Dry reforming of methane to syngas over lanthanum-modified mesoporous nickel aluminate/γ-alumina nanocomposites by one-pot synthesis

La-modified NiAl₂O₄/γ-Al₂O₃?La composites with mesoporous structures were prepared by one-pot template-free strategy and applied for dry reforming of methane (DRM) to syngas. The characterization results confirmed that these materials possessed high specific surface areas, large pore volumes and narrow pore size distributions. The reduced catalysts exhibited excellent catalytic properties as well as long-term stability for DRM reaction. Addition of La showed little influence on the catalyst structure and the mean sizes of metal Ni particles, but could enhance the medium-strength basicity and the accumulation of Ni²⁺ on the catalyst surface, resulting in the enhancement of intrinsic activity, the reduction of apparent activation energy, and the suppression of carbon deposition for DRM reaction. The catalyst containing 3 wt% La possessed the best catalytic performance. The characterization of spent catalysts also demonstrated that La could effectively prevent the phase transformation of γ-alumina in the DRM process.     

Coke-resistance over Rh–Ni bimetallic catalyst for low temperature dry reforming of methane

Methane and carbon dioxide can be converted into syngas using the prospective dry reforming of methane technology. Carbon deposition is a major cause of catalyst deactivation in this reaction, especially at low temperature. The superior stability of bimetallic catalysts has made their development more and more appealing. Herein, a series of bimetallic RhNi supported on MgAl₂O₄ catalysts were synthesized and used for low temperature biogas dry reforming. The results demonstrate that the bimetallic RhNi catalyst can convert CH₄ and CO₂ by up to 43% and 52% over at low reaction temperature (600 °C). Moreover, the reaction rate of CH₄ and CO₂ of RhNi–MgAl₂O₄ remains stable during the 20 h long time stability test, most importantly, there was no obviously carbon deposition observed over the spent catalyst. The enhanced coking resistance should be attributed to the addition of a little amount of noble metal Rh can efficiently suppress dissociation of CH_X1 species into carbon, and the high surface areas of MgAl₂O₄ support can also promote the adsorption and activation of carbon dioxide to generate more O1 species. Balancing the rate of methane dissociation and carbon dioxide activation to inhibit the development of carbon deposition is a good strategy, which provides a guidance for design other high performance dry reforming of methane catalysts.     

Nickel‒cobalt bimetallic catalysts prepared from hydrotalcite-like compounds for dry reforming of methane

Ni–Co/Mg(Al)O alloy catalysts with different Co/Ni molar ratios have been prepared from Ni- and Co-substituted Mg–Al hydrotalcite-like compounds (HTlcs) as precursors and tested for dry reforming of methane. The XRD characterization shows that Ni–Co–Mg–Al HTlcs are decomposed by calcination into Mg(Ni,Co,Al)O solid solution, and by reduction finely dispersed alloy particles are formed. H₂-TPR indicates a strong interaction between nickel/cobalt oxides and magnesia, and the presence of cobalt in Mg(Ni,Co,Al)O enhances the metal-support interaction. STEM-EDX analysis reveals that nickel and cobalt cations are homogeneously distributed in the HTlcs precursor and in the derived solid solution, and by reduction the resulting Ni–Co alloy particles are composition-uniform. The Ni–Co/Mg(Al)O alloy catalysts exhibit relatively high activity and stability at severe conditions, i.e., a medium temperature of 600 °C and a high space velocity of 120000 mL g^?1 h^?1. In comparison to monometallic Ni catalyst, Ni–Co alloying effectively inhibits methane decomposition and coke deposition, leading to a marked enhancement of catalytic stability. From CO₂-TPD and TPSR, it is suggested that alloying Ni with Co favors the CO₂ adsorption/activation and promotes the elimination of carbon species, thus improving the coke resistance. Furthermore, a high and stable activity with low coking is demonstrated at 750 °C. The hydrotalcite-derived Ni–Co/Mg(Al)O catalysts show better catalytic performance than many of the reported Ni–Co catalysts, which can be attributed to the formation of Ni–Co alloy with uniform composition, proper size, and strong metal-support interaction as well as the presence of basic Mg(Al)O as support.     

