Experimental study of syngas production from methane dry reforming with heat recovery strategy

This study employed the concept of heat recovery to design a set of reformer to facilitate the methane dry reforming (MDR), through which syngas (H₂+CO) could be generated. The MDR involves an endothermic reaction and thus additional energy is required to sustain it. According to the concept of industrial heat recovery, the energy required to facilitate the MDR was recovered from waste heat. In addition, after the reforming reaction, the waste heat inside the reformer was used for internal heat recovery to preheat the reactants (CO₂+CH₄) to reduce the amount of energy required for the reforming reaction. Regarding the parameter settings in the experiments, the CH₄ feed flow rate was set at 1–2.5 NL/min and the mole ratio for CO₂/CH₄ was set at 0.43–1.22. Subsequently, an oven was used to simulate a heat recovery environment to facilitate the dry reforming experiment. The experimental results indicated that an increase in oven temperature could increase the reforming reaction temperature and elevate the energy for the reformer. H₂ and CO production could increase when the reformer gained more energy. The high-temperature gas generated from the reforming reaction was applied to facilitate internal heat recovery of reformer and preheat the reactants; thus, the efficiency of reforming and CO₂ conversion were evidently elevated. The theoretical equilibrium analysis indicated that the thermal efficiency of reforming increased with the increase of CO₂/CH₄ molar ratio. While, the thermal efficiency of reforming by experiments decreased with the increase of the CH₄ feed rate, but increased with the increase of CO₂/CH₄. In summary, the experimental results revealed that the overall H₂ was 0.017–0.019 mol/min. In addition, the reforming efficiency was 8.76%–78.08%, the CO₂ conversion was 53.92%–96.43%, and the maximum thermal efficiency of reforming was 102.3%.     

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.     

Zirconia-supported tungsten oxides for cyclic production of syngas and hydrogen by methane reforming and water splitting

ZrO₂-supported tungsten oxides were used for cyclic production of syngas and hydrogen by methane reforming (reduction) and water splitting (re-oxidation). The reduction characteristics of WO₃ to WO₂ and WO₂ to W were examined at various temperatures (1073–1273 K) and reaction times. Significant portions of the tungsten oxides were also reduced by the produced H₂ and CO. The extent of reduction by H₂ varied greatly depending on temperature and WO₃ content and also on the reduction of either WO₃ or WO₂, while that by CO was consistently low. When the overall degree of reduction became sufficiently high, methane decomposition started to proceed rapidly, resulting in considerable carbon deposition and H₂ production. Consequently, the H₂/(CO + CO₂) ratio varied from around 1 to higher than 2. During the repeated cyclic operations with a proper reduction time at a given temperature, the syngas and hydrogen yields decreased gradually while the H₂/(CO + CO₂) ratio remained nearly constant and the carbon deposition was negligible.     

Syngas production from dry reforming of methane over ni/perlite catalysts: Effect of zirconia and ceria impregnation

Ni catalysts with nominal loadings ranging between 2.5 and 20 wt% were synthesized over perlite by wet impregnation, then filtered, washed and calcined at 500 °C. Chemical analyses performed by MP-AES revealed that the maximum Ni content loaded over perlite corresponded to ～15 wt%. Therefore, for comparison reasons, a Ni(20 wt%)/perlite catalyst was prepared by wetness impregnation without performing any washing treatment. The so prepared catalysts were tested in methane dry reforming without performing any pre-treatment reduction. The catalytic performances were compared by increasing the temperature from 500 up to 800 °C under the reaction mixture composed of 15 vol% CH₄ + 15 vol% CO₂/N₂. Ni(15 wt%)/perlite was the most active catalyst among the series of monometallic samples. The effect of co-impregnating perlite with Ni and Zr or Ni and Ce precursors in order to obtain catalysts with final composition, Ni(15 wt%), 10 and 20 wt% as Zr or Ce, perlite (75 or 65 wt%) was, then, investigated. Characterizations performed by XRD, BET, DRS and H₂-TPR evidenced that the physico-chemical and reduction properties are influenced by the Ni content and by the presence of zirconia and ceria oxides. It is worth of noting the increased reducibility of NiO species promoted by zirconia and ceria addition. The catalytic activity in the dry reforming of methane was also affected by the presence of doping oxides, in terms of enhanced CH₄ and CO₂ conversions and higher H₂/CO atomic ratios. Runs tests at 700 °C for 12 h were carried out and the spent catalysts were analysed by TGA and TEM. Over Ni(15 wt%)/perlite large amount of amorphous carbon grows on the surface blocking the active centres, while zirconia and ceria doping improved the resistance to carbon poisoning favouring growing of filamentous carbon residues in small amount.     

