Biohydrogen production from wheat straw hydrolysate using Caldicellulosiruptor saccharolyticus followed by biogas production in a two-step uncoupled process

A two-step, un-coupled process producing hydrogen (H₂) from wheat straw using Caldicellulosiruptor saccharolyticus in a ‘Continuously stirred tank reactor’ (CSTR) followed by anaerobic digestion of its effluent to produce methane (CH₄) was investigated. C. saccharolyticus was able to convert wheat straw hydrolysate to hydrogen at maximum production rate of approximately 5.2 L H₂/L/Day. The organic compounds in the effluent collected from the CSTR were successfully converted to CH₄ through anaerobic digestion performed in an ‘Up-flow anaerobic sludge bioreactor’ (UASB) reactor at a maximum production rate of 2.6 L CH₄/L/day. The maximum energy output of the process (10.9 kJ/g of straw) was about 57% of the total energy, and 67% of the energy contributed by the sugar fraction, contained in the wheat straw. Sparging the hydrogenogenic CSTR with the flue gas of the UASB reactor ((60% v/v) CH₄ and (40% v/v) CO₂) decreased the H₂ production rate by 44%, which was due to the significant presence of CO₂. The presence of CH₄ alone, like N₂, was indifferent to growth and H₂ production by C. saccharolyticus. Hence, sparging with upgraded CH₄ would guarantee successful hydrogen production from lignocellulosic biomass prior to anaerobic digestion and thus, reasonably high conversion efficiency can be achieved.     

CNT/PDMS composite membranes for H2 and CH4 gas separation

Polydimethylsiloxane (PDMS) composites with different weight amounts of multi-walled carbon nanotubes (MWCNT) were synthesised as membranes to evaluate their gas separation properties. The selectivity of the membranes was investigated for the separation of H₂ from CH₄ gas species. Membranes with MWCNT concentrations of 1% increased the selectivity to H₂ gas by 94.8%. Furthermore, CH₄ permeation was almost totally blocked through membranes with MWCNT concentrations greater than 5%. Vibrational spectroscopy and X-ray photoelectron spectroscopy techniques revealed that upon the incorporation of MWCNT a decrease in the number of available Si–CH₃ and Si–O bonds as well as an increase in the formation of Si–C bonds occurred that initiated the reduction in CH₄ permeation. As a result, the developed membranes can be an efficient and low cost solution for separating H₂ from larger gas molecules such as CH₄.     

Techno-economic analysis (TEA) for CO2 reforming of methane in a membrane reactor for simultaneous CO2 utilization and ultra-pure H2 production

Techno-economic analysis (TEA) for CO₂ reforming of methane in a membrane reactor (MR) was conducted by using process simulation and economic analysis. Parametric studies for key operating conditions like a H₂ permeance, a H₂O sweep gas flow rate, operating temperature, and a CO₂/CH₄ ratio were carried out for a conventional packed-bed reactor (PBR) and a MR using Aspen HYSYS^®, a commercial process simulator program and some critical design guidelines for a MR in terms of a H₂O sweep gas flow rate and a CO₂/CH₄ ratio were obtained. Further economic analysis based on process simulation results showed about 42% reduction in a unit H₂ production cost in a MR (6.48 $ kgH₂^?1) than a PBR (11.18 $ kgH₂^?1) mostly due to the elimination of a pressure swing adsorption (PSA) system in a MR. In addition, sensitivity analysis (SA) revealed that reactant price and labor were the most influential economic factors to determine a unit H₂ production cost for both a PBR and a MR. Lastly, profitability analysis (PA) from cumulative cash flow diagram (CCFD) in Korea provided positive net present value (NPV) of $443,760～$240,980, discounted payback period (DPBP) of 3.03–3.18 y, and present value ratio (PVR) of 7.51–4.97 for discount rates from 2 to 10% showing economic feasibility of the use of a MR as simultaneous CO₂ utilization and ultra-pure H₂ production.     