Dry reforming of methane over Ni/MgO–Al2O3 catalysts: Thermodynamic equilibrium analysis and experimental application

In this study, dry reforming of methane (DRM) employing a Ni/MgO–Al₂O₃ catalyst was undertaken to evaluate the effects of temperature (650, 700 and 750 °C), weight hourly space velocity (7.5, 15 and 30 L h⁻¹ g_cat⁻¹) and catalyst MgO content (3, 5 and 10 wt%) on catalytic activity and coke-resistance. The catalysts were prepared by the wet impregnation method and were characterized by wavelength dispersive X-ray fluorescence (XRF), N₂ physisorption, X-ray diffraction (XRD), temperature-programmed reduction (TPR-H₂), temperature-programmed desorption (TPD-NH₃), H₂ chemisorption, thermogravimetric/derivative thermogravimetry analysis (TG/DTG) and scanning electron microscopy (SEM). The best conversions of methane (CH₄) and carbon dioxide (CO₂) and lower coke formation were obtained using higher temperatures, lower WHSV and 5 wt% MgO in the catalyst. The H₂/CO molar ratios obtained were within the expected range for the DRM reaction. The experimental yields of H₂ and CO differed from chemical equilibrium, mainly due to occurrence of the reverse water-gas shift reaction. Thermodynamic analysis of the reaction system, based on minimization of the Gibbs free energy, was performed in order to compare the experimental results with the optimal values for chemical equilibrium conditions, which has indicated that the DRM reaction was favored by higher temperature, lower pressure, and lower CH₄/CO₂ molar ratio.     

Hydrogen generation from liquid reforming of glycerin over Ni–Co bimetallic catalyst

Glycerin is a low cost renewable byproduct of the biodiesel industry, and can be reformed into hydrogen. Here we describe the development of cerium promoted nickel cobalt catalysts on alumina supports for the liquid phase reforming of aqueous glycerine in subcritical water. The bimetallic Ni–Co catalyst was prepared using the urea matrix combustion method over a wide range of compositions both with and without cerium. TPR profiles indicated a synergism between the metals, however, the catalysts deactivated due to carbon deposition as plaques, and in some compositions due to sintering. Cerium (2Ce–Ni₁Co₃) suppressed sintering and lowered methane selectivity by comparison with Ni₁Co₃ alone.     

Anti-sintering mesoporous Ni–Pd bimetallic catalysts for hydrogen production via dry reforming of methane

In this work, a series of mesoporous silica supported nickel or nickel-palladium catalysts were synthesized and performed in dry reforming of methane (DRM) reaction for producing syngas. Compared with the monometallic catalyst, the Ni–Pd bimetallic catalysts, especially synthesized by the OA-assisted route, exhibited promising yields of H₂ and CO in the catalytic DRM reaction, achieved at 63% and 69% over NiPd-SP-OA bimetallic catalyst at the reaction temperature of 700 °C, respectively. TEM image results confirmed that no obvious sintering phenomenon happened on spent NiPd-SP-OA bimetallic catalyst within 1550 min time-on-stream reaction. Based on the results of XRD, XPS and H₂-TPR, it could be known that the superior catalytic performance on NiPd-SP-OA catalyst were main ascribed to the smaller-sized Ni nanoparticles with a uniform metal dispersion and a larger fraction of exposed active sites (Ni⁰).     

Hydrogen production by steam reforming of liquefied natural gas (LNG) over mesoporous nickel–alumina aerogel catalyst

A mesoporous nickel–alumina aerogel catalyst (NiAE-SS) was prepared by a single-step sol–gel method and a subsequent CO₂ supercritical drying method for use in hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel catalyst supported on alumina aerogel (Ni/AE-IP) was also prepared by an impregnation method. The effect of preparation method of supported nickel catalysts on their physicochemical properties and catalytic performance in the steam reforming of LNG was investigated. NiAE-SS catalyst retained superior textural properties compared to Ni/AE-IP catalyst. Nickel species were finely dispersed on the surface of both Ni/AE-IP and NiAE-SS catalysts through the formation of surface nickel aluminate phase. Although both Ni/AE-IP and NiAE-SS catalysts exhibited a stable catalytic performance, NiAE-SS catalyst showed a better catalytic performance than Ni/AE-IP catalyst in terms of LNG conversion and hydrogen yield. High nickel surface area, high nickel dispersion, and well-developed mesoporosity of NiAE-SS catalyst played an important role in enhancing the catalytic performance in the steam reforming of LNG. Uniformly distributed metallic nickel particles in the NiAE-SS catalyst were also responsible for its high catalytic performance.     

