Continuous supercritical water gasification of isooctane: A promising reactor design

A new design of supercritical water gasification system was developed to achieve high hydrogen gas yield and good gas–liquid flow stability. The apparatus consisted of a reaction zone, an insulation zone and a cooling zone that were directly connected to the reaction zone. The reactor was set up at an inclination of 75° from vertical position, and feed and water were introduced at the bottom of the reactor. The performances of this new system were investigated with gasification of isooctane at various experimental conditions – reaction temperatures of 601–676 °C, residence times of 6–33 s, isooctane concentrations of 5–33 wt%, and oxidant (hydrogen peroxide) concentrations up to 4507 mmol/L without using catalysts. A significant increase in hydrogen gas yield, almost four times higher than that from the previous up-down gasifier configuration (B. Veriansyah, J. Kim, J.D. Kim, Y.W. Lee, Hydrogen Production by Gasification of Isooctane using Supercritical Water, Int. J. Green Energy. 5 (2008) 322–333) was observed with the present gasifier configuration. High hydrogen gas yield (6.13 mol/mol isooctane) was obtained at high reaction temperature of 637 °C, a low feed concentration of 9.9 wt% and a long residence time of 18 s in the presence of 2701.1 mmol/L hydrogen peroxide. At this condition, the produced gases mainly consisted of hydrogen (59.5 mol%), methane (14.8 mol%) and carbon dioxide (22.0 mol%), and a small amount of carbon monoxide (1.6 mol%) and C₂–C₃ species (2.1 mol%). Reaction mechanisms of supercritical water gasification of isooctane were also presented.     

Modeling & optimization of renewable hydrogen production from biomass via anaerobic digestion & dry reformation

There is a growing interest in the usage of hydrogen as an environmentally cleaner form of energy for end users. However, hydrogen does not occur naturally and needs to be produced through energy intensive processes, such as steam reformation. In order to be truly renewable, hydrogen must be produced through processes that do not lead to direct or indirect carbon dioxide emissions. Dry reformation of methane is a route that consumes carbon dioxide to produce hydrogen. This work describes the production of hydrogen from biomass via anaerobic digestion of waste biomass and dry reformation of biogas. This process consumes carbon dioxide instead of releasing it and uses only renewable feed materials for hydrogen production. An end-to-end simulation of this process is developed primarily using Aspen HYSYS® and consists of steady state models for anaerobic digestion of biomass, dry reformation of biogas in a fixed-bed catalytic reactor containing Ni–Co/Al₂O₃ catalyst, and a custom-model for hydrogen separation using a hollow fibre membrane separator. A mixture-process variable design is used to simultaneously optimize feed composition and process conditions for the process. It is identified that if biogas containing 52 mol% methane, 38 mol% carbon dioxide, and 10 mol% water (or steam) is used for hydrogen production by dry reformation at a temperature of 837.5 °C and a pressure of 101.3 kPa; optimal values of 89.9% methane conversion, 99.99% carbon dioxide conversion and hydrogen selectivity 1.21 can be obtained.     

Oleic acid gasification over supported metal catalysts in supercritical water: Hydrogen production and product distribution

Oleic acid was examined as a model compound for lipids, which was gasified in supercritical water (SCW) using a batch reactor from 400 to 500 °C at 28 MPa. The influence of operating temperature and several commercial catalysts on the gasification efficiency, hydrogen gas yield, and residual liquid product quality was examined and discussed. The main gaseous components measured were carbon dioxide (CO₂), hydrogen (H₂), methane (CH₄), and traces of carbon monoxide (CO). The residual liquid after reaction was characterized by analyzing the chemical oxygen demand (COD), total organic carbon (TOC), volatile fatty acids (VFAs), and the long chain fatty acids (LCFAs), namely, palmitic, myristic, stearic, linoleic, and oleic acids. The results showed that an increase of temperature coupled with the use of catalyst enhanced the gas yield dramatically. The H₂ yield was 15 mol/mol oleic acid converted using both the pelletized Ru/Al₂O₃ and powder Ni/Silica-alumina catalysts which gave 4 times higher than the equilibrium yield. The COD reduction efficiency ranged from 31% at 400 °C without catalyst to 96 % at 500 °C in the presence of Ni/Silica-alumina catalyst. The composition of residual liquid products was studied using gas chromatography/mass spectrometry (GC-MS), with a generalized reaction pathway for oleic acid decomposition in SCW reported.     