Effect of food to microorganisms (F/M) ratio on biohythane production via single-stage dark fermentation

Hythane is a mixture of hydrogen and methane gases which are generally produced in separate ways. This work studied mesophilic biohythane gas (H₂+CH₄+CO₂) production in a bioreactor via single-stage dark fermentation. The fermentation was conducted in batch mode using mixed anaerobic microflora and food waste and condensed molasses fermentation soluble to elucidate the effects of food to microorganisms (F/M) ratio (ranging from 0.2 to 38.2) on gas production, metabolite variation, kinetics and biohythane-composition indicator performances. The experimental results indicate that the F/M ratio and fermentation time affect biohythane production efficiency with values of peak maximum hydrogen production rate 9.60 L/L-d, maximum methane production rate 0.72 L/L-d, and hydrogen yield (HY) of 6.17 mol H₂/kg COD_added. Depending on the F/M ratios, the H₂, CH₄ and CO₂ biogas components were 10–60%, 5–20% and 35–70%, respectively. Prospects for the further real application for single-stage biohythane fermentation based on the experimental data are proposed. This work characterizes an important reactor operation factor F/M ratio for innovative single-stage dark fermentation.     

Optimized mixed reforming of biogas with O2 addition in spark-discharge plasma

Adding O₂ into biogas to achieve partial oxidation and CO₂ mixed reforming can not only increase H₂ + CO concentration, but also reduce energy cost for H₂ production. In this study, optimized mixed reforming of biogas with O₂ addition in spark-discharge plasma was pursued in combination with thermodynamic-equilibrium calculation. With respect to mixed reforming of biogas with O₂ addition in spark-discharge plasma, combination coefficients of independent reactions were given to quantitatively evaluate the mixed extent at various O₂/(CH₄–CO₂) ratios. Compared thermodynamic-equilibrium with experimental results, it can be concluded that the optimal O₂/(CH₄–CO₂) ratio for optimized mixed reforming of biogas in spark-discharge plasma was about 0.7. When total-carbon conversion was relatively high (>75%), H₂ + CO concentration on wet basis was the highest and energy cost for H₂ production was the lowest at O₂/(CH₄–CO₂) = 0.7, and their experimental results were closest to their thermodynamic-equilibrium values.     

Trace metals supplementation enhanced microbiota and biohythane production by two-stage thermophilic fermentation

The effect of trace metals supplementation into palm oil mill effluent on biohythane production and responsible microbial communities in thermophilic two-stage anaerobic fermentation was investigated. High biohythane yields were linked to Ni/Co/Fe supplementation (10, 6 and 20 mg L⁻¹, respectively) with maximum H₂ and CH₄ yields of 139 mL H₂ gVS⁻¹ and 454 mL CH₄ gVS⁻¹, respectively. The Ni/Co/Fe supplementation resulted in higher numbers of Bacillus sp., Clostridium sp. and Thermoanaerobacterium sp. together with increasing hydrogenase expression level leading to increasing hydrogen yields of 90.4%. The numbers of Methanosarcina, Methanomassiliicoccus, and Methanoculleus were enhanced by Ni/Co/Fe addition, accompanied by 21.7% higher methane yields. No correlation between methyl coenzyme-M reductase expression level and methane yields was observed. The Ni/Co/Fe supplementation improved gas production in the two-stage biohythane process via enhancing a number of viable hydrogen-producing bacteria together with hydrogenase activity in H₂ stage and enhancing number methanogens in the CH₄ stage.     