Hydrogen production by steam reforming of liquefied natural gas (LNG) over ordered mesoporous nickel–alumina catalyst

An ordered mesoporous nickel–alumina catalyst (denoted as OMNA) was prepared by a single-step evaporation-induced self-assembly method, and it was applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, a nickel catalyst supported on ordered mesoporous alumina support (denoted as Ni/OMA) was also prepared by an impregnation method. Although both Ni/OMA and OMNA catalysts retained unidimensionally ordered mesoporous structure, textural properties of the catalysts were significantly affected by the preparation method. Nickel species were finely dispersed in the OMNA catalyst as a form of surface nickel aluminate with a high degree of nickel-saturation. On the other hand, both bulk nickel oxide and surface nickel aluminate phases were formed in the network of Ni/OMA catalyst. Nickel species in the OMNA catalyst exhibited not only high reducibility but also strong resistance toward sintering during the reduction process, compared to those in the Ni/OMA catalyst. Both Ni/OMA and OMNA catalysts showed a stable catalytic performance without catalyst deactivation during the steam reforming of LNG due to the confinement effect derived from well-developed ordered mesoporous structure in the catalysts. However, OMNA catalyst with small crystallite size of metallic nickel exhibited higher LNG conversion and hydrogen yield than Ni/OMA catalyst. Furthermore, OMNA catalyst was more active in the steam reforming of LNG than non-ordered mesoporous nickel–alumina catalysts prepared by common surfactant-templating methods using cationic, anionic, and non-ionic surfactants.     

Dry reforming of methane to synthesis gas on NiO–MgO nanocrystalline solid solution catalysts

The catalytic performance of nickel–magnesia catalysts in CO₂ reforming of methane and the factors influencing carbon deposition during the reaction were investigated by a comparative study of different reduced Ni_xMg_1−xO solid solution catalysts. With the characterization results of X-ray diffraction (XRD), BET surface area, scanning electron microscopy (SEM) and thermal gravimetric analysis (TGA) it was found that the excellent anti-coking performance of reduced solid solution catalyst with low Ni content is attributable to high dispersion of reduced Ni species, basicity of support surface and nickel–support interaction.     

Effect of alkaline earth oxides on nickel catalysts supported over γ-alumina for butanol steam reforming: Coke formation and deactivation process

Nickel catalysts were synthesized by the wet impregnation of three different supports: γ-Al₂O₃ and alumina promoted with either 10 wt % of MgO or 10 wt% of CaO. The catalysts were evaluated in butanol steam reforming at 500 °C, atmospheric pressure, GHSV of 500,000 h⁻¹ and 10% v/v butanol in the feed. Both promoters decreased catalyst acidity and increased basicity. The catalyst promoted with MgO exhibited the lowest acidity (1.1 μmolNH₃ m⁻²), whereas that promoted with CaO, the highest basicity (870.7 μmolCO₂ m⁻²). The promotion with MgO led to the highest hydrogen yield (66%) and stability, associated with its highest nickel dispersion (3.4%), lowest acidity and lowest coke formation normalized by carbon converted (3.0 mmol L mol⁻¹). The catalyst promoted with CaO presented the most severe deactivation, associated with its lowest dispersion (1.0%) and the highest amount of encapsulated coke (3.5 mmol L mol⁻¹).     

Investigation of effects of sulfur on dry reforming of biogas over nickel–iron based catalysts