Effect of nickel loading on hydrogen production and chemical oxygen demand (COD) destruction from glucose oxidation and gasification in supercritical water

Gasification and partial oxidation of 0.25 molar glucose solution was conducted over different metallic nickel (Ni) loadings (7.5, 11, and 18 wt%) on different catalyst supports (θ-Al₂O₃ and γ-Al₂O₃) in supercritical water. Experiments were carried out at three different temperatures (T) of 400, 450, and 500 °C at constant pressure of 28 MPa and a 30 min reaction time (t). For comparison, some experiments were conducted using high loading commercial catalyst (65 wt% Ni on Silica–alumina). Hydrogen peroxide (H₂O₂) was used as a source of oxygen in the partial oxidation experiments. Oxygen to carbon molar ratios (MR) of 0.5–0.9 were examined to increase the hydrogen production via carbon monoxide (CO) production. Results showed that in the absence of the catalyst, the optimum molar ratio was 0.8 i.e. 80% of the amount of oxygen required for complete oxidation of glucose. At a molar ratio of 0.8, the hydrogen yield was 0.3 mol/mol, as compared to 0.2 mol/mol glucose at molar ratio of 0.5 and 0.9. This optimized oxygen dose was adopted as a base line for catalysts evaluation. The main gaseous products were carbon dioxide (CO₂), carbon monoxide (CO), hydrogen (H₂), and methane (CH₄). Results also showed that the presence of Ni increased the total gas yield increased in the 7.5–18 wt Ni/Al₂O₃ catalyst. An increase in MR from 0.55 to 0.8 increased the of carbon dioxide and hydrogen yields from 1.8 to 3.8 mol/mol glucose and from 0.9 to 1.1 mol/mol. The carbon monoxide and methane yields remain constant at 2 and 0.5 mol/mol glucose, respectively. The introduction of hydrogen peroxide (H₂O₂) prior to the feed injection inhibited the catalyst activity and did not increase the hydrogen yield whereas the introduction of H₂O₂ after 15 min of reaction time increased the hydrogen yield from 0.62 mol/mol to 1.5 mol/mol. This study showed that approximately the same hydrogen yield can be obtained from the synthesized low nickel alumina loading (18 wt%) catalyst as with the 65 wt% nickel on silica–alumina loading commercial catalyst. The highest H₂ yield of 1.5 mol/mol glucose was obtained with commercial Ni/silica–alumina with a BET surface area of 190 m²/g compared to 1.2 mol/mol with the synthesized Ni/θ alumina with a BET surface area of 46 m²/g.     

Autothermal reforming of methane for producing high-purity hydrogen in a Pd/Ag membrane reactor

Autothermal reforming of methane includes steam reforming and partial oxidizing methane. Theoretically, the required endothermic heat of steam reforming of methane could be provided by adding oxygen to partially oxidize the methane. Therefore, combining the steam reforming of methane with partial oxidation may help in achieving a heat balance that can obtain better heat efficacy. Membrane reactors offer the possibility of overcoming the equilibrium conversion through selectively removing one of the products from the reaction zone. For instance, only can hydrogen products permeate through a palladium membrane, which shifts the equilibrium toward conversions that are higher than the thermodynamic equilibrium. In this study, autothermal reforming of methane was carried out in a traditional reactor and a Pd/Ag membrane reactor, which were packed with an appropriate amount of commercial Ni/MgO/Al₂O₃ catalyst. A power analyzer was employed to measure the power consumption and to check the autothermicity. The average dense Pd/Ag membrane thickness is 24.3 μm, which was coated on a porous stainless steel tube via the electroless palladium/silver plating procedure. The experimental operating conditions had temperatures that were between 350 °C and 470 °C, pressures that were between 3 atm and 7 atm, and O₂/CH₄ = 0–0.5. The effects of the operating conditions on methane conversion, permeance of hydrogen, H₂/CO, selectivities of CO_x, amount of power supply, and the carbon deposition of the catalyst after the reaction is thoroughly discussed in this paper. The experimental results indicate that an optimum methane conversion of 95%, with a hydrogen production rate of 0.093 mol/m². S, can be obtained from the autothermal reforming of methane at H₂O/CH₄ = 1.3 and O₂/CH₄ near 0.4, at which the reaction does not consume power, and the catalysts are not subject to any carbon deposition.     