Hydrogen generation from polyethylene by milling and heating with Ca(OH)2 and Ni(OH)2

A process to produce hydrogen from polyethylene [–CH₂–]_n (PE) is developed by milling with Ca(OH)₂ and Ni(OH)₂ followed by heating the milled product. Characterizations by a set of analytical methods of X-ray diffraction (XRD), infrared spectroscopy (FT-IR), thermogravimetry–mass spectroscopy (TG/MS) and gas chromatography (GC) were performed on the milled and heated samples to monitor the process. It has been observed that addition of nickel hydroxide as well as increases in milling time and rotational speed of the mill is beneficial to the gas generation, mainly composed of H₂ and CH₄, CO, CO₂. Gaseous compositions from the milled samples vary depending on the added molar ratio of calcium hydroxide. H₂ emission occurs between 400 and 500 °C, and H₂ concentration of 95% is obtained from the mixture of PE/Ca(OH)₂/Ni(OH)₂ (C:Ca:Ni = 6:14:1) sample, and the concentrations of CO and CO₂ remain below 0.5%. The process offers a novel approach to treat waste plastic by transforming it into hydrogen.     

Biohythane production in two-stage anaerobic digestion system

Hydrogen (H₂) and methane (CH₄) are the potential alternative energy carriers with autonomous extensive and viable importance. These fuels could complement the advantages, and discard the disadvantages of each other, if produced simultaneously. Considering their complementary properties, co-production of a mixture of H₂ and CH₄ in the form of biohythane in two-stage anaerobic digestion (AD) process is gaining more interest than their individual production. Biohythane is a better transportation fuel than compressed natural gas (CNG) in terms of high range of flammability, reduced ignition temperature as well as time, without nitrous oxide (NOx) emissions, improved engine performance without specific modification, etc. Other than production of biohythane, performing two-stage AD is advantageous over one-stage AD due to short HRT, high energy recovery, high COD removal, higher H₂ and CH₄ yields, and reduced carbon dioxide (CO₂) in biogas. For improved biohythane production, various aspects of two-stage AD need to be emphasized. Keeping the facts in mind, the process of two-stage AD along with microbial diversity in comparison to one-stage AD has been discussed in the previous sections of this review. For large scale commercial production, and utilization of biohythane in automobile sector, its execution needs evaluation of process parameters, and problems associated with two-stage AD. Hence, the later part of this review describes the production process of biohythane, concerned microbial diversity, operational process parameters, major challenges and their solutions, applications, and economic evaluation for enhanced production of biohythane.     

Tri-reforming of methane over Ni@SiO2 catalyst

A nickel-silica core@shell catalyst was applied for a methane tri-reforming process in a fixed-bed reactor. To determine the optimal condition of the tri-reforming process for production of syngas appropriate for methanol synthesis the effect of reaction temperature (550–750 °C), CH₄:H₂O molar ratio (1:0–3.0) and CH₄:O₂ molar ratio (1:0–0.5) in the feedstock was investigated. CH₄ conversion rate and H₂/CO ratio in the produced syngas were influenced by the feedstock composition. Increasing the amount of steam above the proportion of CH₄:H₂O 1:0.5 reduced the H₂:CO molar ratio in produced syngas to ∼1.5. Increasing oxygen partial pressure improved methane conversion to 90% at 750 °C. At low ∼550 °C reaction temperature the tri-reforming process was not effective with low hydrogen production (H₂ yield ∼20%) and very low <5% CO₂ conversion. Increasing reaction temperature increased hydrogen yield to ∼85% at 750 °C. From all the tested reaction conditions the optimal for tri-reforming over the 11%Ni@SiO₂ catalyst was: feed composition with molar ratio CH₄:CO₂:H₂O:O₂:He 1:0.5:0.5:0.1:0.4 at T = 750 °C. The results were explained in the context of characterisation of the catalysts used. The obtained results showed that the tri-reforming process can be applied for production of syngas with composition suitable for methanol synthesis.     