The aim of this study is to maintain and increase the activity of the catalyst in the presence of H₂S with the addition of iron to the Ni catalyst. Alumina-supported monometallic iron and bimetallic nickel-iron catalysts with different weight percentages (8% Fe, 3% Ni – 3% Fe and 8% Ni – 8% Fe) were synthesized using the wet impregnation method in this study. Alumina was prepared by the sol-gel method. The activities of these synthesized catalysts in the methane dry reforming reaction were investigated at different H₂S concentrations (0 ppm, 2 ppm, and 50 ppm) with a total flow rate of 60 mL/min containing an equimolar ratio of CH₄, CO₂, and Ar at 750 °C and atmospheric pressure. To investigate the effect of sulfur compounds on the catalytic activity, the catalysts were also exposed to different gas compositions such as the mixture of H₂S + He, H₂S + CO₂ + He, and H₂S + CO₂ + CH₄ + He. In this case, FT-IR with a gas cell was used to determine the components in the gas stream at the reactor outlet. To explain catalytic performance, characterization studies were carried out using XRD, N₂ adsorption/desorption, DRIFT, SEM, TGA, and XPS analysis. All-synthesized materials showed Type-IV isotherm with a hysteresis loop corresponding to an ordered mesoporous structure. The DRIFT analysis showed a decrease in the Lewis acid sites after the addition of iron into the Ni-catalysts. In the activity test carried out in the presence of 50 ppm H₂S, it was observed that the iron-containing 8Ni–8Fe@SGA catalyst increased the sulfur resistance slightly, compared to the monometallic 8Ni@SGA catalyst. TGA analysis showed that Fe addition reduced coke deposition, as the Ni–Fe catalyst had a lower nickel crystal size than the Ni-based catalyst. FTIR analysis with a gas cell showed that sulfur in H₂S transformed to other sulfur compounds such as COS and/or SO₂ during dry reforming of biogas over alumina-supported Ni–Fe catalysts.     

Aqueous phase reforming of ethylene glycol over bimetallic platinum-cobalt on ceria–zirconia mixed oxide

The roles of cobalt promoter on the bimetallic platinum-cobalt supported on the CeO₂-ZrO₂ mixed oxide were investigated for aqueous phase reforming reaction of ethylene glycol (EG) to verify the effects of cobalt to an enhanced activity and stability of PtCo/CeO₂-ZrO₂, where the CeO₂-ZrO₂ mixed oxide was prepared by sol–gel method at a fixed Ce/(Ce + Zr) molar ratio of 0.4. The enhanced catalytic activity for an aqueous-phase reforming (APR) as well as water gas shift (WGS) reaction of EG was observed on the PtCo/CeO₂-ZrO₂ at a Co/Pt molar ratio of 0.5. The higher activity and stability on the PtCo/CeO₂-ZrO₂ at an optimal Co/Pt ratio were mainly attributed to an enhanced WGS activity and less aggregation of active metals due to a high dispersion of platinum nanoparticles with a proper interaction between platinum and oxophilic cobalt nanoparticles. A facile reduction behavior of the supported bimetallic platinum-cobalt nanoparticles through an enhanced hydrogen spillover on the platinum nanoparticles also increased CC cleavage reaction of EG with the suppressed deposition of inactive coke precursors on the partially reduced active nanoparticles. These synergy effects of platinum-cobalt nanoparticles with a close interaction and a less aggregation of active metals were responsible for an enhanced APR and WGS activity on the PtCo/CeO₂-ZrO₂ at an optimal Ce/(Ce + Zr) ratio as well.     

Steam reforming of liquefied natural gas (LNG) for hydrogen production over nickel–boron–alumina xerogel catalyst

A series of mesoporous nickel–boron–alumina xerogel (x-NBA) catalysts with different boron/nickel molar ratio (x = 0–1) were prepared by an epoxide-driven sol–gel method. The effect of boron/nickel molar ratio on the catalytic activities and physicochemical properties of nickel–boron–alumina xerogel catalysts was investigated in the steam reforming of liquefied natural gas (LNG). All the mesoporous x-NBA catalysts showed similar surface area. Introduction of boron increased interaction between nickel and support. In addition, introduction of boron into x-NBA catalysts reduced methane activation energy and increased nickel surface area. Promotion of boron had a positive effect on the catalytic activity due to the increase of adsorbed methane and nickel surface area. The amount of adsorbed methane and nickel surface area exhibited volcano-shaped trends with respect to boron/nickel molar ratio. LNG conversion and hydrogen yield increased with increasing the amount of adsorbed methane and with increasing nickel surface area. Among the catalysts, 0.3-NBA, which retained the largest amount of adsorbed methane and the highest nickel surface area, showed the best catalytic performance. It was also revealed that x-NBA catalysts showed strong coke resistance during the steam reforming reaction.     