Synthesis, characterization and catalytic performances of Ce-SBA-15 supported nickel catalysts for methane dry reforming to hydrogen and syngas

A series of Ce-incorporated SBA-15 mesoporous materials were synthesized through direct hydrothermal synthesis method and further impregnated with 12 wt.% Ni. The samples were characterized by ICP-AES, XRD, N₂ physisorption, XPS, TPR, H₂ chemisorption, TGA, temperature-programmed hydrogenation (TPH) and TEM measurements. The low-angle XRD and N₂ physisorption results showed the Ce successfully incorporated into the framework of SBA-15. The catalytic properties of these catalysts were investigated in methane reforming with CO₂. The Ce/Si molar ratio had a significant influence on the catalytic performance. The highest catalytic activity and long-term stability were obtained over the Ni/Ce-SBA-15 (Ce/Si = 0.04) sample. The improved catalytic behavior could be attributed to the cerium impact in the framework of SBA-15, where cerium promoted the dispersion of nano-sized Ni species and inhibited the carbon formation. In comparison with the effect of CeO₂ crystallites in SBA-15, cerium in the framework of SBA-15 promoted the formation of the nickel metallic particles with smaller size. The XRD and TGA results exhibited that carbon deposition was responsible for activity loss of Ni/SBA-15 and Ni/Ce-SBA-15 (Ce/Si = 0.06) catalysts. TEM results showed that the hexagonal mesopores of SBA-15 were still kept intact after reaction and the pore walls of SBA-15 prevented the aggregation of nickel.     

Development of nanosilica-based catalyst for syngas production via CO2 reforming of CH4: A review

The alarming global warming issue has sparked interest in researchers to mitigate greenhouse gas emissions via CO₂ reforming of CH₄ (CRM). Regrettably, the main drawback of CRM is catalyst deactivation because of coking and metal sintering. Therefore, exceptional resistance towards coking and sintering is crucial to formulate viable CRM catalysts. This article reviewed the latest development of nanosilica-based catalysts (mesoporous nanosilica, dendritic fibrous nanosilica, green nanosilica, and core@shell nanosilica) for CRM application. The physicochemical properties of nanosilica supports could be modulated by synthesis methods to improve their resistance towards coking and sintering. Furthermore, this review compiled the influence of catalytic properties of nanosilica supported catalysts, such as active metal dispersion, crystallite size, acid-basic properties, oxygen mobility, reducibility, porosity, and morphology on CRM. To conclude, nanosilica supports with strong metal-support interaction, homogeneous metal dispersion, appropriate crystallite size, and moderate acidity/basicity, exhibited satisfactory catalytic activity, thermal stability, and resistance towards coking and sintering. The fundamental study and depth understanding on this catalysis field is of worth in configuring robust catalysts for future industrial applications success of CRM reaction with superb activity and carbon resistance for CRM.     

Synthesis strategies of Zr- and Y-promoted mixed oxides derived from double-layered hydroxides for syngas production via dry reforming of methane

