Oxidative steam reforming of methane to synthesis gas in microchannel reactors

Oxidative steam reforming of methane to synthesis gas (syngas) over an alumina supported bimetallic Pt–Rh catalyst was comparatively investigated in coated and packed microchannel reactors. In the first configuration, thin layers of catalysts are coated on opposite walls of a single microchannel, while the second one is described by particulate catalysts packed into an empty microchannel of dimensions identical with the first one. Both geometries are compared on the basis of methane conversion and CO selectivity measured at different values of parameters, namely reaction temperature (773–923 K), molar steam-to-carbon (S/C = 0–3.0) and oxygen-to-carbon (O₂/C = 0.47–0.63) ratios in the feed, and contact time (0.36–0.71 mg min cm⁻³). Although methane conversions are found to be comparable, the coated catalyst gave significantly higher CO selectivities than the packed counterpart in the whole parameter range. Increase in all of the parameter values led to improvement in methane conversion, while CO selectivity increased only with temperature and contact time. Molar H₂/CO ratios obtained in the coated microchannel reactor are found to vary between 1.0 and 3.0 which are at least three times smaller than those produced in the packed microchannel reactor. Catalyst deactivation is not detected in both configurations. Stable operation up to 72 h over coated microchannel verified mechanical and chemical stability of the Pt–Rh coating that produced syngas with H₂/CO ratio of 2.12 at temperatures lower than employed in industrial reformers. Different flow distribution properties of coated and packed microchannels seem to play roles in affecting the product distribution.     

Metal foam-supported Pd–Rh catalyst for steam methane reforming and its application to SOFC fuel processing

Pd–Rh/metal foam catalyst was studied for steam methane reforming and application to SOFC fuel processing. Performance of 0.068 wt% Pd–Rh/metal foam catalyst was compared with 13 wt% Ni/Al₂O₃ and 8 wt% Ru/Al₂O₃ catalysts in a tubular reactor. At 1023 K with GHSV 2000 h⁻¹ and S/C ratio 2.5, CH₄ conversion and H₂ yield were 96.7% and 3.16 mol per mole of CH₄ input for Pd–Rh/metal foam, better than the alumina-supported catalysts. In 200 h stability test, Pd–Rh/metal foam catalyst exhibited steady activity. Pd–Rh/metal foam catalyst performed efficiently in a heat exchanger platform reactor to be used as prototype SOFC fuel processor: at 983 K with GHSV 1200 h⁻¹ and S/C ratio 2.5, CH₄ conversion was nearly the same as that in the tubular reactor, except for more H₂ and CO₂ yields. Used Pd–Rh/metal foam catalyst was characterized by SEM, TEM, BET and CO chemisorption measurements, which provided evidence for thermal stability of the catalyst.     

Comparison of compact reformer configurations for on-board fuel processing

Two compact reformer configurations in the context of production of hydrogen in a fuel processing system for use in a Proton Exchange Membrane Fuel Cell (PEMFC) based auxiliary power unit in the 2–3 kW range are compared using computer-based modeling techniques. Hydrogen is produced via catalytic steam reforming of n-heptane, the surrogate for petroleum naphtha. Heat required for this endothermic reaction is supplied via catalytic combustion of methane, the model compound for natural gas. The combination of steam reforming and catalytic combustion is modeled for a microchannel reactor configuration in which reactions and heat transfer take place in parallel, micro-sized flow paths with wall-coated catalysts and for a cascade reactor configuration in which reactions occur in a series of adiabatic packed-beds, heat exchange in interconnecting microchannel heat exchangers being used to maintain the desired temperature. Size and efficiency of the fuel processor consisting of the reformer, hydrogen clean-up units and heat exchange peripherals are estimated for either case of using a microchannel and a cascade configuration in the reforming step. The respective sizes of fuel processors with microchannel and cascade configurations are 1.53 × 10⁻³ and 1.71 × 10⁻³ m³. The overall efficiency of the fuel processor, defined as the ratio of the lower heating value of the hydrogen produced to the lower heating value of the fuel consumed, is 68.2% with the microchannel reactor and 73.5% with the cascade reactor mainly due to 30% lower consumption of n-heptane in the latter. The cascade system also offers advanced temperature control over the reactions and ease of catalyst replacement.     