Hydrogen production by steam reforming of liquefied natural gas (LNG) over trimethylbenzene-assisted ordered mesoporous nickel–alumina catalyst

A trimethylbenzene (TMB)-assisted ordered mesoporous nickel–alumina catalyst (denoted as TNA) was prepared by a single-step evaporation-induced self-assembly (EISA) method, and it was applied to the hydrogen production by steam reforming of liquefied natural gas (LNG). For comparison, an ordered mesoporous nickel–alumina catalyst (denoted as NA) was also prepared by a single-step EISA method in the absence of TMB. Pore volume and average pore diameter of TNA catalyst were larger than those of NA catalyst due to structural modification caused by TMB addition in the preparation of TNA catalyst. In addition, TNA catalyst showed less ordered mesoporous array than NA catalyst. Both NA and TNA catalysts exhibited diffraction patterns corresponding to nickel aluminate phase, and they retained surface nickel aluminate phase with high stability and reducibility. Crystallite size of metallic nickel in the reduced TNA catalyst was smaller than that in the reduced NA catalyst due to strong nickel–alumina interaction of surface nickel aluminate phase over TNA catalyst. In the hydrogen production by steam reforming of LNG, TNA catalyst with small crystallite size of metallic nickel showed a better catalytic performance than NA catalyst in terms of LNG conversion and hydrogen yield. Furthermore, steam reforming reaction rather than water–gas shift reaction favorably occurred over TNA catalyst.     

Co–Ni alloy supported on CeO2 as a bimetallic catalyst for dry reforming of methane

Dry reforming of methane (DRM) is an effective route to convert two major greenhouse gas (CH₄ and CO₂) to syngas (H₂ and CO). Herein, in this work, monometallic Ni/CeO₂ and a series of bimetallic Co–Ni/CeO₂ catalysts with Co/Ni ratios between 0 and 1.0 have been tested for DRM process at 600–850 °C, atmospheric pressure and a CH₄/CO₂ ratio of 1. The catalysts were characterized by X-ray diffraction, hydrogen-temperature programmed reduction, CO₂-Temperature programmed desorption, X-ray photoelectron spectroscopy, and thermogravimetric analysis. The catalyst with a Co/Ni ratio of 0.8 (labeled as 0.8 Co–Ni/CeO₂) exhibited the highest catalytic activity (CH₄ and CO₂ initial conversion for 80% and 85% at 800 °C, respectively) and the highest stability (less carbon deposition after 600min). This improved activity can be attributed to the Co–Ni alloy, which formed after reduction. Its weak chemisorption with hydrogen results in inhibition of reverse water gas shift reaction. In addition, Co-promoted the adsorption of surface oxygen enhances carbon removal, making it more stable.     

Low-temperature partial oxidation of methane over Pd–Ni bimetallic catalysts supported on CeO2

Monometallic Pd and Ni and bimetallic Pd–Ni catalysts supported on CeO₂ are prepared via mechanochemical and conventional incipient wetness impregnation methods and tested for the production of syngas by the partial oxidation of methane. Compared with monometallic Ni/CeO₂ and Pd/CeO₂, bimetallic Pd–Ni/CeO₂ catalysts show considerable higher methane conversion and syngas yield. Additionally, the bimetallic catalysts prepared by ball milling produce syngas at lower temperature. Different preparation parameters, such as metal loading, Pd/Ni ratio, milling energy, milling time and order of incorporation of the metals are examined. The best performance is obtained with a bimetallic catalyst prepared at 50 Hz for 20 min with only 0.12 wt% Pd and 1.38 wt% Ni. Stability tests demonstrate superior stability for bimetallic Pd–Ni/CeO₂ catalysts prepared by a mechanochemical approach. From the characterization results, this is explained in terms of an impressive dispersion of metal species with a strong interaction with the surface of CeO₂.     