Hydrogen production and CO2 fixation by flue-gas treatment using methane tri-reforming or coke/coal gasification combined with lime carbonation

The production of hydrogen and the fixation of CO₂ can be achieved by treatment of flue gases derived from fossil fuel fired power plants via catalytic methane tri-reforming or by coal gasification in the presence of CaO. A two-step process is designed to be carried out in two reactors: a) a catalytic gasifier or steam-reformer, operating exothermally at 900–1000 K, with inputs of the flue gas, a carbonaceous source, steam and air, as well as CaO from the calciner, and outputs of H₂, and of “spent” CaCO₃ to the calciner; b) a calciner, operating endothermally at 1100–1300 K, with inputs of spent CaCO₃ from the gasifier, make-up fresh CaCO₃, and outputs of CO₂, as well as of CaO, partly recycled to the gasifier and partly processed in a cement plant. Thermochemical equilibrium calculations along with mass/energy balances indicate that for flue-gas treatment by tri-reforming, CO₂ emission avoidance of up to ∼59% and fossil fuel savings of up to ∼75% may be attained when concentrated solar energy is supplied as high-temperature process heat for the calcination step, all relative to conventional H₂ production by coal gasification. If instead fossil fuel would be used to drive the calcination step, the CO₂ emission avoidance and the fuel savings would be only 20% and 67%, respectively. Estimated annual H₂ production from a coal-fired 500 MWe burner by the proposed flue-gas treatment using either CH₄-tri-reforming or coal gasification would amount to 0.7 × 10⁶ or 0.6 × 10⁶ metric tons H₂, respectively. Estimated fossil fuel consumption for H₂ production by tri-reforming or coke gasification would be 149 or 143 GJ fuel/ton H₂.     

Ultrasonic spray pyrolysis synthesis of Ag/TiO2 nanocomposite photocatalysts for simultaneous H2 production and CO2 reduction

Simultaneous photocatalytic hydrogen production and CO₂ reduction (to form CO and CH₄) from water using methanol as a hole scavenger were investigated using silver-modified TiO₂ (Ag/TiO₂) nanocomposite catalysts. A simple ultrasonic spray pyrolysis (SP) method was used to prepare mesoporous Ag/TiO₂ composite particles using TiO₂ (P25) and AgNO₃ as the precursors. The material properties and photocatalytic activities were compared with those prepared by a conventional wet-impregnation (WI) method. It was found that the samples prepared by the SP method had a larger specific surface area and a better dispersion of Ag nanoparticles on TiO₂ than those prepared by the WI method, and as a result, the SP samples showed much higher photocatalytic activities toward H₂ production and CO₂ reduction. The optimal Ag concentration on TiO₂ was found to be 2 wt%. The H₂ production rate of the 2% Ag/TiO₂–SP sample exhibited a six-fold enhancement compared with the 2% Ag/TiO₂–WI sample and a sixty-fold enhancement compared with bare TiO₂. The molar ratio of H₂ and CO in the final products can be tuned in the range from 2 to 10 by varying the reaction gas composition, suggesting a viable way of producing syngas (a mixture of H₂ and CO) from CO₂ and water using the prepared Ag/TiO₂ catalysts with energy input from the sun.     

H2 processes with CO2 mitigation: Thermo-economic modeling and process integration

Within the challenge of greenhouse gas reduction, hydrogen is regarded as a promising decarbonized energy vector. The hydrogen production by natural gas reforming and lignocellulosic biomass gasification are systematically analyzed by developing thermo-economic models. Taking into account thermodynamic, economic and environmental factors, process options with CO₂ mitigation are compared and optimized by combining flowsheeting with process integration, economic analysis and life cycle assessment in a multi-objective optimization framework. The systems performance is improved by introducing process integration maximizing the heat recovery and valorizing the waste heat. Energy efficiencies up to 80% and production costs of 12.5–42 $/GJH₂${\text{GJ}}_{{\text{H}}_2}$ are computed for natural gas H₂ processes compared to 60% and 29–61 $/GJH₂${\text{GJ}}_{{\text{H}}_2}$ for biomass processes. Compared to processes without CO₂ mitigation, the CO₂ avoidance costs are in the range of 14–306 $/tCO_2,avoided${\text{t}}_{{\text{CO}}_2,\text{avoided}}$. The study shows that the thermo-chemical H₂ production has to be analyzed as a polygeneration unit producing hydrogen, captured CO₂, heat and electricity.     