Hydrogen production from methane under the interaction of catalytic partial oxidation,water gas shift reaction and heat recovery

Hydrogen production from the combination of catalytic partial oxidation of methane (CPOM) and water gas shift reaction (WGSR), viz. the two-stage reaction, in a Swiss-roll reactor is investigated numerically. Particular emphasis is placed on the interaction among the reaction of CPOM, the cooling effect due to steam injection and the excess enthalpy recovery with heat recirculation. A rhodium (Rh) catalyst bed sitting at the center of the reactor is used to trigger CPOM, and two different WGSRs, with the aids of a high-temperature (Fe–Cr-based) shift catalyst and a low-temperature (Cu–Zn-based) shift catalyst, are excited. Two important parameters, including the oxygen/methane (O/C) ratio and the steam/methane (S/C) ratio, affecting the efficiencies of methane conversion and hydrogen production are taken into account. The predictions indicate that the O/C ratio of 1.2 provides the best production of H₂ from the two-stage reaction. For a fixed O/C ratio, the H₂ yield is relatively low at a lower S/C ratio, stemming from the lower performance of WGSR, even though the cooling effect of steam is lower. On the contrary, the cooling effect becomes pronounced as the S/C ratio is high to a certain extent and the lessened CPOM leads to a lower H₂ yield. As a result, with the condition of gas hourly space velocity (GHSV) of 10,000 h⁻¹, the optimal operation for hydrogen production in the Swiss-roll reactor is suggested at O/C = 1.2 and S/C = 4–6.     

Influence of catalyst and temperature on gasification performance of pig compost for hydrogen-rich gas production

The catalytic steam gasification of pig compost (PC) for hydrogen-rich gas production was conducted in a fixed-bed reactor. The influence of the catalyst and reactor temperature on yield and product composition was studied at the temperature range of 700–850 °C, for weight hourly space velocity (WHSV) in the range of 0.30–0.60 h⁻¹. The results indicate that the developed NiO on modified dolomite (NiO/MD) catalyst reveals better catalytic performance on the tar elimination and hydrogen yield than calcined MD or NiO/γ-Al₂O₃ catalyst. Meanwhile, the lower WHSV and higher reactor temperature can contribute to more hydrogen production and gas yield. Moreover, the char from catalytic steam gasification of PC has a highest ash content of 75.84% at 850 °C. In conclusion, pig compost is a potential candidate for hydrogen gas production through catalytic steam gasification technology.     

Methane membrane steam reforming: Heat duty assessment

Membrane reactors are an innovative technology with huge application potentialities for equilibrium limited endothermic reactions. Assembling a membrane selective to a reaction product avoids the equilibrium conditions to be achieved, supporting the reactions at lower operating temperatures. Taking as an example the natural gas steam reforming, a methane conversion around 98% can be reached imposing an operating temperature of 823 K, much lower than that of the traditional process. In the present paper, a stringent analysis of heat power requirement needed to carry out the natural gas steam reforming process by applying a membrane reactor is made. The simulations allows to understand how the main operating parameters (inlet temperature, inlet methane flow-rate, steam to carbon ratio, ratio between sweeping steam and inlet methane, operating reaction pressure) influence the total heat power required by the process, divided among power contributions for the reaction heat duty, reactant steam and permeation steam generation and preheating. Moreover, the specific thermal energy per mole of pure H₂ is computed and assessed. Optimizing the operating conditions set, a specific thermal energy per mole of pure hydrogen of 92.3 kWh kmol⁻¹ is obtained corresponding to a total thermal power of 687.4 kW required to convert, in a single membrane reactor, a methane flow-rate of 2 kmol h⁻¹ (GHSV = 9.590 h⁻¹) with a conversion around 98%.     