Production of hydrogen by methane catalytic decomposition over Ni–Cu–Fe/Al2O3 catalyst

Catalysts with high nickel concentrations 75%Ni–12%Cu/Al₂O₃, 70%Ni–10%Cu–10%Fe/Al₂O₃ were prepared by mechanochemical activation and their catalytic properties were studied in methane decomposition. It was shown that modification of the 75%Ni–12%Cu/Al₂O₃ catalyst with iron made it possible to increase optimal operating temperatures to 700–750 °C while maintaining excellent catalyst stability. The formation of finely dispersed Ni–Cu–Fe alloy particles makes the catalysts stable and capable of operating at 700–750 °C in methane decomposition to hydrogen and carbon nanofibers. The yield of carbon nanofibers on the modified 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst at 700–750 °C was 150–160 g/g. The developed hydrogen production method is also efficient when natural gas is used as the feedstock. An installation with a rotating reactor was developed for production of hydrogen and carbon nanofibers from natural gas. It was shown that the 70%Ni–10%Cu–10%Fe/Al₂O₃ catalyst could operate in this installation for a prolonged period of time. The hydrogen concentration at the reactor outlet exceeded 70 mol%.     

High temperature iron-based catalysts for hydrogen and nanostructured carbon production by methane decomposition

The production of hydrogen and filamentous carbon by means of methane decomposition was investigated in a fixed-bed reactor using iron-based catalysts. The effect of the textural promoter and the addition of Mo as a dopant affects the catalysts performance substantially: iron catalyst prepared with Al₂O₃ showed slightly higher catalytic performance as compared to those prepared with MgO; Mo addition was found to improve the catalytic performance of the catalyst prepared with MgO, whereas in the catalyst prepared with Al₂O₃ displayed similar or slightly poorer results. Additionally, the influence of the catalyst reduction temperature, the reaction temperature and the space velocity on the hydrogen yield was thoroughly investigated. The study reveals that iron catalysts allow achieving high methane conversions at operating temperatures higher than 800 °C, yielding simultaneously carbon nanofilaments with interesting properties. Thus, at 900 °C reaction temperature and 1 l g⁻¹_cat h⁻¹ space velocity, ca. 93 vol% hydrogen concentration was obtained, which corresponds to a methane conversion of 87%. Additionally, it was found that at temperatures higher than 700 °C, carbon co-product is deposited mainly as multi walled carbon nanotubes. The textural and structural properties of the carbonaceous structures obtained are also presented.     

An experimental investigation into the CO2 gasification of deactivated activated-carbon catalyst used for methane decomposition to produce hydrogen

A series of experiments was conducted to study the CO₂ gasification of a deactivated palm-shell-based activated-carbon (ACPS) catalyst used for the thermocatalytic decomposition of methane to produce hydrogen. This catalyst becomes deactivated due to the accumulation of carbon deposits during the methane-decomposition process. The CO₂ gasification was carried out at 850, 900, 950 or 1000 °C to study the deactivated ACPS, which was used at methane-decomposition temperatures of 850 or 950 °C. A series of six methane-decomposition cycles at 950 °C alternating with five gasification cycles using CO₂ at 900, 950 and 1000 °C was also carried out to evaluate the stability of the catalyst. The experiments were conducted using a thermobalance by monitoring the change in mass of the catalyst with time, i.e., the mass gain during methane decomposition or the mass loss during CO₂ gasification. Gasification of the virgin and deactivated ACPS showed strong temperature dependence, with the half and complete gasification times having an exponential dependence on temperature. The gasification reactivity at different conversions was higher for the virgin ACPS and increased with increases in the decomposition temperatures used for deactivation of the ACPS. The activation energies of virgin ACPS and ACPS deactivated at a decomposition temperature of 850 °C decreased with an increase in conversion, while they increased for the ACPS deactivated at a decomposition temperature of 950 °C; the activation energies varied between 81 and 163 kJ/mol. The gasification reactivity changed with methane conversion, showing maximum values for both the virgin and deactivated ACPS at a decomposition temperature of 950 °C. The initial gasification reactivity of the catalyst decreased after three gasification cycles at 1000 °C, while no significant change was observed with gasification cycles at 950 or 900 °C.     

