A new reforming process based on CH4 decomposition using a hydrogen-permeating membrane reactor

A new reforming process was studied using Ni/SiO₂ with a hydrogen-permeating membrane reactor. Nickel catalyst supported on SiO₂ is highly active for CH₄-H₂O-O₂ reaction in membrane reactor and the reaction close to CH₄ + 0.35O₂ + 1.3H₂O → CO₂ + 3.3H₂ proceeds at 873 K. Since the selectivity to carbon and CO₂ increased and decreased with decreasing contact time respectively, it is considered that the reaction was started by decomposition of CH₄ followed by oxidation of C and water shift reaction. Therefore, the reaction mechanism was different from so-called autothermal reforming (ATR) reaction.     

The oxidative stream reforming of methane to syngas in a thin tubular mixed-conducting membrane reactor

The oxidative stream reforming of methane (OSRM) to syngas, involving coupling of exothermic partial oxidation of methane (POM) and endothermic steam reforming of methane (SRM) processes, was studied in a thin tubular Al₂O₃-doped SrCo_0.8Fe_0.2O_3−δ membrane reactor packed with a Ni/γ-Al₂O₃ catalyst. The influences of the temperature and feed concentration on the membrane reaction performances were investigated in detail. The methane and steam conversions increased with increasing the temperature and high conversions were obtained in 850–900 °C. Different from the POM reaction, in the OSRM reaction the temperature and H₂O/CH₄ profoundly influenced the CO selectivity, H₂/CO and heat of the reaction. The CO selectivity increased with increasing the temperature or decreasing the H₂O/CH₄ ratio in the feed owing to the water gas shift reaction (H₂O + CO → CO₂ + H₂). And the H₂ selectivity based on methane conversion was always 100% because the net steam conversion was greater than zero. The H₂/CO in product could be tuned from 1.9 to 2.8 by adjusting the reaction temperature or H₂O/CH₄. Depending on the temperature or H₂O/CH₄, furthermore, the OSRM process could be performed auto-thermally with idealized reaction condition.     

Surface Reaction Kinetics of the Oxidation and Reforming of CH4 over Rh/Al2O3 Catalysts

An 48‐step sur face reaction mechanism with thermodynamic consistent kinetic data is presented for the catalytic conversion of the gaseous chemical system H₂/O₂/H₂O/CO/CO₂/CH₄ over Rh/Al₂O₃ catalysts. Total and partial oxidation as well as steam reforming and dry reforming of methane over Rh catalysts is studied experimentally and numerically at varying temperature and composition. The results are used to extend the kinetic schemes we developed for H₂ oxidation, CO oxidation kinetics, and the water‐gas‐shift reactions in former studies. Aside from the experiments in a stagnation‐flow reactor presented here, we modeled a number of experiments from the literature to test the newly established kinetic scheme.     

Marked Effect of Various Supports and Additives Upon Liquid Phase Methanol Reforming with Water over Supported Group 8–10 Metal Catalysts

The support effects (SiO₂, TiO₂, Al₂O₃, MgO, CeO₂ and ZrO₂) as well as addition effect of group 6b and 7b elements were studied over various supported group 8–10 metal catalysts. Basic oxide support improved the selectivity to CO₂ and acidic support suppressed the catalytic activity and selectivity. Among the investigated catalysts Pt–Mo/TiO₂ was the most active catalysts, whereas Ir–Re/SiO₂ was the most selective catalysts for H₂ and CO₂ formation. The mechanism of the liquid phase methanol reforming reaction over silica supported Pt–Ru catalyst was studied by kinetic investigations. The rate of H₂ formation over Pt–Ru/SiO₂ catalysts was more than 20 times faster than that over Pt/SiO₂ catalysts with high selectivity for CO₂ (72.3%), indicating a marked addition effect of Ru. In the case of HCHO–H₂O reaction over Pt–Ru/SiO₂, the H₂ formation rate was five times larger than that in the CH₃OH–H₂O reaction but selectivity to CO₂ was only 4%. On the contrary, in the HCOOCH₃–H₂O and HCOOH–H₂O reactions, both high activity and selectivity were observed over Pt–Ru/SiO₂. These results clearly indicate that the CO₂ formation does not proceed via HCHO decomposition and following water gas shift reaction.     

