Combination of Langmuir-Hinshelwood-Hougen-Watson and microkinetic approaches for simulation of biogas dry reforming over a platinum-rhodium alumina catalyst

Dry reforming of CH₄ on a platinum-rhodium alumina catalyst is selected to numerically investigate biogas reforming process. Langmuir-Hinshelwood-Hougen-Watson (LHHW) rate expressions for dry reforming and reverse water-gas shift reactions are presented. Activation energies are estimated by combining microkinetics with the theory of unity bond index-quadratic exponential potential (UBI-QEP). Pre-exponential factors are initially obtained by using the transition state theory (TST) and optimised, later, by minimising errors between modelling and experimental data. Adsorption of CH₄ on the catalyst surface is found to be the rate determining step in the range of relatively low temperature (600–770 °C), while at relatively high temperature (770–950 °C) the thermal cracking of adsorbed CH₄ is the rate controlling step. Small effect of reverse water-gas shift reaction results in the ratio of H₂ to CO produced less than unity for all operating conditions. The simulation shows that the dry reforming process proceeds with reaction rate far from equilibrium state. The presented mechanism is capable of predicting the dependence of biogas dry reforming activities (e.g., reactant conversions, product formations, H₂ to CO ratio, and temperature profile inside the catalyst) on operating conditions (e.g., inlet temperature, heat supplied through the catalyst wall, and composition of biogas at inlet).     

Exergy analysis of hydrogen production via biogas dry reforming

Among the alternative pathways for hydrogen production, the use of biogas from organic waste via dry reforming of methane (DRM), water gas shift reaction and pressure swing adsorption (PSA) is often seen as an interesting option. In this work, the thermodynamic performance of this type of biohydrogen energy system –additionally including a combined-cycle scheme that satisfies the electricity and steam requirements of the process– is evaluated through exergy analysis. The main data needed for the analysis are acquired from a predictive simulation model implemented in Aspen Plus^®. The system shows an exergetic efficiency of 55%, with the DRM and the power generation subsystems arising as the main sources of irreversibility. Furthermore, given the significant influence found for the PSA off-gas on the thermodynamic performance of the system, two alternative process configurations based on the use of this stream are evaluated. In this regard, full recirculation of the PSA off-gas to the DRM reactor is found to improve the system's exergetic performance.     

Durability of a Ni based monolithic catalyst in the autothermal reforming of biogas

A Ni based catalyst supported on a cordierite monolithic substrate was applied to the autothermal reforming (ATR) of biogas to produce hydrogen. When the feed rates of oxygen and steam were constant, the Steam/CH₄ (S/CH₄) and O₂/CH₄ ratios changed because of an increase or decrease in the methane concentration of the biogas. The concentration of methane in the biogas fluctuates roughly between 35% and 65% according to factors such as the properties or amount of the waste. Therefore, the effect of S/CH₄ and O₂/CH₄ ratios on catalyst durability was confirmed by using actual biogas, which was produced by anaerobic fermentation of biomass at the biogasification bench-scale plant in Kyoto. Reforming reactions were carried out at ratios of S/CH₄ = 0–4, O₂/CH₄ = 0.5 and at S/CH₄ = 2, O₂/CH₄ = 0.6. The S/CH₄ range of 0–2.0 and the O₂/CH₄ range of 0.5–0.6 had no effect on the catalyst durability and a S/CH₄ ratio of more than 3.0 led to decreased catalytic performance.     

Utilizing carbon dioxide as a regenerative agent in methane dry reforming to improve hydrogen production and catalyst activity and longevity