Steam reforming of propane in a fluidized bed membrane reactor for hydrogen production

Steam reforming of propane was carried out in a fluidized bed membrane reactor to investigate a feedstock other than natural gas for production of pure hydrogen. Close to equilibrium conditions were achieved inside the reactor with fluidized catalyst due to the very fast steam reforming reactions. Use of hydrogen permselective Pd₇₇Ag₂₃ membrane panels to extract pure hydrogen shifted the reaction towards complete conversion of the hydrocarbons, including methane, the key intermediate product. Irreversible propane steam reforming is limited by the reversibility of the steam reforming of this methane. To assess the performance improvement due to pure hydrogen withdrawal, experiments were conducted with one and six membrane panels installed along the height of the reactor. The results indicate that a compact reformer can be achieved for pure hydrogen production for a light hydrocarbon feedstock like propane, at moderate operating temperatures of 475–550 °C, with increased hydrogen yield.     

Fast start-up of microchannel fuel processor integrated with an igniter for hydrogen combustion

A Pt–Zr catalyst coated FeCrAlY mesh is introduced into the combustion outlet conduit of a newly designed microchannel reactor (MCR) as an igniter of hydrogen combustion to decrease the start-up time. The catalyst is coated using a wash-coating method. After installing the Pt–Zr/FeCrAlY mesh, the reactor is heated to its running temperature within 1 min with hydrogen combustion. Two plate-type heat-exchangers are introduced at the combustion outlet and reforming outlet conduits of the microchannel reactor in order to recover the heat of the combustion gas and reformed gas, respectively. Using these heat-exchangers, methane steam reforming is carried out with hydrogen combustion and the reforming capacity and energy efficiency are enhanced by up to 3.4 and 1.7 times, respectively. A compact fuel processor and fuel-cell system using this reactor concept is expected to show considerable advancement.     

Catalytic steam reforming of bio-oil aqueous fraction for hydrogen production over Ni–Mo supported on modified sepiolite catalysts

Hydrogen will be an important energy carrier in the future and hydrogen production has drawn a great deal of attention to its advantages in efficiency and environmental benefit. Catalytic steam reforming in this study was carried out in a fixed bed tubular reactor with sepiolite catalysts. Sepiolite catalysts modified with nickel (Ni) and molybdenum (Mo) were prepared using the precipitation method. Influential parameters such as temperature, catalyst, steam to carbon ratio (S/C), the feeding space velocity (WHSV), reforming length, and activity of catalyst were investigated and the yields of H₂, CO, CH₄, and CO₂ were obtained. The result of this experiment shows that the acidified sepiolite catalyst with addition of the Ni and Mo greatly improves the activities of catalyst and effectively increases the yield of hydrogen. The favorable reaction condition is as follows: reaction temperature is 700–800 °C; S/C is 16–18; the feeding space velocity is 1.5–2.2 h⁻¹, respectively.     

Carbon nanotubes and hydrogen production from the reforming of toluene

Catalytic steam reforming of liquid hydrocarbons is one of the promising alternatives for hydrogen production. However, coke deposition on the reacted catalyst results in catalyst deactivation and also CO₂ emission during reforming are among the main challenges in the process. In this work, the production of high-value carbon nanotubes (CNTs) during hydrogen production from catalytic reforming of toluene has been investigated. Thus, less carbon emission and higher product values can be expected from the process. A two-stage fixed bed pyrolysis-reforming reactor was used in this work. The results showed that the addition of a Ni–Mg–Al catalyst, with an additional downstream stainless steel mesh, increased hydrogen production from 24.8 to 54.8 (mmol H₂ g⁻¹ toluene), when water (steam) was injected at a rate of 0.01 g min⁻¹. CNTs were also produced in the process in the presence of the Ni–Mg–Al catalyst and with a water injection rate of 0.01 g min⁻¹ had the highest band ratio of G′/G when analyzed by Raman spectrometry, indicating the highest purity of CNTs. In addition, Raman spectra of the generated CNTs showed that the purity of CNTs was reduced with the addition of water for reforming without the Ni–Mg–Al catalyst. The presence of the Ni–Mg–Al catalyst significantly increased the yield of CNTs formed on the surface of the stainless steel mesh and also improved the quality of the CNTs in relation to the distribution of diameters and their length.     