Ni-based Mg/Al double-layered hydroxides, also called hydrotalcites (HTs), were co-precipitated with Zr (5 wt%) and impregnated with Y (0.2, 0.4, 0.6 wt%), and compared to the catalyst co-precipitated with both Y (0.4 wt%) and Zr (5 wt%). Their performance in dry reforming of methane was determined in the temperature range of 850–600 °C and stability tests at 700 °C for 5 h. The materials were characterized by X-ray powder diffraction, X-ray fluorescence, nitrogen adsorption/desorption, H₂-TPR, CO₂-TPD, hydrogen chemisorption, thermogravimetric analysis, transmission electron microscopy, high-resolution transmission electron microscopy, and Raman spectroscopy. A decrease in reducibility and lower total number of basic sites were observed for the sample promoted only with zirconia compared to the unpromoted material. After promotion with yttrium, no formation of ZrO₂–Y₂O₃ solid solution was evident from XRD. The Ni dispersion was decreased due to decoration of the surface with Y species, leading to blockage of available nickel sites. All Zr and Y promoted samples were, however, more active in DRM than unpromoted HTNi. The co-precipitated Zr and Y catalyst (HTNi-ZrY0.4-cop) exhibited increasing conversion over time, and a H₂/CO close to 1 in the isothermal test at 700 °C. H₂-TPSR on the spent catalysts revealed that the promotion with yttrium favored regeneration of the catalytic bed, consuming the majority of removable coke and decreasing the formation of unreactive coke.     

Biogas reforming over La-promoted Ni/SBA-16 catalyst for syngas production: Catalytic structure and process activity investigation

Biogas, a mixture of CO₂/CH₄, is reasonable for conversion to syngas (H₂/CO) by dry methane reforming (DMR) reaction. The modification of Ni/SBA-16 with a lanthanum promoter using the co-impregnation technique is investigated in this study. The temperature of reaction (600–750 °C), La loading (3.85–11.56 wt%), and Ni loading (10–30 wt%) are the parameters that are varied for maximizing reaction conversions. The synthesized catalysts and SBA-16 supporting material were characterized by several methods before and after reaction. According to the analysis, the existence of La₂O₃ particles on the catalyst's surface has decreased the particle sizes, as well as enhanced their dispersion. Therefore, the maximum CH₄ conversion of 94.21%, CO₂ conversion of 90.12%, H₂ yield of 90.53%, and H₂/CO molar ratio of 2.03 are achieved using 20Ni-5.78La/SBA16 at 700 °C. Besides, this catalyst showed lower deposited coke and higher stability compared with other synthesized catalysts.     

Recent advances in biogas upgrading to value added products: A review

It is undeniable that oil and gas explorations are going on at a frantic pace due to excessive fossil fuel usage across the world. This has compelled us to explore isolated or even uninhabited places to meet the surging demand for oil and gas. There is no doubt that scientists and researchers worldwide are exploring more renewable energy sources to produce value-added products. In the last few years, biogas' usage as a reactant gas in the catalytic reforming process has emanated as an energy carrier to produce energy-efficient products, i.e., syngas and methanol. This review aimed to analyze the research works focusing on the biogas DR reactions and methanol production from biogas. The findings of some experimental studies have been presented in the form of graphs for important selective parameters as case studies. The overall impression from the review suggests that the performance of the reforming catalysts deteriorates regarding different operating conditions. Still, the improvement in syngas production has been reported by neglecting the effect of H₂S impurity. Furthermore, various parameters have been discussed paragraphically to evaluate the catalytic performance in biogas dry reforming reactions and a check on catalyst synthesis methods. After that, a few scattered studies have been discussed on methanol synthesis using biogas as a feedstock.     

Recent experimental advances on the utilization of biochar as a tar reforming catalyst: A review

Biomass gasification to form syngas is a promising renewable energy production process. Here, biomass is exposed to high temperatures in an oxygen-controlled environment where volatiles react to form components of syngas that can be used for energy or chemical production. A limitation to the use of gasification is the generation of tars that condense in downstream equipment causing damage and halting production. Currently tars are removed by physical, thermal, or catalytic processes, all high-cost options. On the other hand, biochar is produced as a solid by-product of gasification, characterized by high surface area, desirable adsorption properties, and relatively low cost. This review details the use of biochar as a catalyst to reform tars, while highlighting recent experimental advances in evaluating the effects of biomass composition, gasification conditions, and pre-treatment and post-treatment options to improve catalytic function. It discusses tar degradation mechanisms and catalyst deactivation and recommends further areas for research.     

