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Syngas production via methane steam reforming with oxygen: plasma reactors versus chemical reactors

This article has been downloaded from IOPscience. Please scroll down to see the full text article. 2001 J. Phys. D: Appl. Phys. 34 2798 (http://iopscience.iop.org/0022-3727/34/18/313) View the table of contents for this issue, or go to the journal homepage for more

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INSTITUTE OF PHYSICS PUBLISHING J. Phys. D: Appl. Phys. 34 (2001) 27982803

JOURNAL OF PHYSICS D: APPLIED PHYSICS PII: S0022-3727(01)23229-X

Syngas production via methane steam reforming with oxygen: plasma reactors versus chemical reactors
Jean Marie Cormier1 and Iulian Rusu2
1 2

GREMI, Universit dOrl ans, 14 rue dIssoudun, BP 6744-45067, Orl ans Cedex 2, France e e e Faculty of Industrial Chemistry, Technical University Gh Asachi, Bd Dimitrie Mangeron 71, Iasi 6600, Romania E-mail: jean-marie.cormier@univ-orleans.fr

Received 22 March 2001, in nal form 8 July 2001 Published 5 September 2001 Online at stacks.iop.org/JPhysD/34/2798 Abstract Steam reforming with oxygen (SRO) is a combination of non-catalytic partial oxidation and steam reforming of methane, industrially used for syngas production. There are several models of the chemical reactors used for this purpose but in the last decade a new direction has developedplasma devices. The aim of the present paper is to make a comparative analysis between the autothermal reformers, including their improved variants, and the plasma reactors. The study is conceived in terms of advantages and disadvantages coming from the exploitation parameters, methane conversion, selectivity, energy efciency and investment costs. Although SRO by means of chemical reactors may be the most efcient, plasma reactors represent an incisive approach by their simplicity, compactness and low price.

1. Introduction
Synthesis gas or syngas is a mixture of hydrogen and carbon monoxide used as a major intermediary for the production of pure hydrogen or other chemical compounds. Among these we have to mention ammonia with its inestimable utility for industry and agriculture and the liquid products derived by the process known as SCL (syngas conversion to liquids) (e.g. methanol and other alcohols, solvents, diesel fuel, jet fuel, gasoline, etc). The growing demand for chemicals derived from syngas has led to the development of several technologies (e.g. FischerTropsch synthesis, NH3 or oxygenate production). These processes are of strategic importance for any country. For example, the synthesis developed by Fischer and Tropsch was used by the Germans during the Second World War to produce fuel from coal. South Africa also produced fuel this way during the political sanctions against the apartheid regime. Today, as the fuels obtained from syngas do not contain sulphur or nitrogen compounds, their combustion in engines leads to reduced environmental pollution. Hydrogen itself was taken into account in the last period as a clean fuel, important steps being made in the research in recent years on the on-board
0022-3727/01/182798+06$30.00 2001 IOP Publishing Ltd

production of hydrogen for automotive applications [1, 2]. Syngas is also the main source of carbon monoxide, which is used in an expanding list of carbonylation reactions. Originally, coal was the primary source of carbon for syngas, but today natural gas has replaced it for economic reasons. Despite the fact that coal reserves are large and the price of coal is lower than that of the hydrocarbons, the investment in a coal-based syngas plant is about three times higher than that required for a natural-gas-based plant [3]. However, there are also technologies producing syngas from petroleum coke, heavy residuals and even biomasses [4, 5]. Natural gas can be processed by several methods, e.g. partial oxidation with oxygen (PO), steam reforming (SR), steam reforming with oxygen (SRO), CO2 reforming (CDR) and CO2 reforming with oxygen (CDRO) [6]. One of the most attractive technologies seems to be the SRO, which is also known as autothermal reforming. The main reasons for recommending this technology over the other variants are the low energy requirements, the high space velocity (at least one order of magnitude relative to traditional SR), a lower process temperature than PO and the H2 /CO ratio is easily regulated by the inlet gas ratio [79]. The process can be performed by means of various reactor models including plasma reactors. 2798