Hydrogen production by steam reforming of dimethyl ether over ZnO–Al2O3 bi-functional catalyst

A series of ZnO–Al₂O₃ catalysts with various ZnO/(ZnO + Al₂O₃) molar ratios have been developed for hydrogen production by dimethyl ether (DME) steam reforming within microchannel reactor. The catalysts were characterized by N₂ adsorption-desorption, X-ray diffraction and temperature programmed desorption of NH₃. It was found that the catalytic activity was strongly dependent on the catalyst composition. The overall DME reforming rate was maximized over the catalyst with ZnO/(ZnO + Al₂O₃) molar ratio of 0.4, and the highest H₂ space time yield was 315 mol h⁻¹·kg_cat⁻¹ at 460 °C. A bi-functional mechanism involving catalytic active site coupling has been proposed to account for the phenomena observed. An optimized bi-functional DME reforming catalyst should accommodate the acid sites and methanol steam reforming sites with a proper balance to promote DME steam reforming, whereas all undesired reactions should be impeded without sacrificing activity. This work suggests that an appropriate catalyst composition is mandatory for preparing good-performance and inexpensive ZnO–Al₂O₃ catalysts for the sustainable conversion of DME into H₂-rich reformate.     

Hydrogen production from ethanol steam reforming in a micro-channel reactor

Ethanol steam reforming was studied over a supported Ir/CeO₂ catalyst in a micro-channel structured reactor. The catalyst coating was deposited on the channel walls and showed a remarkably high homogeneity and an excellent adherence to the stainless steel substrate, leading to stable performance during long-term runs. Hydrogen yields exceeding 40 L_H2 g_cat⁻¹ h⁻¹ were achieved during testing with partial ethanol conversion of 65% and a residence time in the order of a few milliseconds. This hydrogen productivity was found significantly higher than in a comparable conventional fixed-bed reactor hence being extremely promising for hydrogen production in micro fuel cell applications.     

H2 production by low pressure methane steam reforming in a Pd–Ag membrane reactor over a Ni-based catalyst: Experimental and modeling

Nowadays, there is a growing interest towards pure hydrogen production for proton exchange membrane fuel cell applications. Methane steam reforming reaction is one of the most important industrial chemical processes for hydrogen production. This reaction is usually carried out in fixed bed reactors at 30–40 bar and at temperatures above 850 °C. In this work, a dense Pd–Ag membrane reactor packed with a Ni-based catalyst was used to carry out the methane steam reforming reaction between 400 and 500 °C and at relatively low pressure (1.0–3.0 bar) with the aim of obtaining higher methane conversion and hydrogen yield than a fixed bed reactor, operated at the same conditions. Furthermore, the Pd–Ag membrane reactor is able to produce a pure, or at least, a CO and CO₂ free hydrogen stream. A 50% methane conversion was experimentally achieved in the membrane reactor at 450 °C and 3.0 bar whereas, at the same conditions, the fixed bed reactor reached a 6% methane conversion. Moreover, 70% of high-purity hydrogen on total hydrogen produced was collected with the sweep-gas in the permeate stream of the membrane reactor. From a modeling point of view, the mathematical model realized for the simulation of both the membrane and fixed bed reactors was satisfactorily validated with the experimental results obtained in this work.     

