytic plate; Heat integration; Hydrogen

1. Introduction Autothermal processes can be considered as a combination of exothermic (e.g. partial oxidation) and endothermic reactions (e.g. steam reforming) in one reactor. Although the stoichiometry of the reactants can be adjusted to yield an overall reaction enthalpy of zero, the different reaction rates of the exothermic and the endothermic reaction often cause an unbalanced temperature prole. If simple tubular xed bed reactors are used, signicant hot spots in the entrance region can occur, sometimes even followed by a cold spot. During scale-up this problem becomes more and more severe, eventually even being a safety issue if run-away region is reached. In addition, even comparatively moderate hot-spots can shorten catalyst lifetime, decrease selectivity and limit space-time yield. Especially for strongly endothermic reactions, cold spots may lead to limitations due to the thermodynamic equilibrium. In the literature, many ways of controlling hot-spots and cold spots are mentioned, like e.g. catalyst or reactant dilution (with
Corresponding author. Tel.: +41 56 310 27 06; fax: +41 56 310 21 99.

ballast gas or product recirculation). For improved cooling or heating, it was found that direct coating of catalyst on highly conducting metal surfaces is a very promising concept [13], particularly when the cooling/heating agent ows on the back side [46]. Even higher energy ow densities can be reached, if an endothermic reaction takes place on one (catalytically coated) side of a highly conducting plate, while the heat is delivered by a catalytic combustion or another exothermic reaction on the backside [7]. This concept can be realized either using microstructured reactors [8,9] or plate-type geometries [10,11] or ceramic monoliths [12]. 1.1. Autothermal reactor concepts In order to solve the problem of uneven temperature prole in autothermal reactors, the simple removal of heat from the hot-spot region without recovery is not acceptable since the thermal efciency of the reactor is diminished. Some authors suggest to spread the heat over the reactor length by convection [13] or to distribute the heat production by splitting the O2 feed [14]. Periodic ow reversal in the reactor allows to use the heat capacity of the catalyst material to atten temperature proles [15]. Another concept is the distribution of the heat production

E-mail address: tilman.schildhauer@psi.ch (T.J. Schildhauer).

1 Present address: Dow Europe GmbH, Bachtobelstrasse 3, CH-8810 Hor-

gen, Switzerland.

0360-3199/$ - see front matter 2006 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2006.08.059

T.J. Schildhauer, K. Geissler / International Journal of Hydrogen Energy 32 (2007) 1806 1810

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CH3OH + O2 T
Cu/Zn/Al2O3

CO2 + 2 H2

(a) entrance side

z CO2 + 3 H2 CH3OH + H2O

catalytic plate flow redirection

exit side (b)

Fig. 2. Optimum heat transfer between the two sides of the reactor due to the use of catalytically coated plates.

Coated plates

Feed

(c)

Fig. 1. Reactor concept (b) and axial temperature proles for the entrance side (a) and the exit side (c) of the catalytic plate. The full line shows the (theoretical) adiabatic case and the dotted line shows the case with heat conduction (grey arrows).

over one side of a plate by staggered reactant injection to optimize the temperature prole for the endothermic reactions on the backside [16,17]. Schssler [18] embedded catalyst particles in a porous copper matrix which could redistribute the heat between hot and cold spots by its high conductivity. To ensure small heat conduction distances, a very short bed (< 3 mm) is used, combined with a high cross-sectional area folded up to form a compact reactor. Equal ow distribution is realized by means of a diffusion limiting layer coated on the inlet side of the copper matrix. A comprehensive overview of all aspects of integrating heat transfer into chemical reactors is given in [19]. The reactor concept developed at Paul Scherrer Institute [20] suggests a spatial coupling of the exothermic and endothermic reaction zones. This is realized by a reversal of the ow direction after the hot-spot. It allows using released heat at the backside of the contact area, as shown in Fig. 1. For optimized heat transfer between the two sides of the reactor, catalytically coated plates are used. Since the heat of reaction is released in the catalyst particle on the plate surface, only the wall and the catalyst are media for heat transfer between both sides, i.e. no limiting gassolid heat transfer is involved (Fig. 2). A schematic drawing of the complete reactor concept with more than one plate is given in Fig. 3. 1.2. Methanol reforming A typical example of an autothermal process which has been used in this work as model reaction is the methanol reforming. It can be applied as a hydrogen source for polymer electrolyte fuel cells. Since liquid methanol has a higher energy density per volume compared to hydrogen, its use as a hydrogen storage medium for non-stationary fuel cell applications could be advantageous [21].