Flowerlike microspheres catalyst NiO/La2O3 for ethanol-H2 production

Catalysts of nano-sized nickel oxide particles based on flowerlike lanthanum oxide microspheres with high disperse were prepared to achieve simultaneous dehydrogenation of ethanol and water molecules on multi-active sites. XRD, SEM, 77K N₂ adsorption were used to analyze and observe the catalysts’ structure, morphology and porosity. Catalytic parameters with respect to yield of H₂, activity, selectivity towards gaseous products and stability with time-on-stream and time-on-off-stream were all determined. This special morphology NiO/La₂O₃ catalyst represented more than 1000 h time-on-stream stability test and 500 h time-on-off-stream stability test for hydrogen fuel production from ethanol steam reforming at 300 °C without any deactivation. During the 1000 h time-on-stream stability test, ethanol–water mixtures could be converted into H₂, CO, and CH₄ with average selectivity values of 57.0, 20.1, 19.6 and little CO₂ of 3.2 mol%, respectively, and average ethanol conversion values of 96.7 mol%, with H₂ yield of 1.61 mol H₂/mol C₂H₅OH. During the 500 h time-on-off-stream stability test, ethanol–water mixtures could be converted into H₂, CO, CH₄ and CO₂ with average selectivity values of 65.1, 17.3, 15.1 and 2.5 mol%, respectively, and average ethanol conversion values of 80.0 mol%. For the ethanol-H₂ and petrolic hybrid vehicle (EH–HV), the combustion value is the most important factor. So, it was very suitable for the EH–HV application that the low temperature ethanol steam reforming products’ distribution was with high H₂, CO, CH₄ and very low CO₂ selectivity over the special NiO/La₂O₃ flowerlike microspheres.     

Cogeneration of H2 and CH4 from water hyacinth by two-step anaerobic fermentation

A novel reaction mechanism of H₂ and CH₄ cogeneration from water hyacinth (Eichhornia crassipes) was originally proposed to increase the energy conversion efficiency. The glucose and xylose hydrolysates derived from cellulose and hemicellulose are fermented to cogenerate H₂ and CH₄ by two-step anaerobic fermentation. The total volatile solid of hyacinth leaves can theoretically cogenerate H₂ and CH₄ yields of 303 ml-H₂/g-TVS and 211 ml-CH₄/g-TVS, which dramatically increases the theoretical energy conversion efficiency from 19.1% in only H₂ production to 63.1%. When hyacinth leaves are pretreated with 3 wt% NaOH and cellulase in experiments, the cogeneration of H₂ (51.7 ml-H₂/g-TVS) and CH₄ (143.4 ml-CH₄/g-TVS) markedly increases the energy conversion efficiency from 3.3% in only H₂ production to 33.2%. Hyacinth leaves, which have the most cellulose and hemicellulose and the least lignin and ash, give the highest H₂ and CH₄ yields, while hyacinth roots, which have the most ash and the least cellulose and hemicellulose, give the lowest H₂ and CH₄ yields.     

The effects of fuel variability on the electrical performance and durability of a solid oxide fuel cell operating on biohythane

