Biogas dry reforming for hydrogen production over Ni-M-Al catalysts (M = Mg,Li, Ca,La, Cu,Co, Zn)

Biogas can be highlighted as a renewable raw material for the production of hydrogen. In this study, Ni-M-Al catalysts were evaluated to obtain hydrogen from the biogas reforming. The catalysts were synthesized by coprecipitation with Ni and Al with a molar percentage of 55 and 33%, respectively, varying the third component M = Mg, Li, Ca, La, Cu, Co, Zn, with a molar percentage of 11%. The reactions were carried out in a fixed bed tubular reactor using a synthetic biogas (70% of CH₄ and 30% of CO₂). The results showed that the CH₄ conversion increased with the temperature up to 700 °C for La11, Cu11, and Zn11 catalysts. CO₂ conversion increased for all catalysts in the range of 500–700 °C. The H₂/CO molar ratios observed in the reactions were higher than 1 due to the contribution of the CH₄ decomposition reaction. The catalyst containing La presented better stability in the reactions due to the stronger acid sites and high resistance to sintering. Carbon filaments were produced by all catalysts at 600 and 700 °C. Sintering was the main cause of deactivation of the catalysts, except for La11.     

Biogas dry reforming over Ni-Al catalyst: Suppression of carbon deposition by catalyst preparation and activation

Biogas dry reforming is as an alternative renewable route for the hydrogen production. However, the major drawback of this process is the catalyst deactivation by carbon deposition and sintering. In this work, Ni-Al catalysts were studied aiming to suppress the carbon deposition in the dry reforming of biogas. The catalysts were prepared by coprecipitation and evaluated the washing step. The reactions were carried out with unreduced and reduced catalysts in a fixed bed tubular reactor using a synthetic biogas (60% CH₄ and 40% CO₂). The washing and activation steps influenced the characteristics of the catalysts and the catalytic properties in the biogas reforming. The unwashed sample resulted in an oxide containing potassium nickelate with high basicity and low surface area. Both washed samples, reduced and unreduced, showed a high amount of carbon formation, whereas no carbon formation was observed in the unwashed samples for the reactions in the temperature range of 500–750 °C. The unwashed and unreduced sample was the only one that maintained the activity during all the reaction time at 700 °C (40% CH₄ conversion and 75% CO₂ conversion), low coke amount and no evidence of sintering, which was confirmed by XRD, TPO, and SEM analyses. The carbon suppression was related to the nickelate phase and to the Ni carbide formation in the unwashed and unreduced catalyst. In summary, the carbon deposition in biogas dry reforming was completely controlled between 600 and 750 °C using the unwashed and unreduced Ni-Al catalyst.     

System optimization for effective hydrogen production via anaerobic digestion and biogas steam reforming

To construct a system for the effective hydrogen production from food waste, the conditions of anaerobic digestion and biogas reforming have been investigated and optimized. The type of agitator and reactor shape affect the performance of anaerobic digestion reactors. Reactors with a cubical shape and hydrofoil agitator exhibit high performance due to the enhanced axial flow and turbulence as confirmed by simulation of computational fluid dynamics. The stability of an optimized anaerobic digestion reactor has been tested for 60 days. As a result, 84 L of biogas is produced from 1 kg of food waste. Reaction conditions, such as reaction temperature and steam/methane ratio, affect the biogas steam reforming reaction. The reactant conversions, product yields, and hydrogen production are influenced by reaction conditions. The optimized reaction conditions include a reaction temperature of 700 °C and H₂O/CH₄ ratio of 1.0. Under these conditions, hydrogen can be produced via steam reforming of biogas generated from a two-stage anaerobic digestion reactor for 25 h without significant deactivation and fluctuation.     