A review on anode on-cell catalyst reforming layer for direct methane solid oxide fuel cells

The commercialization of solid oxide fuel cells (SOFCs) can be significantly promoted with the direct utilization of methane, which is the primary component in natural gas and the second most abundant anthropogenic greenhouse gas. However, carbon deposition on most commonly used Ni-based anode is the bottle-necking issue inhibiting long-term stability of direct methane SOFCs. To avoid such a problem, methane is typically reformed (internally or externally) in SOFCs. Considering the cost, system simplification, coking resistance, and material selection, the on-cell catalytic reforming layer (OCRL) is one of the most promising designs for direct methane SOFCs. Reforming catalytic materials are typically consisted of active component, substrate and catalytic promoter, all of which have a significant impact on the catalytic activity, sintering resistance and coking resistance of methane reforming catalysts. This review summarizes the influence of the various components, some common OCRL materials and their applications in direct methane SOFCs, reforming and coking resistance mechanism, as well as the remaining challenges. The effective utilization of OCRL plays a pivotal role in promoting the development of direct methane SOFCs and the commercialization of SOFCs.     

A novel approach to improve the mathematical modelling of the internal reforming process for solid oxide fuel cells using the orthogonal least squares method

This paper presents a novel approach to experimental and numerical investigations of the methane/steam reforming reaction process over a nickel/yttria-stabilized zirconia fine powder catalyst. Methane/steam reforming is primarily considered as a hydrogen production process for Solid Oxide Fuel Cells, and therefore its reaction kinetic was investigated experimentally and numerically. The present paper describes the innovative implementation of an orthogonal least squares (generalized least squares: GLS) algorithm for the calculation of the reaction kinetics involving precise information and the uncertainties of the obtained results. The GLS method was applied to evaluate the reaction rate and therefore fractional conversion of methane. An analysis of the mathematical model points out that the experimental inaccuracy could be reduced and allowed for the calculation of the most probable values of kinetic parameters and their uncertainties. The GLS method secures a higher accuracy of measured data and estimates the most probable value of all model parameters.     

Sustainable hydrogen production for fuel cells by steam reforming of ethylene glycol: A consideration of reaction thermodynamics

The use of renewable biomass, such as ethylene glycol (EG), for hydrogen production offers a more sustainable system compared to natural gas and petroleum reforming. For the first time, the reaction thermodynamics of steam reforming and sorption enhanced steam reforming of EG have been investigated. Gibbs free energy minimization method was used to study the effect of pressure (1-5 atm), temperature (500-1100 K) and water to EG ratio (WER 0-8) on the production of hydrogen and the formation of associated by-products (CH₄, CO₂, CO, C). The results suggest that hydrogen production is optimum when steam reforming occurs at atmospheric pressure, 925 K and with a WER of 8. Moreover, working at high temperature (>900 K) and with a WER above 6 inhibits almost entirely the production of methane and carbon. The main source of hydrogen in the system is found to be steam reforming of methane and water gas shift reaction by the analysis of the response reactions (RERs). Hydrogen production is governed by the former reaction at low temperatures while the latter one comes into prominence as temperature increases. By coupling with in situ CO₂ capture using CaO, the formation of CO₂ and CO can be avoided and high purity of hydrogen (>99%) can be achieved.     

Recent advances in catalyst-enhanced LiAlH4 for solid-state hydrogen storage: A review

LiAlH₄ is regarded as a potential material for solid-state hydrogen storage because of its high hydrogen content (10.5 wt%). However, its high decomposition temperature, slow dehydrogenation kinetics and irreversibility under moderate condition hamper its wider applications. Mechanical milling treatment and doping with a catalyst or additive has drawn significant ways to improve hydrogen storage properties of LiAlH₄. Microstructure or nanostructure materials were developed by using a ball milling technique and doping with various types of catalysts or additives which had dramatically improved the efficiency of LiAlH₄. However, the state-of-the-art technologies is still far from meeting the expected goal for the applications. In this paper, the overview of the recent advances in catalyst-enhanced LiAlH₄ for solid-state hydrogen storage is detailed. The remaining challenges and the future prospect of LiAlH₄–catalyst system is also discussed. This paper is the first systematic review that focuses on catalyst-enhanced LiAlH₄ for solid-state hydrogen storage.