Autothermal reforming of methane to syngas for Fischer-Tropsch synthesis with promoted palladium and a fast start-up device

In this study, a Pd catalyst was prepared with promoters such as CeO₂, BaO and SrO in a washcoated form on a metallic monolith for autothermal reforming of methane to syngas for the Fischer-Tropsch synthesis. A reactor was installed with an electric heater in the form of the metallic monolith as a start-up device instead of a burner with which stable and fast start-ups (within 4 min) were achieved. Gas hourly space velocity and O₂/CH₄ governed, methane conversion, while H₂O/CH₄ controlled H₂/CO ratio. A methane conversion of approx. 96%, H₂+CO selectivity of approx. 85%, and H₂/CO of approx. 2.6 were obtained under the conditions of gas hourly space velocity (GHSV) at 103000 h^?1, O₂/CH₄=0.7 and H₂O/CH₄=0.35.     

Hydrogen‐Permeable Tubular Membrane Reactor: Promoting Conversion and Product Selectivity for Non‐Oxidative Activation of Methane over an Fe©SiO2 Catalyst

Non‐oxidative methane conversion over Fe©SiO₂ catalyst was studied for the first time in a hydrogen (H₂) permeable tubular membrane reactor. The membrane reactor is composed of a mixed ionic–electronic SrCe_0.7Zr_0.2Eu_0.1O_3?δ thin film (≈20 μm) supported on the outer surface of a one‐end capped porous SrCe_0.8Zr_0.2O_3?δ tube. Significant improvement in CH₄ conversion was achieved upon H₂ removal from the membrane reactor compared to that in a fixed‐bed reactor. The Fe©SiO₂ catalyst in the H₂ permeable membrane reactor demonstrated a stable ≈30 % C₂₊ single‐pass yield, with up to 30 % CH₄ conversion and 99 % selectivity to C₂ (ethylene and acetylene) and aromatic (benzene and naphthalene) products, at the tested conditions. The selectivity towards C₂ or aromatics was manipulated purposely by adding H₂ into or removing H₂ from the membrane reactor feed and permeate gas streams.     

Partial Oxidation of Methane into Syngas with Oxygen Permeating Ceramic Membrane Reactors

Partial oxidation of methane (CH₄ +1/2O₂ CO + 2H₂) is considered as an alternative reforming reaction to steam reforming for production of syngas. This reaction is a slightly exothermic reaction and produces syngas of H₂/CO = 2, which is suitable for the synthesis of hydrocarbon or methanol. In this paper, the catalytic partial oxidation of CH₄ with a membrane reactor using oxygen permeating ceramic, in particular, LaGaO₃-based oxide, is reported. Supported Ni or Rh catalysts are active and selective for this reaction. On the other hand, a mixed ionic and electronic conducting (MIEC) ceramic membrane is useful for obtaining pure oxygen from air when the gradient in oxygen partial pressure is obtained. As for a MIEC membrane, mixed electronic–oxide ionic conductors of Fe- or Co-based perovskite oxides are widely investigated. However, the improvement in stability in a reducing atmosphere is critically required for the MIEC membrane for the application to the membrane reactor for CH₄ partial oxidation. Perovskite oxides of LaGaO₃ doped with Sr for a La site and a Fe, Co, or Ni for a Ga site, respectively, are promising as the oxygen-separating membrane for CH₄ partial oxidation because of high stability in a reducing atmosphere as well as high permeability of oxygen. The partial oxidation of CH₄ with solid oxide fuel cells (SOFCs) is also described. Simultaneous generation of electrical power and syngas is demonstrated by the fabricated fuel cell type reactor using a LaGaO₃-based oxide electrolyte.     