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Syngas production with SRO: plasmas or chemicals

If syngas processing is of strategic importance, research regarding the use of plasma reactors has also become strategic for different countries. For example, Germany, Japan and the USA employ large funding regarding automotive applications of plasma reactors. The Russian Federal R&D programme in the eld of hydrogen energy and technology for the period 199496 also included in the eight most promising processes for the production and use of hydrogen two concerning plasmachemical technologies [10]. Therefore, the aim of the present paper is to make a comparative analysis of the chemical and plasma reactors used for SRO, in order to estimate the real prospects for plasma processes in this eld.

However, since a plasma is a mixture of electrons, highly excited atoms and molecules, ions, radicals, photons, etc, the chemistry is very complex and the present understanding of it is quite limited. It is difcult to predict theoretically the nal products and their concentration. Unfortunately, most practical achievements are based on experiments.

3. Other methods of syngas production

There is an entire literature concerning the chemical technologies used or proposed for syngas production. Therefore, in this section we shall briey summarize only reports on syngas production by means of plasma methods. The plasmatron experiments performed at Michigan Institute of Technology (MIT) on the PO of methane revealed that for energy inputs of less than 25 MJ kg1 CH4 , hydrogen output reaches 38% of equilibrium levels and the CO output is 65% of equilibrium [14]. In these conditions the resulting energy cost was as high as 267 MJ kg1 H2 because most of the hydrogen turns into water. Czernichowski et al used a gliding arc installation for this process with a similar energy cost [1517]. Chapelle et al have used a classic gliding arc reactor for syngas generation by SR [18]. For an electric power of 1.4 kW and a steam-to-methane ratio of 24, the maximum CH4 conversion was 44%, with an output energy efciency of 33% at an energy cost of about 97 MJ kg1 H2 . CDR is currently of great interest both for the transformation of natural gas and for environmental control. Chapelle et al [18] has performed the reaction in both transferred arc and gliding arc reactors. In the rst case the hydrogen concentration in the exit gases decreased from 48 to 22% for a CO2 /CH4 ratio increasing from 0.5 to 2. The necessary energy for the production of 1 kg of hydrogen was of 234 MJ, corresponding to an energy efciency of about 27%. In the second case the energy cost decreased to 226 MJ kg1 H2 , with an energy efciency of about 31%. The same reaction was performed by means of glow discharges, micro-arc plasmas and dielectric-barrier discharges, but with low energy efciency [19, 20]. The advantage of oxygen addition in the CDRO process is the supply of additional energy for methane conversion, due to a parallel reaction of methane oxidation. Laboratory-scale experiments gave 100% conversion but at a very high energy expenditure (190270 MJ kg1 H2 ), the energy efciency ranging between 23 and 42% [17]. In order to promote an efcient reforming process, Fridmans team has used a pulsed corona discharge reactor with preheating of the inlet gases at about 900 C [21]. They succeeded in lowering the plasma energy cost to 34 MJ kg1 H2 . However, the energy spent for preheating the mixture was about 340 MJ kg1 H2 . The literature also presents results regarding the use of thermal plasmas for syngas production starting from gasoline and diesel fuel, biofuels (canola and corn oil) and even used tires [22, 23].