Thermodynamic and experimental study of combined dry and steam reforming of methane on Ru/ ZrO2-La2O3 catalyst at low temperature

Analysis of the effect of adding small amounts of steam to the methane dry reforming feed on activity and products distribution was performed from thermodynamic equilibrium calculations of the system based on the Gibbs free energy minimization method. This analysis is supported by new insights from the direct experimental investigation of the influence of co-feeding with H₂O over a Ru/ZrO₂-La₂O₃ catalyst. Activity measurements were carried out in a fixed-bed reactor but using the operating conditions applicable in a Pd membrane reactor, that is, at maximum reaction temperature below 550 °C. Experimental results were in good agreement with thermodynamics predictions. It was observed that the addition of H₂O into the dry reforming feed strongly affects activity and products distribution. The co-feeding of steam resulted in increasing methane conversion and hydrogen yield but decreasing carbon dioxide conversion and carbon monoxide yield. At a given temperature, syngas composition (H₂/CO ratio) can be tuned by changing the amount of H₂O co-fed. Interestingly the stability of the Ru/ZrO₂-La₂O₃ catalyst was improved by adding steam to the dry reforming reactant mixtures.     

Hydrogen production from supercritical water reforming of glycerol in an empty Inconel 625 reactor

Glycerol reforming was investigated under supercritical water conditions (450–575 °C, 250 bar). A feed containing 5 wt.% of glycerol was continuously fed to an empty Inconel 625 reactor. The products of the reaction were separated into gas and liquid phases in a condenser. At a feed rate of 2.15 g/min, the glycerol conversion significantly increased from 0.05 to 0.97 when increasing operating temperature from 450 to 575 °C. Although lowering the feed rate (i.e. increasing the residence time) could considerably improve the conversion, carbon formation became a problem especially at high operating temperatures (550–575 °C). The major gaseous products were hydrogen (approximately 60 mol%), carbon monoxide, carbon dioxide and methane with some traces of ethane, ethylene, propane, and propylene. Various liquid products were detected including acetaldehyde, acetol, methanol, acetic acid, propionaldehyde, allyl alcohol, acetone, acrolein, ethanol, ethylene glycol, and acrylic acid but the major liquid components were acetaldehyde and acetol. With a feed glycerol concentration of 2.5 wt.% and operating temperature of 525 °C, glycerol conversion of 0.91 and H₂ yield of 2.86 can be obtained without carbon formation. Finally, it was demonstrated that higher H₂ yield with much lower carbon formation was observed in supercritical water reforming (250 bar) compared to conventional steam reforming at 1 bar under similar temperatures.     

Hydrogen-rich gas from catalytic steam gasification of municipal solid waste (MSW): Influence of catalyst and temperature on yield and product composition

In the present study the catalytic steam gasification of MSW to produce hydrogen-rich gas or syngas (H₂ + CO) with calcined dolomite as a catalyst in a bench-scale downstream fixed bed reactor was investigated. The influence of the catalyst and reactor temperature on yield and product composition was studied at the temperature range of 750–950 °C, with a steam to MSW ratio of 0.77, for weight hourly space velocity of 1.29 h⁻¹. Over the ranges of experimental conditions examined, calcined dolomite revealed better catalytic performance, at the presence of steam, tar was completely decomposed as temperature increases from 850 to 950 °C. Higher temperature resulted in more H₂ and CO production, higher carbon conversion efficiency and dry gas yield. The highest H₂ content of 53.29 mol%, and the highest H₂ yield of 38.60 mol H₂/kg MSW were observed at the highest temperature level of 950 °C, while, the maximum H₂ yield potential reached 70.14 mol H₂/kg dry MSW at 900 °C. Syngas produced by catalytic steam gasification of MSW varied in the range of 36.35–70.21 mol%. The char had a highest ash content of 84.01% at 950 °C, and negligible hydrogen, nitrogen and sulphur contents.     