The study evaluates the effect of forced periodic cycling between methane dry reforming and carbon regeneration using a gasifying agent, such as carbon dioxide. The activity of Ce-promoted Ni–C_O/Al₂O₃ catalyst was evaluated in a methane dry reforming process using a fixed-bed reactor under steady-state and periodic operation. Forced cycling reactions (reforming and regeneration) were conducted by manipulating the reactor feed between methane dry reforming and catalyst gasification using CO₂ at cycle periods of 10, 20, and 30 min, and cycle splits of 0.8, 0.6, and 0.4. The physicochemical properties of fresh and spent catalysts were evaluated using several characterization techniques, such as the BET surface area, H₂-chemisorption, and XRD. The results confirmed that methane dry reforming under periodic cycling provides an opportunity to improve methane conversion and increase the catalyst activity and longevity because of the periodic interruption of coke deposition. In particular, methane conversion deteriorated from 68% to 37% under steady-state within five hours of reforming, whereas a modest decrease in methane conversion (from 68% to 63% for a cycle period of 10 min and cycle split 0.8) was observed under periodic operation conditions. The results of catalyst characterization also demonstrated that the on-line removal of carbon during CO₂ regeneration did not lead to any structural effect on the catalyst properties, and it absolutely restored the catalyst properties up to the values measured for the fresh catalyst.     

Deactivation and regeneration of Ni catalyst during steam reforming of model biogas: An experimental investigation

This paper presents detailed study of biogas reforming. Model biogas with different levels of H₂S is subjected to reforming reaction over supported Ni catalyst in a fixed bed reactor at 700 °C and 800 °C. In order to understand the poisoning effects of H₂S the reactions have been initially carried out without H₂S in the feed stream. Three different H₂S concentrations (20, 50 and 100 ppm) have been considered in the study. The H₂O to CH₄ ratio is maintained in such as way that CO₂ also participates in the reforming reaction. After performing the poisoning studies, regeneration of the catalyst has been studied using three different techniques i) removal of H₂S from the feed stream ii) temperature enhancement and iii) steam treatment. Poisoning at low temperature is not recoverable just by removal of H₂S from the feed stream. However, poisoning at high temperature is easily reversed just by removal of H₂S from the feed stream. Unlike some previous reports by Li et al. (2010) and Rostrup-nielsen (1971) [1,2], catalyst regeneration is achieved in shorter time frames for all the regeneration techniques attempted.     

Syngas production via the biogas dry reforming reaction over Ni supported on zirconia modified with CeO2 or La2O3 catalysts

The catalytic efficiency and bench scale time on steam stability of Ni dispersed on three commercially available catalytic supports (ZrO₂, La₂O₃–ZrO₂ and CeO₂–ZrO₂) has been studied for the dry reforming of methane (DRM) in the temperature range of 500–800 °C and a CH₄/CO₂ ratio equal to 1.5, simulating typical biogas quality. Ni supported on LaZr and CeZr carriers that obeyed enhanced basicity and oxygen ion lability values than Zr, exhibited superior catalytic efficiency and stability. A variety of techniques, namely N₂ physisorption-desorption (BET method), powder X-ray diffraction (XRD), hydrogen temperature programmed reduction (H₂-TPR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, potentiometric titration and inductively coupled plasma emission spectroscopy (ICP), were applied for the characterization of particles morphology, textural, structural and other physical properties of the materials, as well as the type of carbon deposited on the catalytic surface after exposure to DRM reaction conditions. Post-reaction analysis of the deposited carbon on the catalysts surfaces showed that the prominent trend of the carbon deposits on the Ni/Zr and Ni/LaZr samples was to have a filamentous tube like morphology (graphite-2H). In contrast, on the Ni/CeZr used catalyst, the formation of small amount of carbon tube-like architectures was detected. The enhanced basicity and Ni dispersion of the Ni/LaZr and Ni/CeZr samples as well as the high oxygen ion lability of the lattice oxygen in the latter, were considered to be the major factors involved in the superior efficiency and durability of these samples in comparison to Ni/Zr sample.     