2. Syngas production by SRO

SRO is a combination of non-catalytic partial oxidation and steam reforming developed by Haldor Topse in the late 1950s in order to perform reforming in a single reactor [9]. There are probably ve main chemical reactions in the reforming process: CH4 + H2 O CO + 3H2 CH4 + 2H2 O CO2 + 4H2 CH4 + O2 CO2 + 2H2 2CH4 + O2 2CO + 4H2 CO + H2 O CO2 + H2 H298 = 206 kJ H298 = 164.9 kJ H298 = 318.9 kJ H298 = 71.8 kJ H298 = 41 kJ. (1) (2) (3) (4) (5)

Partial oxidation is an exothermic process, while steam reforming is endothermic. The thermal energy generated by the former can be adjusted by its molar air/methane ratio so that the overall autothermal process can be carried out without an extra external heat source for the SR process. Classic thermodynamic analysis performed by Chan and Wang [11] indicated that the optimal operating regime is with an air/methane molar ratio of 3.5 and a 2.5 to 4 water/methane molar ratio. Under these operating conditions, the number of moles of hydrogen per mole of natural gas consumed is 2.192.22. The results also showed that under these conditions, the solid carbon is suppressed, the mole fraction of CO ranges from 2.244.38%, the methane conversion rate is 99.04 99.45% and the operating temperature is between 820 and 871 K. Taking into account the use of plasma reactors, Bromberg and co-workers [12] have simulated the homogeneous SRO process (CH4 + 0.5O2 + 1.88N2 + H2 O) by means of nonequilibrium thermodynamics [13]. This method has been used to determine the reaction trajectory in an adiabatic reactor. The calculations performed for initial temperatures of 500, 1500 and 2000 K indicate that the reaction is characterized by two distinct stages. During the rst stage, complete combustion of part of the methane occurs, producing mainly CO2 and water, increasing the temperature of the system. In the second stage, the remaining methane reacts with CO2 and H2 O producing syngas and decreasing the systems temperature. The calculated rate of methane conversion ranged between 97.5 and 100%, leading to a nal hydrogen mole fraction of about 35% and for the CO 816%.

4. Chemical reactors
The reformer basically consists of a ceramic lined tube and a Ni-based xed catalyst bed for equilibration of the gas 2799

J M Cormier and I Rusu

(gure 1(a)). The preheated feed streams (CH4 + H2 O and H2 O + O2 ) are mixed in a burner placed at the top where partial oxidation of the methane occurs. The nal steam reforming takes place in the catalyst bed below the burner. Typically, the SRO reactor operates at about 2200 K in the combustion zone and 12001400 K in the catalytic zone. Operating pressures range from 12 to 70 atm. Tests carried out on xed bed reactors revealed that one of the most important features concerns the adiabatic working conditions. Methane conversions up to 90% with residence times of up to 0.1 s have been found. Exxon developed a uidized-bed system in which the CH4 /H2 O mixture is fed to the bottom of the reactor and oxygen is fed into the middle of a uidized bed of catalyst (gure 1(b)). The uidized bed offers the advantage of an optimal temperature distribution, with the absence of radial and axial gradients and a lower pressure drop with respect to a xed bed operating at the same dimension and space velocity. The usual catalyst is a Ni catalyst supported on a refractory material containing a variety of promoters. The additives are potassium and/or calcium alkali ions, which mainly serve to suppress excessive carbon deposit on the catalyst [24]. Recent studies show that catalysts based on noble metals seem to be more active for SRO [7, 25]. There are several studies presenting comparisons between different processes of syngas synthesis and the implied economics [9, 2630]. The basis of comparisons rested mainly on four points: raw material consumption, energy consumption and energy recovery, investments and operational costs. The conclusion that one can draw from these studies is that autothermal reforming improves the steam reforming cost by 1020%. This means that the investment varies between 750 and 900 euro per N m3 h1 and a nal hydrogen cost of 0.050.08 euro per Nm3 . The shortcomings of the chemical autothermal reformers concern size, the large investments, the limitations on rapid response, the extreme operating conditions that limit the lifetime of a reactor, heat management (during the front end of the catalyst bed as the methane undergoes total oxidation), safety and operability. Possible improvements of the SRO include the use of membrane technology, the achievement of integrated autothermal reforming/fuel cell systems and periodically operated uidized bed reactors. Conventional SRO often leads to low hydrogen yield since the formed H2 may react with oxygen to yield water. To avoid this problem several authors have proposed a periodic system with a feed composition alternating between CH4 /O2 and CH4 /H2 O mixtures [3133]. It was envisaged that this would promote independent methane oxidation and steam reforming steps, and thus minimize hydrogen reconversion. The results indicate that under periodic cycling, SRO proceeds via the interaction of entities derived from the dissociative adsorption of CH4 and H2 O leading predominantly to CO2 and H2 . A membrane reactor combines the separation properties of a membrane with the performance of a catalytic system (gure 1(c)). The combined efforts of Amoco, BP Chemicals, Praxair, Sasol and Statoil developed an innovative technology, named OTM (oxygen transport membrane) that can convert natural gas to syngas with very high selectivity [7]. In this process, a ceramic perovskite type membrane permits SRO 2800