Syngas production from catalytic gasification of waste polyethylene: Influence of temperature on gas yield and composition

The catalytic steam gasification of waste polyethylene (PE) from municipal solid waste (MSW) to produce syngas (H₂ + CO) with NiO/γ-Al₂O₃ as catalyst in a bench-scale downstream fixed bed reactor was investigated. The influence of the reactor temperature on the gas yield, gas composition, steam decomposition, low heating value (LHV), cold gas efficiency and carbon conversion efficiency was investigated at the temperature range of 700–900 °C, with a steam to waste polyethylene ratio of 1.33. Over the ranges of experimental conditions examined, NiO/γ-Al₂O₃ catalyst revealed better catalytic performance as a view of increasing product gas yield and of decreasing char and liquid yields in the presence of steam. Higher temperature resulted in more H₂ and CO production, higher carbon conversion efficiency and product gas yield. The highest syngas (H₂ + CO) content of 64.35 mol%, the highest H₂ content of 36.98 mol%, and the highest CO content of 27.37 mol%, were achieved at the highest temperature level of 900 °C. Syngas produced with a H₂/CO molar ratio in the range of 0.83–1.35, was highly desirable as feedstock for Fischer–Tropsch synthesis for the production of transportation fuels.     

Characteristics of hydrogen production by a plasma–catalyst hybrid converter with energy saving schemes under atmospheric pressure

This paper investigated the production of hydrogen from methane under atmospheric pressure using a plasma–catalyst hybrid converter with emphasis on energy conservation. A spark discharge was used to ionize the hydrocarbon fuel and air mixture with a catalyst to enhance hydrogen production using two energy saving schemes, namely, heat recycling and heat insulation. The experimental results showed that higher methane feeding rate resulted in higher reformate gas temperature and a corresponding increase in methane conversion efficiency. The energy saving systems also enabled the oxygen/carbon ratio to be decreased to reduce oxidation of hydrogen and carbon monoxide and thereby improving the concentrations of hydrogen and carbon monoxide. By heat recycling, a lower methane feeding rate showed an 8.7% improvement in methane conversion efficiency whilst improvement was not apparent with higher methane supply rates due to the already high conversion efficiency. Moreover, it was shown that hydrogen production increased significantly with the reaction from water–gas shifting under the same operation parameters but with high methane selectivity. The best combination resulting in a total thermal efficiency of 77.11% was 10 L/min methane feeding rate and 0.8 O₂/C ratio. With water–gas shifting (S/C ratio=0.5), an 86.26% hydrogen yield, equating to 17.25 L/min hydrogen production rate could be achieved. The equilibrium production rate was calculated using the commercialized HSC Chemistry software (^©ChemSW Software, Inc.). Good correlation was obtained between the calculations and the experimental results.     

Hydrogen production from 2-propanol over Pt/Al2O3 and Ru/Al2O3 catalysts in supercritical water

One of the alternative energy sources to fossil fuels is the use of hydrogen as an energy carrier, which provides zero emission of pollutants and high-energy efficiency when used in fuel cells, hydrogen internal combustion engines (HICE) or hydrogen-blend gaseous fueled internal combustion engines (HBICE). The gasification of organics in supercritical water is a promising method for the direct production of hydrogen at high pressures, with very short reaction times. In this study, hydrogen production from 2-propanol over Pt/Al₂O₃ and Ru/Al₂O₃ catalysts was investigated in supercritical water. To investigate the influences on hydrogen production, the experiments were carried out in the temperature range of 400–550 °C and in the reaction time range of 10–30 s, under a pressure of 25 MPa. In addition, different 2-propanol concentrations and reaction pressures were tested in order to comprehend the effects on the gasification yield and hydrogen production. It was found that Pt/Al₂O₃ catalyst was much more selective and effective for hydrogen production when compared to Ru/Al₂O₃. During the catalytic gasification of a 0.5 M solution of 2-propanol, a hydrogen content up to 96 mol% for a gasification yield of 5 L/L feed was obtained.     