Dry reforming of biogas in fluidized bed: Process intensification

Biogas is a renewable resource obtained mainly from the anaerobic fermentation of agro-industrial and anthropogenic residues. The production of hydrogen by dry reforming of methane represents a potential application for this renewable energy carrier. This could play a positive contribution towards meeting the challenge of providing a global supply of energetically sustainable and environmentally friendly energy. This work combines a catalytic reaction, a separation and the catalyst regeneration in a single reactor. To this end, a two zone fluidized bed reactor (TZFBR) with hydrogen selective membranes has been employed (TZFBR + MB). The operating conditions for the process of dry reforming of biogas have been optimized experimentally, both in TZFBR and TZFBR + MB. Several catalysts were prepared (Ni/Al₂O₃, NiCe/Al₂O₃, NiCo/Al₂O₃), characterized and tested in reactions in both TZFBR and in TZFBR + MB. Finally, the influence of using oxygen or carbon dioxide as regenerating gases in the process has been studied. Experimental results show the feasibility of using CO₂ for in situ catalyst regeneration, avoiding the potential problems associated with the use of O₂.     

Excess-methane dry and oxidative reforming on Ni-containing hydrotalcite-derived catalysts for biogas upgrading into synthesis gas

The activity of Ni-containing hydrotalcite-derived catalysts was assayed in the excess-methane dry reforming of different CH₄-CO₂ mixtures, aiming to simulate biogas upgrading to hydrogen and/or syngas. These catalysts yielded methane conversions quite far away from the thermodynamically predicted values, pointing to the inhibition of important methane consuming reactions, such as direct methane decomposition (DMD). Adding oxygen to the gas mixture (12.5%) results in increased methane conversions. Almost constant H₂/CO ratios, around 1.5, were measured at any temperature (600–850 °C). However, solid carbon formation was found to take place to a higher extent. The intrinsic properties of the hydrotalcite-derived catalysts tested results in favored reverse water gas shift reaction, leading to CO₂ and H₂ conversion.     

An experimental and theoretical approach for the biogas steam reforming reaction

An experimental and theoretical study for the biogas steam reforming reaction over 5%Ru/Al₂O₃ catalyst have been performed. An apparatus was constructed for the conduction of the experiments, the core of which was a tube reactor, filled with the catalyst in form of pellets. The inlet gas mixture consisted of CH₄ and CO₂ in various composition ratios as a model biogas and steam. A theoretical model of the process was developed. The experimental reactor was modelled as an isothermal pseudo homogeneous fixed bed reactor. Internal and external transport phenomena were neglected and appropriate effectiveness factors were employed instead. A physical properties model was used for the calculation of the physicochemical properties of the real mixture. Five reactant species, CH₄, CO₂, H₂O, CO and H₂, were included in the model, whereas the feed consisted of the first three. Steam reforming and water gas shift were the main reactions. Experimental results and theoretical predictions match closely, stability of the catalyst was assured and an optimal operational window was identified, at GHSV = 10,000–20,000 h⁻¹, T = 700–800 °C, CH₄/CO₂ = 1.0–1.5 and H₂O/CH₄ = 3.0–5.0.     

Effect of substitution by Ni in MgAl2O4 spinel for biogas dry reforming

Mesoporous nanocrystalline Mg_1-xNi_xAl₂O₄ (x = 0.10, 0.13, 0.17 and 0.20) with large surface area were synthesized via a simple one-step sol-gel method using nonprecious metals. The prepared Mg_1-xNi_xAl₂O₄ catalysts exhibit good catalytic performance towards methane and carbon dioxide dry reforming reaction. The catalysts were evaluated by various techniques, including XRD, BET, TPR, TPO, EPR, Chemisorption, SEM and TEM. All the Ni incorporated MgAl₂O₄ samples possessed high BET area (296–305 m² g^?1) and pore volume (0.47–0.56 cm³ g^?1) with small pore size (6.4–7.4 nm) in meso region after calcination at 700 °C. The TPR results suggested strong interaction effect in NiMg and the reducibility property of the catalysts improved with the increase of nickel doping. Mg_0.8Ni_0.2Al₂O₄ exhibited the highest activity for biogas dry reforming with 72.6% CH₄ and 80.7% CO₂ conversion at 700 °C. Electron paramagnetic resonance (EPR) results indicated that the incorporation of Ni in MgAl₂O₄ spinel lattice led to the lattice distortion and formed oxygen vacancies which are a benefit for the dry reforming reaction.     