Holder
Fig. 3. Scheme of the reactor, built up from catalytically coated plates between horse-shoe type spacers that hold the feed capillaries.

The ideal stoichiometry of the process can be found if the exothermal partial oxidation of methanol ( R H1 = 192 kJ/mol) and endothermic steam reforming ( R H2 = 49 kJ/mol) are balanced to an overall reaction enthalpy of ( R H(300 C) = 0 kJ/mol):
1 CH3 OH + 2 O2 CO2 + 2H2 ,

(1) (2) (3)

CH3 OH + H2 O CO2 + 3H2 ,

1 4CH3 OH + 3H2 O + 2 O2 4CO2 + 11H2 .

Thermodynamic analyses have shown, that the autothermal process not only is advantageous over conventional steam reforming in terms of control and transient behaviour but also has the potential of a high well-to-wheel efciency [22,23]. 2. Experimental To prove the concept and to examine the inuence of variation in temperature, space velocity and oxygen concentration, a small test unit was built. It consisted of 10 plates (FeCrAlloy, thickness 0.08 mm) with an active (coated) surface of 36 cm2 each, which were mounted between horseshoe-type spacers. The plates and spacers were pressed together by 10 tie bars to form 11 channels sealed against each other. The whole package was mounted in a thermally insulated stainless steel housing. The active surface was coated with 1.75 mg/cm2 Cu/Zn/Al2 O3

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T.J. Schildhauer, K. Geissler / International Journal of Hydrogen Energy 32 (2007) 1806 1810

330C 310C 290C 270C Fixed bed 1 2 3 4 Length of catalyst bed [cm] Plate type reactor, L = 2

WHSV = 10

pre-heating temperature

Fig. 5. Axial temperature proles of autothermal methanol reforming in a tubular reactor (1.3 times stoichiometric air ow) and the new plate-type reactor (doubled stoichiometric air ow) at equal methanol space velocity of 10 gMeOH (gcat h)1 and similar conversions.

Fig. 4. Experimental set-up before mounting: housing with thermowells (right), horseshoe-type spacers with capillaries (left), end plates.

340 330 temperature [C] 320 310 300 290 280 0

catalyst. The distance between the plates was 3 mm. Nine thermowells were welded into the bottom of the housing. Each held one slidable thermocouple to monitor the axial temperature prole in the middle between two plates. In two channels, three thermowells were located at different lateral positions. The equal distribution of the feed streams over the channels was realized by capillaries tted into the middle beam of each horse shoe-type spacer. This way, the pressure drop through the capillaries was higher than the one through the channels and could easily be controlled by changing the length of the capillary. The equal feed distribution over the channels width was not optimized with this set-up. Fig. 4 shows the single parts of the reactor before installation. The experiments were carried out by pre-heating the reactor under nitrogen to temperatures between 252 and 285 C. After reaching that temperature level, reactant ow was started. A stoichiometric watermethanol mixture with the molar ratio of 3 4 according to Eq. (3) was fed to the reactor via a vaporizer by means of pump (RCT M16, Reichelt Chemietechnik). Synthetic air ow was controlled by an electronic mass ow controller (Bronkhorst). The weight hourly space velocity was varied from 5 to 15 gMeOH (gcat h)1 . Product gas composition was determined by on-line gas chromatography described elsewhere [22]. 3. Results Fig. 5 shows examples of temperature proles for autothermal methanol reforming in both, a tubular reactor lled with 500 mg of the same catalyst and the novel reactor (630 mg catalyst) at equal space velocities of 10 gMeOH (gcat h)1 . For the catalytic plate reactor, the air ow was twice higher than the stoichiometric feed, compared to 1.3-fold stoichiometric air ow

272C, WHSV=5/h, L = 2 reverse side, 272C, WHSV= 5/h, L= 2 272C, WHSV=10/h, L = 2 reverse side, 272C, WHSV= 10/h, L= 2 285C, WHSV=10/h, L = 2 reverse side, 285C, WHSV=10/h, L= 2 285C, WHSV=10/h, L = 1.6 reverse side, 285C, WHSV= 10/h, L= 1.6

4 1 2 3 5 axial position from reactor inlet [cm]

Fig. 6. Axial temperature proles of autothermal methanol reforming in the new plate-type reactor for different methanol space velocities, pre-heating temperatures and multiples L of the stoichiometric air ows.

fed to the tubular reformer. It can be seen that the temperature prole in the new plate reactor remains at with only a minor temperature increase in the entrance region whereas in the tubular reactor a strong hot-spot and a moderate cold spot are observed. Fig. 6 shows the axial temperature proles for the new catalytic plate reactor for different pre-heating temperatures, space velocities and air ows. It can clearly be seen that the overall temperature level increases with increasing pre-heating temperatures, increase in air ow and increasing space velocity. Also the maximum temperature difference in the reactor increases, but stays always moderate. A comparison of the proles for the two space velocities at same pre-heating temperature shows, that the thermal proles of front- and backside of the plate automatically adapt to each other with changing liquid loads and therefore allow high load exibility for transient operation. It was found that the heat losses over the reactor wall due to insufcient insulation were that high, that stable reactor running was not possible with stoichiometric air ow multiples smaller than 1.6.