Calcium looping gasification for high-concentration hydrogen production with CO2 capture in a novel compact fluidized bed: Simulation and operation requirements

The coal/CaO/steam gasification system is one of the clean coal technologies being developed for hydrogen production with inherent carbon dioxide separation. A novel reactor configuration for the system is proposed in this paper. It consists of three major counterparts: a gasifier, a riser and a regenerator. A regenerable calcium-based sorbent CaO is used to remove carbon dioxide. In the gasifier, the coal-steam gasification reaction occurs with in situ carbon dioxide removal by carbonation reaction. The removal of carbon dioxide favors the gasification and water-shift reaction equilibrium and enables the production of a hydrogen-rich gas stream. CaO is regenerated in the regenerator by burning the unreacted char with oxygen, and a pure stream of carbon dioxide is separated after a cyclone. The regenerated CaO then flows into the riser above the gasifier, and removes the carbon dioxide in the outlet gases from the gasifier and drives the water-gas shift reaction forward, further improving the hydrogen purity. In this work, the feasibility and optimum process conditions of the proposed system were described. The hydrogen purity can reach 96 vol% at a steam flow 80 mol/s and CaO recycle rate 30 mol/s when the carbon conversion rate is 0.50. Increasing the steam flow and CaO recycle rate can enhance the hydrogen yield and purity. With the rise of operation pressure from 1 bar to 10 bar, the hydrogen yield and purity decrease and methane yield increases. High pressure leads to higher calcination temperature. At 10 bar, the temperature for CaCO₃ decomposition is approximately 1100 °C, at such temperature, the sorbent is easy to deactivate. The appropriate temperatures in the gasifier and the riser are 700 and 600 °C, respectively. An analysis of heat integration is conducted. The maximum carbon conversion rate is ∼0.65. A hydrogen production efficiency of 58.5% is obtained at a carbon conversion rate 0.50, steam flow 60 mol/s and CaO recycle rate 30 mol/s, with a hydrogen purity of 93.7 vol%.     

Nanocomposite Ni/ZrO2: Highly active and stable catalyst for H2 production via cyclic stepwise methane reforming reactions

This work investigates the catalytic performance of nanocomposite Ni/ZrO₂-AN catalyst consisting of comparably sized Ni (10–15 nm) and ZrO₂ (15–25 nm) particles for hydrogen production from the cyclic stepwise methane reforming reaction with either steam (H₂O) or CO₂ at 500–650 °C, in comparison with a conventional Ni/ZrO₂-CP catalyst featuring Ni particles supported by large and widely sized ZrO₂ particles (20–400 nm). Though both catalysts exhibited similar activity and stability during the reactions at 500 and 550 °C, they showed remarkably different catalytic stabilities at higher temperatures. The Ni/ZrO₂-CP catalyst featured a significant deactivation even during the methane decomposition step in the first cycle of the reactions at ≥600 °C, but the Ni/ZrO₂-AN catalyst showed a very stable activity during at least 17 consecutive cycles in the cyclic reaction with steam. Changes in the catalyst beds at varying stages of the reactions were characterized with TEM, XRD and TPO–DTG and were correlated with the amount and nature of the carbon deposits. The Ni particles in Ni/ZrO₂-AN became stabilized at the sizes of around 20 nm but those in Ni/ZrO₂-CP kept on growing in the methane decomposition steps of the cyclic reaction. The small and narrowly sized Ni particles in the nanocomposite Ni/ZrO₂-AN catalyst led to a selective formation of filamentous carbons whereas the larger Ni particles in the Ni/ZrO₂-CP catalyst a preferred formation of graphitic encapsulating carbons. The filamentous carbons were favorably volatilized in the steam treatment step but the CO₂ treatment selectively volatilized the encapsulating carbons. These results identify that the nature but not the amount of carbon deposits is the key to the stability of Ni/ZrO₂ catalyst and that the nanocomposite Ni/ZrO₂-AN would be a promising catalyst for hydrogen production via cyclic stepwise methane reforming reactions.     