Oscillations during partial oxidation of methane to synthesis gas over Ru/Al2O3 catalyst (Special column of methane transformation, Article)

Oscillations in temperatures of catalyst bed as well as concentrations of gas phase species at the exit of reactor were observed during the partial oxidation of methane to synthesis gas over Ru/Al₂O₃ in the temperature range of 600 to 850 °C. XRD, H₂-TPR and in situ Raman techniques was used to characterize the catalyst. Two types of ruthenium species, i.e. the ruthenium species weakly interacted with Al₂O₃ and that strongly interacted with the support, were identified by H₂-TPR experiment. These species are responsible for two types of oscillation profiles observed during the reaction. The oscillations were the result of these ruthenium species switching cyclically between the oxidized state and the reduced state under the reaction condition. These cyclic transformations, in turn, were the result of temperature variations caused by the varying levels of the strongly exothermic CH₄ combustion and the highly endothermic CH₄ reforming (with H₂O and CO₂) reactions (or the less exothermic direct partial oxidation of methane to CO and H₂), which were favored by the oxidized and the metallic sites, respectively. The major pathway of synthesis gas formation over the catalyst was via the combustion-reforming mechanism.     

From CH4 reforming with CO2 to pyrolysis over a platinum catalyst

At temperatures up to 1100°C, CH₄ and CO₂ react over a Pt wire to give mainly the reforming product CO, even at a CH₄/CO₂ ratio of 4.3. But if coke is present on the wire, the dominant reaction becomes the pyrolysis of CH₄ to form mainly C₂H₂ and C₆H₆. Thus, surface carbon poisons the reforming reaction and is autocatalytic for CH₄ pyrolysis. Higher temperatures and larger CH₄/O₂ ratios favor the formation of coke and the pyrolysis reaction. Molecular oxygen and, to a lesser extent, water have the opposite effect.     

Production of hydrogen by oxidative steam reforming of methanol over Cu/SiO2 catalysts

Selective production of hydrogen by oxidative steam reforming of methanol (OSRM) was studied over Cu/SiO₂ catalyst using fixed bed flow reactor. Textural and structural properties of the catalyst were analyzed by various instrumental methods. TPR analysis illustrates that the reduction temperature peak was observed between 510?K and 532?K at various copper loadings and calcination temperatures and the peaks shifted to higher temperature with increasing copper loading and calcination temperature. The XRD and XPS analysis demonstrates that the copper existed in different oxidation states at different conditions: Cu₂O, Cu⁰, CuO and Cu(OH)₂ in uncalcined sample; CuO in calcined sample: Cu₂O and metallic Cu after reduction at 600?K and Cu⁰ and CuO after catalytic test. TEM analysis reveals that at various copper loadings, the copper particle size is in the range between 3.0?nm and 3.8?nm. The Cu particle size after catalytic test increased from 3.6 to 4.8?nm, which is due to the formation of oxides of copper as evidenced from XRD and XPS analysis. The catalytic performance at various Cu loadings shows that with increasing Cu loading from 4.7 to 17.3?wt%, the activity increases and thereafter it decreases. Effect of calcination shows that the sample calcined at 673?K exhibited high activity. The O₂/CH₃OH and H₂O/CH₃OH molar ratios play important role in reaction rate and product distribution. The optimum molar ratios of O₂/CH₃OH and H₂O/CH₃OH are 0.25 and 0.1, respectively. When the reaction temperature varied from 473 to 548?K, the methanol conversion and H₂ production rate are in the range of 21.9–97.5% and 1.2–300.9?mmol?kg^?1?s^?1, respectively. The CO selectivity is negligible at these temperatures. Under the optimum conditions (17.3?wt%, Cu/SiO₂; calcination temperature 673?K; 0.25 O₂/CH₃OH molar ratio, 0.5 H₂O/CH₃OH molar ratio and reaction temperature 548?K), the maximum hydrogen yield obtained was 2.45?mol of hydrogen per mole of methanol. The time on stream stability test showed that the Cu/SiO₂ catalyst is quite stable for 48?h.     

Semiconductor Photocatalysts for Non-oxidative Coupling,Dry Reforming and Steam Reforming of Methane

Methane is one of the promising alternatives of petroleum, which should be used for not only a fuel but also a resource for hydrogen and more useful chemicals as with the petroleum. However, the selective methane conversion to them is still difficult in contrast to the combustion. Three types of photocatalytic reactions for methane conversion, i.e., the photocatalytic non-oxidative coupling of methane (2CH₄ → C₂H₆ + H₂), the photocatalytic dry reforming of methane (CH₄ + CO₂ → 2CO + 2H₂) and the photocatalytic steam reforming of methane (CH₄ + 2H₂O → 4H₂ + CO₂), can take place around room temperature or at a mild condition such as 473 K using photoenergy and semiconductor photocatalyst. In the present short review, the details of each photocatalytic reaction and the design concept of the semiconductor photocatalysts for each photocatalytic methane conversion were summarized and discussed.     