with separation of oxygen. Air and methane are introduced into opposite sides of the membrane, the oxygen dissociated into ions diffuses through the membrane reacting with methane to give oxidation products. Air Products, the US Department of Energy, Ceramatec and other partners have developed a similar reactor technology [34, 35]. The laboratory-scale apparatus has operated with methane at 730 atm and an air feed to the interior membrane at atmospheric pressure. In the second phase, an engineering process development unit will test subscale membranes under full operating conditions at a nominal 700 m3 per day. The weak point of the membrane reactors is the mass transfer, which is limited if the membrane does not have sufcient ux to satisfy the productivity of the catalyst. Other practical issues, such as membrane pore blockage and thermal and mechanical stability have limited for the moment the usefulness of these systems. Variants of the membrane reactors are the solid oxide fuel cells (SOFC) and, in the last decade, there has been an increased interest in the use of SOFC to produce H2 [1, 36, 37]. The membrane in this case is also an electrode (the anode), made of porous carbon plates laced with a catalyst. The hydrogen combines with HO ions to produce water vapour and electric power. Therefore, the chemical energy is converted directly into electricity. On the anode side, the natural gas is rst ejected into a reforming chamber where it draws waste thermal energy from the stack and is converted into H2 and CO. It then ows into the anode manifold where most of the H2 and CO is oxidized. This gas stream is then partly recycled to the reforming chamber where the resulting water is used as a reagent. On the cathode side, air is rst blown into a heat exchanger where it reaches nearly operating temperature. The air is brought up to the operating temperature by combustion of the remaining H2 and CO from the anode. The oxygen in the cathode manifold is converted into an oxygen ion that travels back to the anode. For hydrogen users, the CO can be converted by the established mode into CO2 and H2 using a shift reactor followed by CO2 separation. For a cell voltage ranging between 0.5 and 0.8 V, the thermodynamic calculations show an efciency of electricity and hydrogen generation of about 80% [37]. The system is simple, efcient, tolerant to impurities and uses cheap catalysts. Due to the high operating temperatures air compression is not required. Another advantage is that both hydrogen and CO are used in the cell. While in other cases, CO is a poison, in SOFC it is a fuel. Moreover, SOFCs can provide an effective energy conversion system even for smallscale plants. Tanaka et al [38] have designed a combined cycle system with a solid oxide fuel cell and gas turbine. According to their economic calculations the total electricity generation efciency can rise up to 6070%. The gas turbine accounts for the greatest investment input (35%), with the next highest being the fuel cell module (including the reformer23%), followed by the heat exchanger (20%). Although the unit investment cost is higher than that for a large-scale coal power plant it can still be considered as a competitive alternative for urban areas. However, a cheaper reformer would decrease the investment costs. Among the disadvantages we have to mention that the SOFCs run at temperatures of 8001000 C and, therefore,

Syngas production with SRO: plasmas or chemicals

CH4 + H2O H2O + O2 Syngas Syngas Exhaust

Burner

Cyclone Membrane Catalyst bed Fluidised bed

O2 Catalyst bed

Syngas (a)

CH4 + H2O (b)

Reactants (c)

Figure 1. Different kinds of chemical reformers.