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temperature next to hotspot [C]

295 290 285 280 275 270 265 260 00:00 01:00 02:00 03:00 04:00 run time [hh : mm] 05:00 06:00 T reactor

Table 1 Experimental data

WHSV (1/h) L T pre-heating ( C) Conversion (%) H2 -yield (%) CO (mol%) Hot-spot ( C) 5 1.6 270 79 66 0.37 273 10 1.6 270 73 63 0.30 285 15 1.6 270 68 59 0.31 294 10 1.6 290 80 71 0.50 304 10 1.6 305 93 83 0.68 321

pre heating

catalyst

Fig. 7. Reactor temperature next to the hot-spot as a function of the time for WHSV of 15 gMeOH (gcat h)1 and stoichiometric air ow multiple L of 1.6.

T 325 315 Hot spot [C] 305 295 285 275 260 1 0.8 0.6 0.4 0.2 0 310 CO-concentration [mol-%] Hydrogen Yield

z-axis
Fig. 9. Integrating pre-heating function by partially not coating the plate.

270

280

290

300

pre-heating temperature [C]

Fig. 8. Hot-spot temperatures (squares), hydrogen yields (diamonds) and CO-concentrations (triangles) at varying pre-heating temperatures (WHSV = 10 gMeOH (gcat h)1 , stoichiometric air ow multiple L = 1.6).

develops stable temperature proles at any reactor inlet temperature above the light-off temperature. Therefore, the reactor can be adapted to different conditions and loads by simply changing the stoichiometric air ow multiple L, either heating up the reactor to a higher temperature level by overstoichiometric oxidation or cooling it down by favouring the steam reforming due to understoichiometric oxidation. 4. Conclusions It has been proved that the reactor works thermally stable at high conversions and regulates itself for changing loads. Low hot-spots (max. 23 K) and a mirror hot-spot at the reverse side of the plate atten considerably the axial temperature prole that improves the catalyst life-time. The concept allows easy scale-up by adding more plates to the reactor without changing the heat transfer conditions. The low-pressure drop minimizes power loss from gas compression. As the catalyst is xed on the plates, it shows high mechanical stability against the vibrations and shocks typically occurring in mobile applications. If necessary, the mass transfer rates from the gas phase to the coated plates surface can be adapted by the use of corrugated coated sheets to form an open cross ow structure. For different reaction systems, two or more different catalysts can be coated on the surfaces, as suggested by Piga and Verykios [24]. A non-reactive heat exchanging zone for pre-heating of the feed can easily be integrated by partly not coating the plates (Fig. 9). By (partly) feeding of reactant (e.g. air, oxygen) into the ow reversal zone, even more freedom in reactor design can be reached.

In ve experiments, it could be shown that the reactor runs stable (516 h). At a pre-heating temperature of ca. 270 C and 1.6-fold stoichiometric air ow with respect to Eq. (3), the space velocity was changed from 5 to 10 and then to 15 gMeOH (gcat h)1 . These changes in space velocity made the conversions drop from 79% over 73% to 68%, while the hotspots increased from 273 over 285 C to 294 C. Fig. 7 shows the reactor temperature next to the hot-spot for the experiment at 15 gMeOH (gcat h)1 . The regular temperature minima every hour are caused by the direction change of the pump piston. At a space velocity of 10 gMeOH (gcat h)1 , the reactor temperature level was increased to 290 C and then to ca. 305 C. As shown in Fig. 8, this led to conversions of about 80% and then 93%, the hot-spots increased to 304 C and then 321 C. The hydrogen yield could be improved to 71% and even 83% (related to Eq. (3)). For all experiments low CO-fractions (produced by reverse water gas shift reaction) were measured. As expected from equilibrium, CO-production increases with higher temperatures, from 0.3 to 0.68 mol%. Table 1 gives an overview over all results. The variation of the temperature at constant space velocity of 10 gMeOH (gcat h)1 shows that the autothermal reactor