Hydrogen Production From Crude Bio-oil and Biomass Char by Electrochemical Catalytic Reforming

We reports an efficient approach for production of hydrogen from crude bio-oil and biomass char in the dual fixed-bed system by using the electrochemical catalytic reforming method. The maximal absolute hydrogen yield reached 110.9 g H₂/kg dry biomass. The product gas was a mixed gas containing 72%H₂, 26%CO₂, 1.9%CO, and a trace amount of CH₄. It was observed that adding biomass char (a by-product of pyrolysis of biomass) could remarkably increase the absolute H₂ yield (about 20%-50%). The higher reforming temperature could enhance the steam reforming reaction of organic compounds in crude bio-oil and the reaction of CO and H₂O. In addition, the CuZn-Al₂O₃ catalyst in the water-gas shift bed could also increase the absolute H₂ yield via shifting CO to CO₂.     

Ion cyclotron resonance studies of some reactions of C+ ions

Product distributions and rate constants for the reaction of ground state C⁺ ions with O₂, NO, HCl, CO₂, H₂S, H₂O, HCN, NH₃, CH₄, H₂CO, CH₃OH, and CH₃NH₂ have been measured. Rate constants were obtained using ion cyclotron resonance trapped ion methods at JPL, and product distributions were obtained using a tandem (Dempster-ICR) mass spectrometer at the University of Utah. Rapid carbon isotope exchange has also been observed in C⁺-CO collisions.     

Combination of glow-discharge and arc plasmas for CF4 abatement

Decomposition of CF₄ by glow-discharge and arc plasmas was studied using a tubular quartz reactor, a disk type, and a T-type quartz reactor. The effects of different metal electrodes, input voltage, and reactor type on the efficiency of CF₄ total destruction (DRE) were studied. The T-shape reactor was more efficient in CF₄ destruction than either the disk or tubular type due to a combined effect of glow discharge and arc plasmas. Several hydrogen and oxygen sources, such as H₂O, H₂, O₂, and CH₄, were used to convert CF₄. Using H₂ and O₂ as the hydrogen and oxygen sources presented better DRE than using H₂O. The effect of different hydrogen and oxygen sources on the conversion of CF₄ followed the trend: (H₂ + O₂) > (CH₄ + O₂) > H₂O. The maximum DRE of 95% was observed with 0.5% CF₄ using H₂ and O₂. A mass spectrometer and an emission spectroscope equipped with a charge-coupled detector (CCD) were used to characterize the products and intermediates. Mass spectrometric studies indicated that the reaction products were HF, CO₂, and trace amounts of NO. N₂ first negative and second positive emission lines were observed in the glow discharge plasmas as well as in the arc plasmas of N₂. However, C and F intermediates were observed only in arc plasmas of CF₄. Reactions occurring in the glow discharge plasmas and arcs seem to follow different mechanisms.     

Syngas production in a novel perovskite membrane reactor with co-feed of CO2

Partial oxidation of methane（POM） co-fed with CO₂ to syngas in a novel catalytic BaCo_0.6Fe_0.2Ta_0.2O_3-δ oxygen permeable membrane reactor was successfully reported.Adding CO₂ to the partial oxidation of methane reaction not only alters the ratio of CO/H₂,but also increases the oxygen permeation flux and CH₄ conversion.Around 96%CH₄ conversion with more than 93%CO₂ conversion and 100%CO selectivity is achieved,which shows an excellent reaction performance.A steady oxygen permeation flux of 15 mL/（cm² min） is obtained during the 100-h operation,which shows good stability as well.     