Hydrogen production by steam reforming of liquefied natural gas (LNG) over mesoporous nickel–phosphorus–alumina aerogel catalyst

A mesoporous nickel–phosphorus–alumina aerogel catalyst (NPAA) was prepared by a single-step epoxide-driven sol–gel method and a subsequent supercritical CO₂ drying method for use in the hydrogen production by steam reforming of liquefied natural gas (LNG). In order to investigate the effect of drying method of nickel–phosphorus–alumina catalysts on their physicochemical properties and catalytic activities, a mesoporous nickel–phosphorus–alumina xerogel catalyst (NPAX) was also prepared by a single-step epoxide-driven sol–gel method and a subsequent evaporative drying method for comparison purpose. It was found that supercritical CO₂ drying method was effective for enhancing textural properties of NPAA catalyst. Although both NPAX and NPAA catalysts retained surface nickel aluminate phase, NPAA catalyst showed stronger metal-support interaction than NPAX catalyst. XRD patterns of reduced NPAX and NPAA catalysts revealed that NPAA catalyst retained smaller metallic nickel crystallite than NPAX catalysts. It was also observed that the reduced NPAA catalyst exhibited high nickel dispersion, large amount of strong hydrogen-binding sites, and large amount of methane adsorption compared to the reduced NPAX catalyst. In the steam reforming of LNG, NPAA catalyst with high affinity toward methane showed a better catalytic performance than NPAX catalyst.     

Water-gas shift assisted autothermal reforming of methane gas – transient and cold start studies

A study has been carried out to investigate the dynamic behaviour of water-gas shift assisted autothermal reforming (ATR-WGS) utilising a 2-D heterogeneous kinetic model. The purpose of this study is to gain insights to the dynamic changes of ATR-WGS during cold start and when subjected to a sudden change in square-pulse flow rate. In addition to analysis of ATR-WGS, the model can also aid in guiding the design of a feedback controller aimed at improving the dynamic response of the system. Cold start time for ATR-WGS reactor was found to be longer than autothermal reforming (ATR) reactor due to the addition of a slower water-gas shift (WGS) process. It was also observed that WGS plays an important role in the final products of the reaction. In addition to these findings, the investigations in the transient performance of ATR-WGS showed that there are serious overshoot/undershoot of performance related parameters in the transients, whose values are quite different from those under steady state conditions.     

Syngas production from methane dry reforming via optimization of tungsten trioxide-promoted mesoporous γ-alumina supported nickel catalyst

Syngas production via dry reforming of methane was conducted over 5 wt%Ni + xWO₃/γ-Al₂O₃ (x = 1, 3, 5, 7, or 9 wt%) catalysts at 700 °C and ambient pressure for 7.5 h in a tubular fixed-bed reactor. Textural, morphological, and catalytic properties were investigated in relation to the weight percent of tungsten trioxide loading. The physicochemical properties of the catalysts were evaluated using XRD, N₂-physisorption, TGA, H₂-TPR, CO₂-TPD, NH₃-TPD, SEM, EDX, and Raman techniques. N₂-physisorption analysis showed that tungsten trioxide promoter had a minor impact on the textural properties upon varying its weight percentage loading. With increasing tungsten trioxide loading, the total amount of reducible NiO-interacting species was increased over the catalyst surface. 5Ni+5WO₃/γ-Al₂O₃ catalyst showed stable 79% CH₄ conversions and 83% CO₂ conversion with the lowest carbon deposition due to the presence of stable metallic Ni species (derived from reducible NiAl₂O₄ and NiWOAl), the highly acidic sites, and moderate basic sites.     

An investigation on the role of ytterbium in ytterbium promoted γ-alumina-supported nickel catalysts for dry reforming of methane

Addition of low quantities of ytterbium to sol–gel prepared Ni/γ-Al₂O₃ catalysts has been shown to lead to significant increases in catalytic activity and long term stability in the catalytic conversion of CO₂ and CH₄ into syngas (H₂ and CO). The role of ytterbium in these catalysts was investigated in this study through detailed investigations on the structure and composition of ytterbium promoted Ni/γ-Al₂O₃ catalysts using the following techniques: synchrotron X-ray diffraction, X-ray Photoemission Spectroscopy, Transmission Electron Microscopy, Scanning Electron Microscopy/Energy Dispersive X-ray analysis, Temperature Programmed Reduction techniques and N₂ adsorption–desorption isotherms. The results obtained indicated that ytterbium, at small quantities (up to 2 wt%), interacted strongly with the support which in turn altered the interaction between nickel and the support (most notably it was found to completely inhibit the formation of NiAl₂O₄). This decreased interaction between Ni and the support also led to a higher quantity of Ni being present in the catalyst in the form of Ni.