Influence of the operating parameters over dry reforming of methane to syngas

The influence of operating parameters over dry reforming of methane reaction was evaluated using a Ni-based catalyst obtained after calcination of a hydrotalcite-like precursor. The studied variables were mass to flow ratio (W/F), reaction temperature and CO₂/CH₄ ratio. Maximum methane and carbon dioxide conversions were achieved at W/F ratios above 0.21 g h L⁻¹. The higher the W/F ratio was, the lower amount of water was formed, which led to a higher H₂/CO ratio. The increase in reaction temperature produced an increase in conversions. Water concentration in the outlet stream showed a maximum at 600 °C. At this temperature, reverse water–gas-shift reaction (RWGS) was favoured because it is endothermic. However, steam reforming and carbon gasification were also favoured and they consumed great part of the water produced. CO₂/CH₄ ratios above 1 led to a higher CH₄ conversion but selectivity to hydrogen decreased because RWGS reaction was favoured. When CO₂/CH₄ was below unity, CH₄ conversion decreased but less amount of water was produced so a higher H₂ selectivity was achieved. The catalyst exhibited good stability over dry reforming of methane under all the tested conditions, which may be ascribed to its high basicity. This property improved CO₂ adsorption and then RWGS reaction and carbon gasification.     

Effect of pollutants on biogas steam reforming

This study reports the influence of biogas poisoning on a Ni based catalyst working under steam reforming conditions (atmospheric pressure, T = 1073 K and H₂O/CH₄ = 2 mol/mol). A biogas stream composed by CH₄ and CO₂ with a ratio 55/45 vol.%, added with different chemical species (H₂S, hydrocarbons mixture and D5) as contaminants, was used as inlet gas stream.First, effect of poisoning on Ni catalyst were separately evaluated and the boundary concentrations for each contaminants were revealed (0.4 ppm, 200 ppm and 0.5 ppm for H₂S, hydrocarbons and D5 respectively) to assure Ni stable performances on time on stream (100 h at 50,000 h^?1 of GHSV). Successively, a comparison between Ni catalytic behaviors in presence of two combined poisoning in the biogas (H₂S + Hydrocarbons and Hydrocarbons + D5) was carried out.It was found that the effect of combined poisoning, even though it considered in moderate concentration, is harmful for Ni catalyst activity. Methane conversion on time on stream was reduced from 86% to 40% after 50 h, when the couple of poisoning Hydrocarbons + D5 was added to the inlet gas stream, while a lower deactivation pattern (about 73%) was leaded by couple H₂S + Hydrocarbons. Both poisoning mixtures promoted coke deposition on Ni catalyst surface (about ≥0.5 mgC/g_cat·h) independently by poisoning chemical characteristics probably due to adsorption/deposition of contaminants on catalytic sites.     

Internal reforming SOFC running on biogas

Direct feeding of biogas to SOFC, which is derived from municipal organic wastes, has been investigated as a carbon-neutral renewable energy system. CH₄/CO₂ ratio in the actual biogas fluctuated between 1.4 and 1.9 indicating biogas composition is strongly affected by the kinds of organic wastes and the operational conditions of methane fermentation. Using anode-supported button cells, stable operation of biogas-fueled SOFC was achieved with the internal reforming mode at 800 °C. Cell voltage above 0.8 V was recorded over 800 h at 200 mA cm⁻². It has been revealed that air addition to actual biogas reduced the risk of carbon formation and led to more stable operation without compromising cell voltage due to the lowering of anodic overvoltage.     

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.     

Design and optimization of reforming hydrogen production reaction system for automobile fuel cell

Mathematical modeling and simulation analysis of the dimethyl ether steam reforming reaction system were carried out in the study. The numerical results of simulation and experiment were consistent. The effects of reaction conditions on the conversion of dimethyl ether and hydrogen production were analyzed. The internal structure of the reforming reactor was adjusted to obtain higher hydrogen production efficiency. The study established the reforming hydrogen production industry system, and analyzed the thermal efficiency of the system. The results show that when the temperature of the conversion bed is 673 K, the inlet flow rate of the mixture gas is 0.5 ms^?1 and the ratio of water to ether is 3, the dimethyl ether steam reforming reaction system could obtain the dimethyl ether conversion rate of 90%, the hydrogen production rate of 88% and system thermal efficiency of 74%.     