Hydrogen production from biogas reforming and the effect of H2S on CH4 conversion

Biogas produced during anaerobic decomposition of plant and animal wastes consists of high concentrations of methane (CH₄), carbon dioxide (CO₂) and traces of hydrogen sulfide (H₂S). The primary focus of this research was on investigating the effect of a major impurity (i.e., H₂S) on a commercial methane reforming catalyst during hydrogen production. The effect of temperature on CH₄ and CO₂ conversions was studied at three temperatures (650, 750 and 850 °C) during catalytic biogas reforming. The experimental CH₄ and CO₂ conversions thus obtained were found to follow a trend similar to the simulated conversions predicted using ASPEN plus. The gas compositions at thermodynamic equilibrium were estimated as a function of temperature to understand the intermediate reactions taking place during biogas dry reforming. The exit gas concentrations as a function of temperature during catalytic reforming also followed a trend similar to that predicted by the model. Finally, catalytic reforming experiments were carried out using three different H₂S concentrations (0.5, 1.0 and 1.5 mol%). The study found that even with the introduction of small amount of H₂S (0.5 mol%), the CH₄ and CO₂ conversions dropped to about 20% each as compared to 65% and 85%, respectively in the absence of H₂S.     

Production and purification of hydrogen by biogas combined reforming and steam-iron process

Cobalt ferrite and hematite with minor additives have been tested for production and purification of high purity hydrogen from a synthetic biogas by steam-iron process (SIP) in a fixed bed reactor. A catalyst based in nickel aluminate has been included in the bed of solids to enhance the rate of the reaction of methane dry reforming (MDR). The reductants resulting from MDR are responsible for reducing the oxides based on iron that will, in the following stage, be oxidized by steam to release hydrogen with less than 50 ppm of CO. Coke minimization along reduction stages forces to operate such reactors above 700 °C for reductions, and as low as 500 °C for oxidations to avoid coke gasification. To avoid problems such as reactor clogging by coke in reductions and/or contamination of hydrogen by gasification of coke along oxidations, steam in small proportions has been included in the feed with the aim of minimizing or even avoiding formation of carbonaceous depositions along the reduction stage of SIP. Since steam is an oxidant, it exerts an inhibiting effect upon reduction of the oxide, that slows down the efficiency of the process. It has been proved that co-feeding low proportions of steam with an equimolar mixture of CH₄ and CO₂ (simulating a poor heating value desulphurized biogas) is able to avoid coke deposition, allowing the operation of both, reductions and oxidations, in isothermal regime (700 °C). Empirical results have been contrasted with data found in literature for similar processes based in MDR and combined (or mixed) reforming process (CMR), concluding that the combination of MDR + SIP proposed in this work, taking apart economic aspects and complex engineering, shows similar yields towards hydrogen, but with the advantage of not requiring a subsequent purification process.     

Steam reforming of methane over unsupported nickel catalysts

This paper describes a study of steam reforming of methane using unsupported nickel powder catalysts. The reaction yields were measured and the unsupported nickel powder surface was studied to explore its potential as a catalyst in internal or external reforming solid oxide fuel cells. The unsupported nickel catalyst used and presented in this paper is a pure micrometric nickel powder with an open filamentary structure, irregular ‘fractal-like’ surface and high external/internal surface ratio. CH₄ conversion increases and coke deposition decreases significantly with the decrease of CH₄:H₂O ratio. At a CH₄:H₂O ratio of 1:2 thermodynamic equilibrium is achieved, even with methane residence times of only ∼0.5 s. The CH₄ conversion is 98 ± 2% at 700 °C and no coke is generated during steam reforming which compares favorably with supported Ni catalyst systems. This ratio was used in further investigations to measure the hydrogen production, the CH₄ conversion, the H₂ yield and the selectivity of the CO, and CO₂ formation. Methane-rich fuel ratios cause significant deviations of the experimental results from the theoretical model, which has been partially correlated to the adsorption of carbon on the surface according to TEM, XPS and elemental analysis. At the fuel: water ratio of 1:2, the unsupported Ni catalyst exhibited high catalytic activity and stability during the steam reforming of methane at low-medium temperature range.     