Hydrogen production from methane using vanadium-based catalytic membrane reactors

The application of vanadium-based membranes as the hydrogen separation membrane for a catalytic membrane reactor system was investigated for the direct production of hydrogen from methane. The methane conversion and hydrogen production rates of the catalytic membrane reactor system with Pd-coated 100 μm-thick vanadium-based membranes were comparable with the reactor using 50 μm-thick Pd–Ag alloy membrane at all temperatures examined. The methane conversion rates of the catalytic membrane reactor with the Pd-coated vanadium-based membranes were approximately 35% and 62% at 623 K and 773 K, respectively. The hydrogen production rates were around 660  μmol min⁻¹ at 623 K, and reached over 1710  μmol min⁻¹ at 773 K. The relationship between the methane conversion rates and hydrogen permeation fluxes of the catalytic membrane reactor confirmed that the removal of hydrogen from the reaction site enhances the methane decomposition reaction. Further, the vanadium based membrane exhibited good stability against Fe in a hydrogen containing atmosphere.     

Methanol steam reforming in a planar wash coated microreactor integrated with a micro-combustor

A numerical simulation of methanol steam reforming in a microreactor integrated with a methanol micro-combustor is presented. Typical Cu/ZnO/Al₂O₃ and Pt catalysts are considered for the steam reforming and combustor channels respectively. The channel widths are considered at 700 μm in the baseline case, and the reactor length is taken at 20 mm. Effects of Cu/ZnO catalyst thickness, gas hourly space velocities of both steam reforming and combustion channels, reactor geometry, separating substrate properties, as well as inlet composition of the steam reforming channel are investigated. Results indicate that increasing catalyst thickness will enhance hydrogen production by about 68% when the catalyst thickness is increased from 10 μm to 100 μm. Gas space velocity of the steam reforming channel shows an optimum value of 3000 h⁻¹ for hydrogen yield, and the optimum value for the space velocity of the combustor channel is calculated at 24,000 h⁻¹. Effects of inlet steam to carbon ratio on hydrogen yield, methanol conversion, and CO generation are also examined. In addition, effects of the separating substrate thickness and material are examined. Higher methanol conversion and hydrogen yield are obtained by choosing a thinner substrate, while no significant change is seen by changing the substrate material from steel to aluminum with considerably different thermal conductivities. The produced hydrogen from an assembly of such microreactor at optimal conditions will be sufficient to operate a low-power, portable fuel cell.     

Enhancement of pure hydrogen production through the use of a membrane reactor

Pure hydrogen production is of great interest as it is an energy carrier which can be used in PEM fuel cells for power production. Methane Steam Reforming (MSR) is commonly used for hydrogen production although the produced hydrogen is not free of other components. Membrane Reactors (MR) enable a pure hydrogen product stream and allows the reaction to take place at significantly lower temperatures (lower than 550 °C) than in conventional reactors (greater than 800 °C) with comparable methane conversion. This is achieved by hydrogen removal through a permselective Pd–Ag based membrane that cause a favorable shift in chemical equilibrium towards hydrogen production. In the present study, a two-dimensional, nonlinear, and pseudo-homogeneous mathematical model of a catalytic fixed-bed membrane reactor for methane steam reforming over a nickel-based foam supported catalyst is presented. Simulated results referring to the distribution of species, methane conversion, temperature and hydrogen flowrate along the reactor for different radial positions are obtained and analyzed. The performance of structured catalyst and catalyst supported on foam configurations under the same operating conditions is also studied. Experimental results for the membrane facilitate the identification of suitable operating conditions.     