Cathode Insulator Air Anode Cooling water

(2) W/2 W

W/2 (1) (3)

Cooling water
Figure 3. Diagram of a microwave plasmatron.

(4)

Reactants

Syngas
Figure 2. Diagram of a thermal plasma reactor.

several minutes of fuel burning is required to reach operating temperature. This delay is considered to be a shortcoming for automotive applications. However, most of the cells generate H2 at 1 atm or less and for bulk production this will then require higher compression to apply the chemical technology [24].

5. Plasma reactors
Depending on their energy, temperature and ionic density, plasmas are usually classied as either thermal plasmas or non-thermal (non-equilibrium) plasmas. Generally, the plasma used for chemical applications is required to provide a high operating power together with a very selective energy input while simultaneously maintaining a non-equilibrium condition [15]. Thermal plasma reactors (plasmatrons) have different constructive variants (induction, DC and microwave plasmatrons) [18, 39]. Basically, the plasmatron comprises two watercooled metallic tubular electrodes (gure 2). A spark occurs

in the gap between the electrodes, and the incoming feedstock gas blows the arc into the arc chamber. The working gas can be injected directly or tangentially into the gap between electrodes. Applying an external magnetic eld can enhance the gas rotation. The electrodes are usually made of copper but it is possible to use some new improved alloys, such as beryllium bronze and tungstencoppernickel. The SRO reaction performed by Bromberg and his team [40] by the means of a plasmatron, without a catalyst, resulted in a hydrogen yield of 40% (dened as the ratio of hydrogen released to hydrogen content in methane) for an input power of 3.5 kW. At low values of input power, the homogeneous plasma process resulted in low methane conversions (about 40%). The devices productivity was about 4000 m3 h1 H2 per cubic metre of reactor. The minimum power consumption without heat recovery was about 100 MJ kg1 H2 . Furthermore, in order to decrease this specic power consumption a nickel-based catalyst on an alumina support was used through. The hydrogen yield increased by up to 80%, for an input power of 2.7 kW and a methane conversion rate of 70%. The plasma composition of the reformate was of 35%H2 , 5%CH4 , 3.7%CO, 15%CO2 , 41%N2 and traces of C2 hydrocarbons. The required specic energy was reduced to less than 17 MJ kg1 H2 . The productivity also increased to about 10 000 m3 h1 H2 per cubic metre of reactor. The main drawback of using thermal plasmas is the overheating of the reaction media, when the reagents in all 2801

J M Cormier and I Rusu

A no d e s V1 C a tho d e
V2

V3

G a s o utle t

D isc ha rge s

T M ea su re
G a s inle t

T M e a su r e
C he m ic a l d ia gno stic s

Figure 4. Diagram of a three-discharge glidarc reactor. Table 1. Comparative data for SRO reactors. Investment cost (euro/Nm3 h1 H2 ) Chemical reactors Plasma reactors 750900 65 H2 cost (euro/Nm3 ) 0.050.08 0.23 Investment cost SOFC-GT-SRO system (euro/W) 5.12 4.59