Fragmentation of some 4<Emphasis Type="Italic">H</Emphasis>-pyran-4-one and pyridin-4-one derivatives under electron impact

Fragmentation of 13 compounds of the 4H-pyran-4-one and pyridin-4-one series under electron impact involves formation of rearrangement ions stabilized by multiple bonds and oxygen atoms (mostly [RC≡O]⁺ and RCH=OR′]⁺), as well of neutral molecules with low enthalpies of formation (CO, H₂O, CH₂O, CO₂, CH₂=C=O, C₃O₂, and RCOOH; R = H, Me, HC≡C, HOC≡C).     

Hydrogen production from simulated hot coke oven gas by catalytic reforming over Ni/Mg（Al）O catalysts

Hydrogen production by catalytic reforming of simulated hot coke oven gas (HCOG) with toluene as a model tar compound was investigated in a fixed bed reactor over Ni/Mg(Al)O catalysts. The catalysts were prepared by a homogeneous precipitation method using urea hydrolysis and characterized by ICP, BET, XRD, TPR, TEM and TG. XRD showed that the hydrotalcite type precursor after calcination formed (Ni, Mg)Al₂O₄ spinel and Ni-Mg-O solid solution structure. TPR results suggested that the increase in Ni/Mg molar ratio gave rise to the decrease in the reduction temperature of Ni²⁺ to Ni⁰ on Ni/Mg(Al)O catalysts. The reaction results indicated that toluene and CH₄ could completely be converted to H₂ and CO in the catalytic reforming of the simulated HCOG under atmospheric pressure and the amount of H₂ in the reaction effluent gas was about 4 times more than that in original HCOG. The catalysts with lower Ni/Mg molar ratio showed better catalytic activity and resistance to coking, which may become promising catalysts in the catalytic reforming of HCOG.     

Combination of CO2 reforming and partial oxidation of CH4 over Ni/Al2O3 catalysts using fluidized bed reactor

The effects of the Ni loading, total feed flow rate, prereduction temperature, reaction temperature and feed gas ratio for combination of CO₂ reforming and partial oxidation of CH₄ over Ni/Al₂O₃ were investigated using a fluidized bed reactor. Methane conversion to syngas was drastically enhanced using a fluidized bed reactor over Ni/Al₂O₃ catalyst calcined at high temperature. The fluidized bed and the fixed bed reactor were compared and a promoting mechanism of the fluidized bed reactor was proposed. This revised version was published online in August 2006 with corrections to the Cover Date.     

High-Efficient Conversion of CO<Subscript>2</Subscript> in AC-Pulsed Tornado Gliding Arc Plasma

An AC-pulsed tornado gliding arc plasma was employed for CO₂ conversion via CO₂ decomposition and dry reforming reactions. A stable and high-efficient constant arc length discharge mode was obtained in this plasma reactor. And then, CO₂ conversion was studied under this discharge mode. In the case of CH₄/CO₂ = 0, CO₂ was converted to CO and O₂ via the CO₂ decomposition reaction. Energy efficiency of 29 % was attained at CO₂ conversion of 6 %. With strong reducing agent CH₄ added into CO₂, the main contributor of CO₂ conversion changed from CO₂ decomposition to dry reforming of CH₄. Conversions of CH₄ and CO₂, energy efficiency and energy cost changed sharply at CO₂/CH₄ ratios lower than 1/4, while they changed slowly at CH₄/CO₂ ratios above 1/4. In the case of CH₄/CO₂ = 2/3, energy efficiency of 68 % and syngas energy cost of 1.6 eV/mole were achieved at CH₄ conversion of 29 % and CO₂ conversion of 22 %.     

Computational fluid dynamics study of the dry reforming of methane over Ni/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst in a membrane reactor. Coke deposition

This work investigates the dry reforming of CH₄ as an important process for the conversion of greenhouse gases to synthesis gas. The mixture of methane and CO₂ is readily available in the greenhouse gas which makes realization of dry reforming of methane process more convenient. The paper is an attempt to numerically analyse by computational fluid dynamics (CFD) the coking and gasification mechanisms in the lab-scale membrane module with a fixed-bed supported nickel catalyst (Ni/Al₂O₃). The concentrations and molar fluxes obtained by the simulation are compared with the experimental profiles to validate the CFD model. It was found that working in a catalytic fixed-bed membrane reactor, in the case of the dry reforming of methane and under specific conditions, was not critical, from the point of view of catalyst deactivation.