Production of hydrogen and methane by one and two stage fermentation of food waste

Anaerobic digestion is an attractive process for generation of hydrogen and methane, which involves complex microbial processes on decomposition of organic wastes and subsequent conversion of metabolic intermediates to hydrogen and methane. Comparative performance of a sequential hydrogen and methane fermentation in two stage process and methane fermentation in one stage process were tested in batch reactor at varying ratios of feedstock to microbial inoculum (F/M) under mesophilic incubation. F/M ratios influence biogas yield, production rate, and potential. The highest H₂ and CH₄ yields of 55 and 94 mL g⁻¹ VS were achieved at F/M of 7.5 in two stage process, while the highest CH₄ yield of 82 mL g⁻¹ VS in one stage process was observed at the same F/M. Acetic and butyric acids are the main volatile fatty acids (VFAs) produced in the hydrogen fermentation stage with the concentration range 10–25 mmol L⁻¹. Little concentrations of VFAs were accumulated in methane fermentation in both stage processes. Total energy recovery in two stage process is higher than that in one stage by 18%. This work demonstrated two stage fermentation achieved a better performance than one stage process.     

Pathways of ethanol steam reforming over ceria-supported catalysts

Ceria-supported Pt, Ir and Co catalysts are prepared herein by the deposition–precipitation method and investigated for their suitability in the steam reforming of ethanol (SRE) at a temperature range of 250–500 °C. SRE is tested in a fixed-bed reactor under an H₂O/EtOH molar ratio of 13 and 20,000 h⁻¹ GHSV. Possible pathways are proposed according to the assigned temperature window to understand the different catalysts attributed to specific reaction pathways. The Pt/CeO₂ catalyst shows the best carbon–carbon bond-breaking ability and the lowest complete ethanol conversion temperature of 300 °C. Acetone steam reforming over the Ir/CeO₂ catalyst at 400 °C promotes a hydrogen yield of up to 5.3. Lower reaction temperatures for the water–gas shift and acetone steam reforming are in evidence for the Co/CeO₂ catalyst, whereas the carbon deposition causes its deactivation at temperature over 500 °C.     

Hydrogen-methane production from pulp & paper sludge and food waste by mesophilic–thermophilic anaerobic co-digestion

The present study focused on the mesophilic anaerobic bio-hydrogen production from PPS (pulp & paper sludge) and FW (food waste), and the subsequent anaerobic digestion of the effluent for the methane production under thermophilic conditions by a two-stage process. The maximum hydrogen yield of 64.48 mL g⁻¹ VS_fed and methane yield of 432.3 mL g⁻¹ VS_fed were obtained when PPS and FW were applied with 1: 1 VS ratio as the feedstock. No VFA were cumulated in the reactor during the period of hydrogen - methane fermentation, as well as no NH₃–N and Na⁺ inhibition were found in the process. 71%–87% removal efficiencies of SCOD were attained for hydrogen and methane co-production. pH 4.8–6.4 and alkalinity 794–3316 mg CaCO₃ L⁻¹ for H₂ fermentation, as well as pH 6.5–8.8 and alkalinity 4165–4679 mg CaCO₃ L⁻¹ for CH₄ fermentation, were achieved without any adjustment. This work showed that anaerobic co-digestion of PPS and FW for hydrogen-methane co-production was a stable, reliable and effective way for energy recovery and bio-solid waste stabilization by the two-stage mesophilic–thermophilic process.     

Simultaneous coproduction of hydrogen and methane from sugary wastewater by an “ACSTRH–UASBMet” system

A two-phase “ACSTR_H–UASB_Met” system has been investigated at the stepwise decreased HRT for the simultaneous production of hydrogen and methane in this study. Hydrogen could be continuously produced from the two-phase hydrogen fermentation of sugary wastewater in ACSTR and effluents from hydrogen fermentation were converted into methane in UASB reactor. At optimum conditions (HRT_H: 5 h, HRT_Met: 15 h), the highest hydrogen production rate of 5.69 (±0.06) mmol L⁻¹ h⁻¹ was obtained from sugary wastewater and methane was continuously produced from effluents of hydrogen fermentation with a production rate of 3.74 (±0.13) mmol L⁻¹ h⁻¹. The total bioenergy recovery by coproduction of hydrogen and methane from sugary wastewater reached 19.37 W and a total of 92.41% of substrate was converted to the biogas (hydrogen and methane) with two-phase anaerobic fermentation.