Syngas production from methane dry reforming over Ni/SBA-15 catalyst: Effect of operating parameters

The influence of operating conditions including reactant partial pressure and reaction temperature on the catalytic performance of 10%Ni/SBA-15 catalyst for methane dry reforming (MDR) reaction has been investigated in this study. MDR reaction was carried out under atmospheric pressure at varying CH₄/CO₂ volume ratios of 3:1 to 1:3 and 923–1023 K in a tubular fixed-bed reactor. SBA-15 supported Ni catalyst exhibited high specific surface area of 444.96 m² g^?1 and NiO phase with average crystallite size of 27 nm was detected on catalyst surface by X-ray diffraction and Raman measurements. H₂ temperature-programmed reaction shows that NiO particles were reduced to metallic Ni⁰ phase with degree of reduction of about 90.1% and the reduction temperature depended on the extent of metal-support interaction and confinement effect of mesoporous silica support. Catalytic activity appeared to be stable for 4 h on-stream at 973–1023 K whilst a slight drop in activity was observed at 923 K probably due to deposited carbon formed by thermodynamically favored CH₄ decomposition reaction. Both CH₄ and CO₂ conversions increased with rising reaction temperature and reaching about 91% and 94%, respectively at 1023 K with CO₂ and CH₄ partial pressure of 20 kPa. CH₄ conversion improved with increasing CO₂ partial pressure, ${\mathit{P}}_{\mathit{C}{\mathit{O}}_{\mathit{2}}}$ and exhibited an optimum at ${\mathit{P}}_{\mathit{C}{\mathit{O}}_{\mathit{2}}}$ of 30–50 kPa depending on reaction temperature whilst a substantial decline in CO₂ conversion was observed with growing ${\mathit{P}}_{\mathit{C}{\mathit{O}}_{\mathit{2}}}$. Additionally, CH₄ and CO₂ conversions decreased significantly with rising CH₄ partial pressure because of increasing carbon formation rate via CH₄ cracking in CH₄-rich feed. Post-reaction characterization shows that active Ni metal phase was not re-oxidized to inactive metal oxide during MDR reaction. The heterogeneous nature of deposited carbons including carbon nanofilament and graphite was detected on catalyst surface by Raman measurement.     

A review on reforming bio-ethanol for hydrogen production

Bio-ethanol is a prosperous renewable energy carrier mainly produced from biomass fermentation. Reforming of bio-ethanol provides a promising method for hydrogen production from renewable resources. Besides operating conditions, the use of catalysts plays a crucial role in hydrogen production through ethanol reforming. Rh and Ni are so far the best and the most commonly used catalysts for ethanol steam reforming towards hydrogen production. The selection of proper support for catalyst and the methods of catalyst preparation significantly affect the activity of catalysts. In terms of hydrogen production and long-term stability, MgO, ZnO, _CeO2${\mathrm{CeO}}_2$, and _La2O3${\mathrm{La}}_2{\mathrm{O}}_3$ are suitable supports for Rh and Ni due to their basic characteristics, which favor ethanol dehydrogenation but inhibit dehydration. As Rh and Ni are inactive for water gas shift reaction (WGSR), the development of bimetallic catalysts, alloy catalysts, and double-bed reactors is promising to enhance hydrogen production and long-term catalyst stability. Autothermal reforming of bio-ethanol has the advantages of lesser external heat input and long-term stability. Its overall efficiency needs to be further enhanced, as part of the ethanol feedstock is used to provide low-grade thermal energy. Development of millisecond-contact time reactor provides a low-cost and effective way to reform bio-ethanol and hydrocarbons for fuel upgrading. Despite its early R&D stage, bio-ethanol reforming for hydrogen production shows promises for its future fuel cell applications.     