Numerical analysis of a 20-kWe biogas steam reformer in PEMFC applications

This study supports the development of a 20-kW_e biogas reformer for PEMFC applications. Biogas contains a high concentration of carbon dioxide (CO₂) in the feedstock, which can act as a reforming agent but increases the carbon monoxide (CO) concentration in the product. The feedstock composition and the external heat supply impact both the methane (CH₄) conversion and the CO concentration in the product; thus, a numerical model is developed to investigate these impacts. As the CO₂ content in the feedstock or the external heat supply increases, both the CH₄ conversion and the CO concentration in the product increase. A high CO₂ concentration or a high operating temperature stimulates the reforming reactions but also shifts the equilibrium to favor CO production. However, the performance can be improved by controlling the heat supply method. Using a more uniform temperature distribution at approximately 650 °C, the CO concentration decreases while the CH₄ conversion increases. This finding suggests the importance of temperature control in biogas steam reforming.     

Using multi-criteria and thermodynamic analysis to optimize process parameters for mixed reforming of biogas

Syngas is a gas mixture that can be obtained from a variety of raw materials and used as source of hydrogen. Biogas is an interesting raw material from which to produce syngas via thermo-catalytic reforming because it is abundant, can be obtained from low-cost feedstock, and is potentially carbon-neutral. However, difficulties arise because biogas composition changes from source to source, the reforming process can be quite energy-intensive and there is associated catalyst deactivation through carbon deposition. Mixed reforming of biogas with steam and/or air shows benefits in terms of carbon deposition and energy requirements, but the reaction network is complicated and finding the optimal operating conditions is not trivial. Although several analytical techniques have been used in the literature to find the optimal process conditions, a direct comparison is difficult due to the different criteria and/or boundaries considered. This paper aims to develop a novel and comprehensive methodology for identifying the optimal thermodynamic operating conditions (temperature and feed ratios) for mixed reforming of biogas with air and steam, based on equilibrium data manipulated via two multi-criteria decision making (MCDM) techniques in series, namely the entropy and the TOPSIS methods. The optimal scenario is when biogas made of 50–60% CH₄ in CO₂ is reacted in the reforming reactor at CH₄/CO₂/O₂/H₂O = 1/1–0.67/0–0.1/3–2.4 and 790-735 °C, resulting in a product stream composed of 66–65% H₂, 0.8–1% CO and 33-28% CO₂ on a dry basis after the water-gas shift section. At these conditions the hydrogen yield and the conversion of methane in the biogas can be simultaneously maximized, while the yield of solid carbon and the net energy requirement of the overall process can be minimized. In conjunction with the numerical results, the main outcome of this paper is the development of a novel method based on MCDM techniques for the optimization of the operating conditions in a network of reactions.     

Biogas dry reforming using Ni–Al-LDH catalysts reconstructed with Mg and Zn

The reconstruction of NiAl-LDH by incorporating Mg or Zn using a memory effect was investigated aiming to improve the basic properties of the catalysts and evaluated in the dry reforming of Biogas. Samples were characterized by XRD, CO₂?TPD, N₂-physisorption, TPR, and TPO. Biogas dry reforming experiments were carried out using a feed of CH₄/CO₂/N₂ = 1.5/1/7.5 in the temperature range of 500–750 °C with in situ reduced samples. The washing step strongly influences the LDH reconstruction. The unwashed samples showed the reconstruction of the LDH structure, presented a low specific area, and high basicity, responsible for decreasing carbon formation during reactions. The washed samples did not exhibit the LDH reconstruction property but showed a high specific area and low basicity. The metal used in the reconstruction influences the crystallinity, basicity, and reducibility of the materials. Samples with Zn showed higher crystallinity and reducibility, whereas the samples with Mg showed higher basicity. Among all the catalysts, reconstruction with Zn and subsequent washing leads to the best results with CH₄ and CO₂ conversion of 73% and 90%, respectively, and an H₂/CO ratio of approximately 2. This can be attributed to the Ni–Zn alloy formation and to the reducing properties suitable for the range between 600 and 700 °C. This catalyst showed the highest resistance to sintering in the stability test at 700 °C.     