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T.J. Schildhauer, K. Geissler / International Journal of Hydrogen Energy 32 (2007) 1806 1810 [5] Degnan TF, Wei J. The co-current reactor heat exchanger part II. Experimental results. AIChE J 1980;26(1):607. [6] Kohnke H-J. Entwicklung eines Methanolreformers basierend auf dem Plattenkonzept. Dissertation Universitt Gesamthochschule Kassel; 1995. [7] Gaiser G. Reactor for catalytically processing gaseous uids. U.S. Patent No. 5700434; 1997. [8] Charlesworth R, Gough A, Ramshaw C. Combustion and steam reforming of methane on thin layer catalysts for use in catalytic plate reactors. Proceedings IMechE C510/099/95; 1995. p. 859. [9] Janicke M, Holzwarth A, Fichtner M, Schubert K, Schth F. A microstructured catalytic reactor/heat exchanger for the controlled catalytic reaction between O2 and H2 . Stud Surf Sci Catal 2000;130: 43742. [10] Zanr M, Gavriilidis A. Modelling of a catalytic plate reactor for dehydrogenation-combustion coupling. Chem Eng Sci 2001;56(8): 267183. [11] Polman EA, Der Kinderen JM, Thuis FMA. Novel compact steam reformer for fuel cells with heat generation by catalytic combustion augmented by induction heating. Catal Today 1999;47:34751. [12] Frauhammer J, Eigenberger G, Hippel Lv, Arntz D. A new reactor concept for endothermic high-temperature reactions. Chem Eng Sci 1999;54:366170. [13] Jenkins JW. Catalytic hydrogen generator for the use with methanol. United States Patent 4,789,540 to Johnson Matthey plc; 1988. [14] Edwards N. Self-sustaining hydrogen generator. United States Patent 5,762,658 to Johnson Matthey plc; 1998. [15] Glckler B, Kolios G, Eigenberger G. Autothermal methane steam reforming. Chem Eng Sci 2003;58:593601. [16] Kolios G, Frauhammer J, Eigenberger G. Efcient reactor concepts for coupling of endothermic and exothermic reactions. Chem Eng Sci 2002;57:150510. [17] Morillo A, Merten C, Eigenberger G, Hermann I, Lemken D. Kompaktes Faltreaktorkonzept zur autothermen Dampfreformierung mit integrierter Verdampfung und Shiftstufe. Chemie Ingenieur Technik 2003;75(12): 6872. [18] Schssler M. Entwicklung eines kaltstartfhigen Reaktors fr die autotherme Reformierung von Methanol. In: Fortschrittsbericht VDI, editor, V.V. GmbH, vol. Reihe 6. Dsseldorf; Energietechnik, 1998. [19] Kolios G, Gritsch A, Glckler B, Eigenberger G. Enhancing productivity and thermal efciency of high-temperature endothermic processes in heat-integrated xed-bed reactors. In: Sundmacher K, SeidelMorgenstern A, Kienle A, editors. Integrated Chemical Processes. VCH: Wiley; 2005. [20] Geissler K, Schildhauer T. Katalytischer Plattenreaktor mit interner Wrmerekuperation, Swiss Patent Application No. 1124/00; 2000. [21] Brown LF. A comparative study of fuel cells for on-board hydrogen production for fuel cell-powered automobiles. Int J Hydrogen Energy 2001;26:38197. [22] Geissler K, Newson E, Vogel F, Truong TB, Hottinger P, Wokaun A. Autothermal methanol reforming for hydrogen production in fuel cell applications. Phys Chem Chem Phys 2001;3:28993. [23] Ahmed S, Krumpelt M. Hydrogen from hydrocarbon fuels for fuel cells. Int J Hydrogen Energy 2001;26:291301. [24] Piga A, Verykios ME. An advanced reactor conguration for the partial oxidation of methane to synthesis gas. Catal Today 2000;60:6371.

Ceramic Ceramic monolith monolith

Fig. 10. Applying ceramic monoliths to the ow redirection concept by checker wise feeding the monoliths channels.

The same reactor concept could also be realized with other constructions, e.g. a folded separation sheet between the two compartments, as used by Morillo et al. [17], or state-of-theart ceramic monoliths, where the channels are fed in a checker wise pattern from one side, as suggested by Frauhammer et al. [12], and the other side stays open for the ow redirection (Fig. 10). Principially, the reactor concept can be adapted to autothermal reforming of any hydrocarbon feed, e.g. methane, LPG or petrol. Acknowledgements Peter Binkert and Fritz von Roth are gratefully acknowledged for their help in the mechanical engineering and the manufacturing of the plate-type reactor. Sdchemie AG (D) supplied commercial catalysts under a condentiality agreement. References
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