Biohythane is typically composed of 60/30/10 vol% CH₄/CO₂/H₂ and can be produced via two-stage anaerobic digestion of renewable and low carbon biomass with much greater efficiency compared with CH₄/CO₂ biogas. This work investigates the effects of fuel variability on the electrical performance and fuel processing of a commercially available anode supported solid oxide fuel cell (SOFC) operating on biohythane mixtures at 750 °C. Cell electrical performance was characterised using current-voltage curves and electrochemical impedance spectroscopy. Fuel processing was characterised using quadrupole mass spectroscopy. It is shown that when H₂/CO₂ is blended with CH₄ to make biohythane, the SOFC efficiency is significantly increased, high SOFC durability is achieved, and there are considerable savings in CH₄ consumption. Enhanced electrical performance was due to the additional presence of H₂ and promotion of CH₄ dry reforming, the reverse Boudouard and reverse water-gas shift reactions. These processes alleviated carbon deposition and promoted electrochemical oxidation of H₂ as the primary power production pathway. Substituting 50 vol% CH₄ with 25/75 vol% H₂/CO₂ was shown to increase cell power output by 81.6% at 0.8 V compared with pure CH₄. This corresponded to a 3.4-fold increase in the overall energy conversion efficiency and a 72% decrease in CH₄ consumption. A 260 h durability test demonstrated very high cell durability when operating on a typical 60/30/10 vol% CH₄/CO₂/H₂ biohythane mixture under high fuel utilisation due to inhibition of carbon deposition. Overall, this work suggests that decarbonising gas grids by substituting natural gas with renewably produced H₂/CO₂ mixtures (rather than pure H₂ derived from fossil fuels), and utilising in SOFC technology, gives considerable gains in energy conversion efficiency and carbon emissions savings.     

One-stage H2 and CH4 and two-stage H2 + CH4 production from grass silage and from solid and liquid fractions of NaOH pre-treated grass silage

In the present study, mesophilic CH₄ production from grass silage in a one-stage process was compared with the combined thermophilic H₂ and mesophilic CH₄ production in a two-stage process. In addition, solid and liquid fractions separated from NaOH pre-treated grass silage were also used as substrates. Results showed that higher CH₄ yield was obtained from grass silage in a two-stage process (467 ml g⁻¹ volatile solids (VS)_original) compared with a one-stage process (431 ml g⁻¹ VS_original). Similarly, CH₄ yield from solid fraction increased from 252 to 413 ml g⁻¹ VS_original whereas CH₄ yield from liquid fraction decreased from 82 to 60 ml g⁻¹ VS_original in a two-stage compared to a one-stage process. NaOH pre-treatment increased combined H₂ yield by 15% (from 5.54 to 6.46 ml g⁻¹ VS_original). In contrast, NaOH pre-treatment decreased the combined CH₄ yield by 23%. Compared to the energy value of CH₄ yield obtained, the energy value of H₂ yield remained low. According to this study, highest CH₄ yield (495 ml g⁻¹ VS_original) could be obtained, if grass silage was first pre-treated with NaOH, and the separated solid fraction was digested in a two-stage (thermophilic H₂ and mesophilic CH₄) process while the liquid fraction could be treated directly in a one-stage CH₄ process.     

Hydrogen permeation through a Pd-based membrane and RWGS conversion in H2/CO2, H2/N2/CO2 and H2/H2O/CO2 mixtures

This study investigated the effect of gases such as CO₂, N₂, H₂O on hydrogen permeation through a Pd-based membrane −0.012 m² – in a bench-scale reactor. Different mixtures were chosen of H₂/CO₂, H₂/N₂/CO₂ and H₂/H₂O/CO₂ at temperatures of 593–723 K and a hydrogen partial pressure of 150 kPa. Operating conditions were determined to minimize H₂ loss due to the reverse water gas shift (RWGS) reaction. It was found that the feed flow rate had an important effect on hydrogen recovery (HR). Furthermore, an identification of the inhibition factors to permeability was determined. Additionally, under the selected conditions, the maximum hydrogen permeation was determined in pure H₂ and the H₂/CO₂ mixtures. The best operating conditions to separate hydrogen from the mixtures were identified.     