Biogas reforming for hydrogen production over mesoporous Ni2xCe1−xO2 catalysts

Biogas reforming for hydrogen production over mesoporous Ni_2xCe_1−xO₂ catalysts were proposed in this study. Mesoporous Ni_2xCe_1−xO₂ (x = 0.05, 0.13, 0.2) was prepared by a reverse precipitation method. The effects of nickel content were investigated in physicochemical properties and catalytic activities. All of the catalysts were reduced with 10% H₂/Ar at 600 °C before reactions, the reduced catalysts were found to be active for both dry and steam reforming of methane (CH₄:CO₂:H₂O = 3:1:2) to produce hydrogen and syngas. The studies were firstly carried out by temperature program reaction from 400 °C to 900 °C to verify the activity of temperature dependency. The long-term stability analysis was also studied at 700 °C for 24 h. Commercial catalyst (R67) was also employed for a comparative purpose.     

Simulation of steam reforming of biogas in an industrial reformer for hydrogen production

The paper aims to investigate the steam reforming of biogas in an industrial-scale reformer for hydrogen production. A non-isothermal one dimensional reactor model has been constituted by using mass, momentum and energy balances. The model equations have been solved using MATLAB software. The developed model has been validated with the available modeling studies on industrial steam reforming of methane as well as with the those on lab-scale steam reforming of biogas. It demonstrates excellent agreement with them. Effect of change in biogas compositions on the performance of industrial steam reformer has been investigated in terms of methane conversion, yields of hydrogen and carbon monoxide, product gas compositions, reactor temperature and total pressure. For this, compositions of biogas (CH₄/CO₂ = 40/60 to 80/20), S/C ratio, reformer feed temperature and heat flux have been varied. Preferable feed conditions to the reformer are total molar feed rate of 21 kmol/h, steam to methane ratio of 4.0, temperature of 973 K and pressure of 25 bar. Under these conditions, industrial reformer fed with biogas, provides methane conversion (93.08–85.65%) and hydrogen yield (1.02–2.28), that are close to thermodynamic equilibrium condition.     

Catalytic supercritical water gasification mechanism of coal

Catalytic supercritical water gasification (SCWG) for H₂ production is a hopeful way of coal conversion to replace the traditional coal utilization mode. At present, the detailed catalytic mechanism in the process remains unknown. Herein, a comprehensive catalytic SCWG mechanism of coal is proposed by establishing a novel catalytic kinetic model. It shows that catalysts (K₂CO₃) break up the coal matrix by a cyclic redox reaction to produce plenty of mesopores, accelerating steam reforming of fixed carbon and coal pyrolysis. Water-gas shift reaction is facilitated by K₂CO₃ via formation of formate, which then promotes steam reforming of CH₄ at high temperature (≥700 °C) due to the decreasing CO. The proposed mechanism provides important insights in catalytic SCWG process of coal.     

Development and validation of a Ni-based catalyst for carbon dioxide dry reforming of methane process coupled to solid oxide fuel cells

Recent studies propose dry reforming as a potential alternative to steam reforming. A number of advantages come mainly from the substitution of steam with CO₂, representing a potential strategy for CO₂ and waste heat reuse in both carbon-intensive industry (e.g. steel) and power generation applications (e.g. dry reforming coupling to solid oxide fuel cells).The objective of this study is the development, by means of an ultrasound assisted synthesis technique, of a novel 15%Ni -6%ZrO₂ –3%CaO -Al₂O₃ catalyst with high surface area and metal dispersion, to achieve high values of methane conversion and stable performance, obtained by significantly limiting carbon deposition at temperature in the range 700–750 °C. In this range, compatible with the dry reformer-SOFC thermal integration, conventional catalysts seriously suffer from coking tolerance issues.The catalyst exhibited very promising results with high methane conversion rates of 93% at 750 °C and 1.25 CO₂/CH₄ ratio at the reactor inlet (dilution: in SiC 4:1 in volume), stable over 450 h of operation, with no significant changes in outlet gas composition and relevant modifications on material structure as revealed by SEM/EDX, XRD and Raman, analysis.     