degrees of freedom uniformly consume energy. It is the high electron temperature that determines the reaction evolution in non-thermal plasmas, while the gas temperature can remain as low as room temperature. Non-thermal plasmas have several types if discharge: glow, corona, dielectric barrier, microwave, radiofrequency and gliding arc [41, 42]. The microwave discharge operates at very high frequencies, with which only light electrons can follow the oscillations of the electric eld. Therefore, this discharge is far from local thermodynamic equilibrium and has the advantage that it can be used in a wide pressure range. The electron temperatures in a microwave discharge are mainly dened by the electric eld (Eel ) in the discharge and by the pressure (P ); however the maximization of the Eel /P ratio at the discharge axis may be sufcient for electrodynamic stabilization [43]. This can be achieved by the interference of microwaves. Practically, the radiation is introduced into the microwave device along a waveguide (1), the power W being divided into two identical coherent components (W/2) by means of a metal pin (2) mounted in a metal cylinder (3) (gure 3). The discharge is formed into a dielectric tube (4), Eel taking the highest value in its central plane. This is due to the fact that the system is symmetrical with respect to the electric eld. Scientists from Kurchatov Institute of Moscow have studied the SRO experimentally (5% oxygen for a ratio H2 O/CH4 < 1) using such a continuous microwave discharge plasmatron [43, 44]. The discharge power was up to 200 kW, the frequency was 915 MHz, the gas-ow rate up to 200 m3 h1 , and the gas pressure in the reaction zone varied in the range 0.11 atm. In this case the energy consumption was of 4247 MJ kg1 H2 for a methane conversion rate higher than 90%. Quite recently, a simpler alternative approach for plasma SRO has been proposedthe gliding arc [15, 45]. In this cold plasma the ionization processes induced by the electric eld dominate the thermal ones and give relatively high-energy 2802

electrons as well as excited ions, atoms or molecules that promote selective chemical transitions efciently. Such a gliding arc occurs when the plasma is generated between two or more diverging electrodes placed in a fast gas ow [46]. The average residence time of the reagents in the reaction zone is about 103 s. This fact allows very high specic throughputs in the reaction zone, which generally exceed, by four orders of magnitude, other chemical methods, including electrochemical and thermal ones. The literature presents several studies modelling the behaviour of glidarcs trying to predict the working parameters in different experimental conditions [4753]. The electrical circuit of a gliding arc consists of a high voltage generator (up to 10 kV) used to ignite the discharge and a second power generator with a voltage up to 1 kV and a total current up to 10 A. Current limitation is achieved by means of inductance. The experiments for generating syngas by SRO in gliding arc reactors have only been performed in the laboratory. Researchers from GREMI, Universit dOrl ans, have used a e e reactor with an inner cone-shaped electrode and an external metallic tube as a second electrode. This plasma reactor generates turning gliding arc discharges, produced by the radial injection of the gas mixture. Approximately 40% of the methane submits to chemical transformation at a conversion cost of about 89 MJ kg1 H2 and to 125 kJ mole1 of converted methane, when a ratio of H2 O/CH4 = 4.5 was used through. The electric power ranged between 0.1 and 0.3 kW with an output energy efciency of 40%. The productivity was as high as 10 000 m3 h1 H2 per m3 of reactor, operating at atmospheric pressure. Further tests started in Spring 2001 with a multiple discharge reactor (gure 4) using various catalysts. We now present some preliminary results concerning the costs of syngas production by means of plasma reformers. There are three major costs in the manufacturing of hydrogenrich gas: the natural gas cost, the electricity cost and the

Syngas production with SRO: plasmas or chemicals

investment for the reactor system. For both the plasmatron and the turning gliding-arc reactor a capital cost of 0.6 euro per Watt of electrical power, that means about 65 euro per Nm3 h1 of hydrogen is estimated. This includes the cost of the power supply and the reactor. The calculation assumes that the capital equipment depreciates over a three-year period. For a specic energy consumption of 16 MJ kg1 H2 the cost of the produced hydrogen is about 0.23 euro m3 . However, larger systems will produce hydrogen at lower costs and one must appreciate the high productivity of plasma reactors, due to their low dimensions.

6. Conclusion
SCL is becoming increasingly important for economic, environmental and strategic reasons. Different authors admit that a 25% capital cost reduction in current technology would have a major impact on the overall economics of SCL [11, 17, 54]. Plasma reactors represent an incisive approach by their simplicity, compactness and low price (see table 1). For small-scale units providing hydrogen for fuel cells, not only for automotive applications, the choice of technology may be dictated by such parameters as simplicity and quick response to transients. Although SRO by means of chemical reactors may be the most efcient, the use of plasma reactors may quite soon become the preferred choice. Much more work has to be done on the use of catalysts and reactor design (including heat recovery).

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