Enhanced H2 fermentation of organic waste by CO2 sparging

This study aimed to improve the productivity of dark fermentative hydrogen production from organic waste. An anaerobic sequencing batch reactor was used for hydrogen fermentation and it was fed with food waste (VS 4.4 ± 0.2% containing 27 g carbohydrate-COD/L) at various CO₂ sparging rates (40–120 L/L/d), hydraulic retention times (HRTs; 18–42 h), and solid retention times (SRTs; 18–160 h). CO₂ sparging increased the H₂ productivity by 5–36% at all the examined conditions, confirming the benefit of the replacement of headspace gas by CO₂. The maximum H₂ production was obtained by CO₂ sparging at 80 L/L/d, resulting in the H₂ productivity of 3.18 L H₂/L/d and the H₂ yield of 97.3 mL H₂/g VS_added. Increase of n-butyrate and isopropanol yields were concurrent with the enhanced H₂ yield by CO₂ sparging. Acidogenic efficiency, the sum of H₂, organic acid, and alcohol, in the CO₂-sparged reactor ranged from 47.9 to 56.0%, which was comparable to conventional acidogenesis. Thermodynamic analysis confirmed that both CO₂ sparging and CO₂ removal were beneficial for H₂-producing reactions, but CO₂ sparing has more profound effect than CO₂ removal on inhibiting H₂-consuming reactions.     

Influence of CO2, CH4, and initial temperature on H2/CO laminar flame speed

The objective of this study is to investigate the impact of syngas composition by varying the H₂/CO ratio (1:3, 1:1, and 3:1 by volume), the CO₂ dilution (0%–40%), and methane addition (0%–40%) on laminar flame speed. Thus, laminar flame speeds of premixed syngas–air mixtures were measured for different equivalence ratios (0.8–2.2) and inlet temperatures (295–450 K) using the Bunsen-burner method. It was found that laminar flame speed increases with increasing H₂/CO ratio, while CO₂ dilution or CH₄ addition decreased it. The location of the maximum flame speed shifts to richer mixtures with decreasing H₂/CO ratio, while it shifts to leaner mixtures with the addition of CH₄ due to its inherent slower flame speed. The location of the maximum flame speed is also shifted towards leaner mixtures with the addition of CO₂ due to the preponderance of the reduction of the adiabatic flame temperature with increasing dilution. Comparison between experimental and numerical results shows a better agreement using a modified mechanism derived from GRI-Mech 3.0. A correlation, based on the experimental results, is proposed to calculate the laminar flame speed over a wide range of equivalence ratios, inlet temperatures, and fuel content.     

Effect of preparation methods on the performance of Ni/Al2O3 catalysts for aqueous-phase reforming of ethanol: Part I-catalytic activity

The effect of preparation method on the performance of Ni/Al₂O₃ catalysts for aqueous-phase reforming of ethanol (EtOH) has been investigated. The first catalyst was prepared by a sol–gel (SG) method and for the second one the Al₂O₃ support was made by a solution combustion synthesis (SCS) route and then the metal was loaded by standard wet impregnation. The catalytic activity of these catalysts of different Ni loading was compared with a commercial Al₂O₃ supported Ni catalyst [CM (10%)] at different temperatures, pressures, feed flow rates, and feed concentrations. Based on the product distribution, the proposed reaction pathway is a mixture of dehydrogenation of EtOH to CH₃CHO followed by C–C bond breaking to produce CO + CH₄ and oxidation of CH₃CHO to CH₃COOH followed by decarbonylation to CO₂ + CH₄. CH₄(C₂H₆ and C₃H₈) also can form via Fischer–Tropsch reactions of CO/CO₂ with H₂. The CH₄ (C₂H₆ and C₃H₈) reacts to form hydrogen and carbon monoxide through steam reforming, while CO converts to CO₂ mostly through the water–gas shift reaction (WGSR). SG catalysts showed poorer WGSR activity than the SCS catalysts. The activation energies for H₂ and CO₂ production were 153, 155 and 167 kJ/mol and 158, 160 and 169 kJ/mol for SCS (10%), SG (10%), and CM (10%) samples, respectively.