Biogas steam reformer for hydrogen production: Evaluation of the reformer prototype and catalysts

This work aims to investigate a biogas steam reforming prototype performance for hydrogen production by mass spectrometry and gas chromatography analyses of catalysts and products of the reform. It was found that 7.4% Ni/NiAl₂O₄/γ-Al₂O₃ with aluminate layer and 3.1% Ru/γ-Al₂O₃ were effective as catalysts, given that they showed high CH₄ conversion, CO and H₂ selectivity, resistance to carbon deposition, and low activity loss. The effect of CH₄:CO₂ ratio revealed that both catalysts have the same behavior. An increase in CO₂ concentration resulted in a decrease in H₂/CO ratio from 2.9 to 2.4 for the Ni catalyst at 850 °C, and from 3 to 2.4 for the Ru catalyst at 700 °C. In conclusion, optimal performance has been achieved in a CH₄:CO₂ ratio of 1.5:1. H₂ yield was 60% for both catalysts at their respective operating temperature. Prototype dimensions and catalysts preparation and characterization are also presented.     

Continuous sorption-enhanced steam reforming of glycerol to high-purity hydrogen production

In this study, the continuous sorption-enhanced steam reforming of glycerol to high-purity hydrogen production by a simultaneous flow concept of catalyst and sorbent for reaction and regeneration using two moving-bed reactors has been evaluated experimentally. A Ni-based catalyst (NiO/NiAl₂O₄) and a lime sorbent (CaO) were used for glycerol steam reforming with and without in-situ CO₂ removal at 500 °C and 600 °C. The simultaneous regeneration of catalyst and sorbent was carried out with the mixture gas of N₂ and steam at 900 °C. The product gases were measured by a GC gas analyzer. It is obvious that the amounts of CO₂, CO and CH₄ were reduced in the sorption-enhanced steam reforming of glycerol, and the H₂ concentration is greatly increased in the pre-CO₂ breakthrough periods within 10 min both 500 °C and 600 °C. The extended time of operation for high-purity hydrogen production and CO₂ capture was obtained by the continuous sorption-enhanced steam reforming of glycerol. High-purity H₂ products of 93.9% and 96.1% were produced at 500 °C and 600 °C and very small amounts of CO₂, CH₄ and CO were formed. The decay in activity during the continuous reaction-regeneration of catalyst and sorbent was not observed.     

Hydrogen production for fuel cells through methane reforming at low temperatures

Hydrogen production for fuel cells through methane (CH₄) reforming at low temperatures has been investigated both thermodynamically and experimentally. From the thermodynamic equilibrium analysis, it is concluded that steam reforming of CH₄ (SRM) at low pressure and a high steam-to-CH₄ ratio can be achieved without significant loss of hydrogen yield at a low temperature such as 550 °C. A scheme for the production of hydrogen for fuel cells at low temperatures by burning the unconverted CH₄ to supply the heat for SRM is proposed and the calculated value of the heat-balanced temperature is 548 °C. SRM with and/or without the presence of oxygen at low temperatures is experimentally investigated over a Ni/Ce–ZrO₂/θ-Al₂O₃ catalyst. The catalyst shows high activity and stability towards SRM at temperatures from 400 to 650 °C. The effects of O₂:CH₄ and H₂O:CH₄ ratios on the conversion of CH₄, the hydrogen yield, the selectivity for carbon monoxide, and the H₂:CO ratio are investigated at 650 °C with a constant CH₄ space velocity. Results indicate that CH₄ conversion increases significantly with increasing O₂:CH₄ or H₂O:CH₄ ratio, and the hydrogen content in dry tail gas increases with the H₂O:CH₄ ratio.     

Hydrogen production via steam reforming of coke oven gas enhanced by steel slag-derived CaO

Steel slag, a waste from steelmaking plant, has been proven to be good candidate resources for low-cost calcium-based CO₂ sorbent derivation. In this work, a cheap and sintering-resistance CaO-based sorbent (CaO (SS)) was prepared from low cost waste steel slag and was applied to enhance catalytic steam reforming of coke oven gas for production of high-purity hydrogen. This steel slag-derived CaO possessed a high and stable CO₂ capture capacity of about 0.48 g CO₂/g sorbent after 35 adsorption/desorption cycles, which was mainly ascribed to the mesoporous structure and the presence of MgO and Fe₂O₃. Product gas containing 95.8 vol% H₂ and 1.4 vol% CO, with a CH₄ conversion of 91.3% was achieved at 600 °C by steam reforming of COG enhanced by CaO (SS). Although high temperature was beneficial for methane conversion, CH₄ conversion was remarkably increased at lower operation temperatures with the promotion effects from CaO (SS), and CO selectivity has been also greatly decreased. Reducing WHSV could increase methane conversion and reduce CO selectivity due to longer reactants residence time. Reducing C/A could increase methane conversion and hydrogen recovery factor, and also decrease CO selectivity. When being mixed with catalyst during SE-SRCOG, CaO (SS) with a uniform size distribution favored methane conversion due to the high utilization efficiency of catalyst. Promising stability of CaO (SS) in cyclic reforming/calcination tests was evidenced with a hydrogen recovery factor >2.1 and CH₄ conversion of 82.5% at 600 °C after 10 cycles using CaO (SS) as sorbent.     