Methane dry reforming using oil palm shell activated carbon supported cobalt catalyst: Multi-response optimization

Dry reforming of methane with carbon dioxide was investigated using oil palm shell activated carbon (OPS-AC) supported cobalt catalyst. The cobalt loaded OPS-AC catalysts were prepared by wet-impregnation method and characterized using SEM, FESEM, BET, TPR and TPD. Surface morphology of OPS-AC supported cobalt catalysts exhibited higher porosity, surface area and micropore volume with different densities of cobalt particles and support. Furthermore, greater amount of H₂ chemisorbed and acidity were observed with increasing cobalt contents. Response surface methodology (RSM) was employed to design the experiments based on factorial central composite design. Catalytic testing was performed using a micro reactor system by varying four variables: temperature, gauge pressure, CH₄/ CO₂ ratio and gas hourly specific velocity (GHSV). H₂ and CO yields were analyzed and quantified by gas chromatography with thermal conductivity detector (TCD). Both responses (H₂ and CO) yields were optimized simultaneously using desirability function analysis. Reaction temperature was the most influential variable with high desirability prevalent for both responses. The optimum response values of H₂ and CO yields corresponded to 903 °C, 0.88 bar(g), CH₄/ CO₂ = 1.31 and GHSV = 4,488 mL/h.g-catalyst.     

Biogas reforming for hydrogen enrichment by ceria decorated over nickel catalyst supported on titania and alumina

Catalytic dry reforming of biogas for hydrogen enrichment was studied over cerium oxide promoted nickel catalysts supported on titanium dioxide and aluminium oxide. The catalysts were prepared by wet impregnation method and characterized by H₂-TPR, XRD, BET and FESEM techniques. Their catalytic performance in the biogas dry reforming reaction was studied at temperature ranges from 650 to 850 °C, with a CH₄/CO₂ ratio of 1.5:1. The H₂-TPR results revealed that 11 wt % Ni impregnation on TiO₂ support makes the catalyst with strong metal-support interaction which moderates the metal sintering. Also, the addition of CeO₂ effectively improved the CH₄ and CO₂ conversions as well as H₂ enrichment. At 850 °C, 11 wt % Ni/TiO₂ catalyst leads to 70.5% CH₄ conversion with 32.0% H₂ enrichment, whereas, Ni_0·11/Ce_0.20 (Al₂O₃TiO₂) yielded high CH₄ conversion (84.9%) with 40.6% of H₂ enrichment. No significant change in the activity of the catalyst was observed with 8.8 wt % of carbon deposited on the Ni_0·11/Ce_0.20 (Al₂O₃TiO₂) catalyst, after 7 h of continuous reforming. Moreover, under combined (dry and oxidative) reforming of biogas, the stoichiometric H₂/CO ratio (1.2) was observed at 0.47 O₂/CH₄ ratios with negligible carbon deposition. Thus, Ni_0·11/Ce_0.20 (Al₂O₃TiO₂) catalyst exhibited better activity and selectivity with high catalyst stability at 850 °C.     

Experimental study of dry reforming of biogas in a tubular anode-supported solid oxide fuel cell

The performance of a tubular Ni/YSZ anode supported SOFC directly fed by an anaerobic digestion simulated biogas, with an extra addition of carbon dioxide to operate in conservative operating conditions to avoid coking on the anode support, was investigated. The fuel cell has been tested at a fixed oven temperature of 800 °C and under biogas/CO₂ mixtures with different volumetric ratios, fuel utilization (FU) and current densities. Polarization curves and performance maps were obtained to better understand the influence of the investigated operational parameters on the cell behavior. Furthermore, since the tubular geometry enables an easy separation of the anode and cathode exhaust gases, the anode off-gas has been collected and monitored through a gas-chromatograph under open circuit voltage to investigate on the catalytic behavior of a Ni-based state-of-the-art anode. For corresponding operative conditions, performances of the cell for biogas/CO₂ 1/1.5 (i.e. CH₄/CO₂ 30/70) and 1/2 (i.e. CH₄/CO₂ 24/76) were at least 2% and 4% lower than the case 1/1 (i.e. CH₄/CO₂ 20/80), respectively. The highest efficiency of 43.4% was reached at 17.5 A and FU = 70%.