Thermodynamics of hydrogen production by the steam reforming of butanol: Analysis of inorganic gases and light hydrocarbons

The thermodynamics of butanol steam reformation for the production of hydrogen were simulated using a Gibbs free-energy-minimisation method with water–butanol molar feed ratios (WBFR) between 1 and 18, a pressure range of 1–50 bar and reaction temperatures from 300 to 900 °C. The differences in H₂ and CO production were calculated as functions of WBFR and temperature at 1 bar. On the basis of the equilibrium calculations with higher-hydrocarbon compounds excluded, the optimal operating conditions obtained were 600–800 °C, 1 bar and WBFR = 9–12. At these conditions, the yield of hydrogen and carbon monoxide was maximised and methane selectivity minimised. The yield of hydrogen was in the range of 75.13–81.27% (wet basis) with selectivities of 46.20–54.96%. This was achieved at a temperature of 800 °C and WBFR from 9 to 12. Carbon monoxide yield ranged between 65.48 and 55.57% (wet basis), with selectivities ranging from 14.56 to 10.66%. The formation of coke was completely inhibited at these operating conditions. In order to evaluate the effect of methane on coke formation at lower temperatures, simulations were performed in two sets, i.e., primary products (H₂, CO, CO₂ and C) including or excluding methane. The results indicate that some coke can be hydrogenated to methane at 300 °C and WBFR = 3, and that higher pressure favours hydrogenation reactions. Higher pressure had a negative effect on hydrogen and carbon monoxide yields.     

Life cycle assessment of hydrogen production by methane decomposition using carbonaceous catalysts

Methane decomposition to yield hydrogen and carbon (CH₄ ? 2H₂ + C) is one of the cleanest alternatives, free of CO₂ emissions, for producing hydrogen from fossil fuels. This reaction can be catalyzed by metals, although they suffer a fast deactivation process, or by carbonaceous materials, which present the advantage of producing the catalyst from the carbon obtained in the reaction. In this work, the environmental performance of methane decomposition catalyzed by carbonaceous catalysts has been evaluated through Life Cycle Assessment tools, comparing it to other decomposition processes and steam methane reforming coupled to carbon capture systems. The results obtained showed that the decomposition using the autogenerated carbonaceous as catalyst is the best option when reaction conversions higher than 65% are attained. These were confirmed by 2015 and 2030 forecastings. Moreover, its environmental performance is highly increased when the produced carbon is used in other commercial applications. Thus, for a methane conversion of 70%, the application of 50% of the produced carbon would lead to a virtually zero-emissions process.     

Development of a high-efficiency hydrogen generator for fuel cells for distributed power generation

A collaborative effort between Intelligent Energy and Cal Poly Pomona has developed an adsorption enhanced reformer (AER) for hydrogen generation for use in conjunction with fuel cells in small sizes. The AER operates at a lower temperature (about 500 °C) and has a higher hydrogen yield and purity than those in the conventional steam reforming. It employs ceria supported rhodium as the catalyst and potassium-promoted hydrotalcites to remove carbon dioxide from the products. A novel pulsing feed concept is developed for the AER operation to allow a deeper conversion of the feedstock to hydrogen. Continuous production of near fuel-cell grade hydrogen is demonstrated in the AER with four packed beds running alternately. In the best case of methane reforming, the overall conversion to hydrogen is 92% while the carbon dioxide and carbon monoxide concentrations in the production stream are on the ppm level. The ratio of carbon dioxide in the regeneration exhaust to the one in the product stream is on the order of 10³.     

Optimization of bio-ethanol autothermal reforming and carbon monoxide removal processes

Experimental investigation of bio-ethanol autothermal reforming (ATR) and water-gas shift (WGS) processes for hydrogen production and regression analysis of the data is performed in the study. The main goal was to obtain regression relations between the most critical dependent variables such as hydrogen, carbon monoxide and methane content in the reformate gas and independent factors such as air-to-fuel ratio (λ), steam-to-carbon ratio (S/C), inlet temperature of reactants into reforming process (T_ATRin), pressure (p) and temperature (T_ATR) in the ATR reactor from the experimental data. Purpose of the regression models is to provide optimum values of the process factors that give the maximum amount of hydrogen. The experimental ATR system consisted of an evaporator, an ATR reactor and a one-stage WGS reactor. Empirical relations between hydrogen, carbon monoxide, methane content and the controlling parameters downstream of the ATR reactor are shown in the work. The optimization results show that within the considered range of the process factors the maximum hydrogen concentration of 42 dry vol. % and yield of 3.8 mol mol⁻¹ of ethanol downstream of the ATR reactor can be achieved at S/C = 2.5, λ = 0.20-0.23, p = 0.4 bar, T_ATRin = 230 °C, T_ATR = 640 °C.