Structural design of self-thermal methanol steam reforming microreactor with porous combustion reaction support for hydrogen production

To replace the traditional electric heating mode and increase methanol steam reforming reaction performance in hydrogen production, methanol catalytic combustion was proposed as heat-supply mode for methanol steam reforming microreactor. In this study, the methanol catalytic combustion microreactor and self-thermal methanol steam reforming microreactor for hydrogen production were developed. Furthermore, the catalytic combustion reaction supports with different structures were designed. It was found that the developed self-thermal methanol steam reforming microreactor had better reaction performance. Compared with A-type, the △T_max of C-type porous reaction support was decreased by 24.4 °C under 1.3 mL/min methanol injection rate. Moreover, methanol conversion and H₂ flow rate of the self-thermal methanol steam reforming microreactor with C-type porous reaction support were increased by 15.2% under 10 mL/h methanol-water mixture injection rate and 340 °C self-thermal temperature. Meanwhile, the CO selectivity was decreased by 4.1%. This work provides a new structural design of the self-thermal methanol steam reforming microreactor for hydrogen production for the fuel cell.     

Biogas upgrade to syn-gas (H2-CO) via dry and oxidative reforming

Fuel reforming processes are primarily used to generate hydrogen for fuel cells and in automotive internal combustion engines to improve combustion characteristics and emissions. In this study, biogas is used as the fuel source for the reforming process as it has desirable properties of being both renewable and clean. Two reforming processes (dry reforming and combined dry/oxidative reforming) are studied. Both processes are affected by the gas stream temperature and reactor space velocity with the second process being affected by O₂/CH₄ ratio as well. Our results imply that oxidative reforming is the dominant process at low exhaust temperatures. This provides heat for the dry reforming of biogas and the overall reforming is exothermic. Increase in O₂/CH₄ ratio at low temperature promotes hydrogen production. At high exhaust temperatures (>600 °C), dry reforming of biogas is dominant and the overall reaction is net endothermic.     

A thermodynamic analysis of biogas partial oxidation to synthesis gas with emphasis on soot formation

A thermodynamic analysis of synthesis gas production via partial oxidation (POX) of biogas is performed in the present article. Chemical equilibrium calculations are conducted for partial oxidation of (CH₄+CO₂) mixtures based on Gibbs free energy minimization method emphasizing soot formation. Regarding precise evaluation of carbon dioxide effects on the reforming characteristics, the obtained results are compared with the experimental data. Furthermore, the effects of steam injection at the inlet of the reformer on the coking behavior and syngas production yield are studied. To investigate the effects of the equivalence ratio (?), temperature and pressure, a broad parametric study is performed. The results reveal that the process temperature plays a pivotal role in enhancing the syngas production and soot abatement. It is also found that the pressure has an impractical effect on the syngas production yield, leading to the soot formation and decrease in both hydrogen and carbon monoxide yields. Furthermore, increasing the inlet CO₂/CH₄ makes the thermal reforming efficiency to rise at an equivalence ratio lower than 3. Meanwhile, increasing the steam to methane (S/C) ratio reduces carbon formation and enhances hydrogen production. Nonetheless, when the S/C ratio is larger than 2 at ? = 2.5 and 1 at ? = 3, the enhancement of hydrogen generation is minimized and even tends to become impractical. Therefore, near adiabatic and atmospheric condition at ? = 2.5–3 with S/C < 1 are recommended as the optimum operating routes for partial oxidation of biogas.