Production of renewable hydrogen by aqueous-phase reforming of glycerol over Ni–Cu catalysts derived from hydrotalcite precursors

Ni–Cu catalysts derived from hydrotalcite-like compounds were prepared and evaluated in aqueous-phase reforming of glycerol. The catalysts were characterized by chemical composition, textural analysis, crystalline structure and reducibility. The reaction was carried out in a batch reactor with solution of 10 wt.% glycerol, at 250 and 270 °C. A maximum glycerol conversion of 60% was achieved at 270 °C. In the gas phase, the H₂ selectivity was always higher than 80% and formation of CO was very low (<3%) at 250 °C. The addition of Cu decreased the formation of methane. H₂ is consumed during the reaction at 270 °C, mainly for Cu-containing catalysts, with simultaneous formation of propylene glycol in the liquid phase. Acetol, lactic acid and acetaldehyde were also formed in the liquid phase, at both temperatures.     

Nickel versus cobalt catalysts for hydrogen production by ethanol steam reforming: Ni–Co–Zn–Al catalysts from hydrotalcite-like precursors

The urea hydrolysis method allowed to prepare well-crystallized Ni–Co–Zn–Al Layered Double Hydroxides to be used as precursors of mixed oxide catalysts for the Ethanol Steam Reforming (ESR) reaction. The calcination of the layered precursors gives rise to high surface area mixed oxides, being actually a mixture of a rock salt phase (NiO), a wurtzite phase (ZnO) and a spinel phase.     

Renewable hydrogen production from steam reforming of glycerol by Ni–Cu–Al,Ni–Cu–Mg,Ni–Mg catalysts

H₂ production from glycerol steam reforming by the Ni–Cu–Al, Ni–Cu–Mg, Ni–Mg catalysts was evaluated experimentally in a continuous flow fixed-bed reactor under atmospheric pressure within a temperature range from 450 to 650 °C. The catalysts were synthesized by the co-precipitation methods, and characterized by the elemental analysis, BET, XRD and SEM. The GC and FTIR were applied to analyze the products from steam reforming of glycerol. The coke deposited on the catalysts was measured by TGA experiments during medium temperature oxidation. The results showed that glycerol conversion and H₂ production were increased with increasing temperatures, and glycerol decomposition was favored over its steam reforming at low temperatures. The Ni–Cu–Al catalyst containing NiO of 29.2 wt%, CuO of 31.1 wt%, Al₂O₃ of 39.7 wt% performed high catalytic activity, and the H₂ selectivity was found to be 92.9% and conversion of glycerol was up to 90.9% at 650 °C. The deactivation of catalysts due to the formation and deposition of coke was observed. An improved iterative Coats–Redfern method was used to evaluate the non-isothermal kinetic parameters of coke removal from catalysts, and the results showed the reaction order of n = 1 and 2 in the Fn nth order reaction model predicted accurately the main phase in the coke removal for the regeneration of Ni–Mg and Ni–Cu–Al catalysts, respectively.     

Preparation of Ni–Cu/Mg/Al catalysts from hydrotalcite-like compounds for hydrogen production by steam reforming of biomass tar

Ni–Cu/Mg/Al bimetallic catalysts were prepared by the calcination and reduction of hydrotalcite-like compounds containing Ni²⁺, Cu²⁺, Mg²⁺, and Al³⁺, and tested for the steam reforming of tar derived from the pyrolysis of biomass at low temperature. The characterizations with XRD, STEM-EDX, and H₂ chemisorption confirmed the formation of Ni–Cu alloy particles. The Ni–Cu/Mg/Al bimetallic catalyst with the optimum composition of Cu/Ni = 0.25 exhibited much higher catalytic performance than the corresponding monometallic Ni/Mg/Al and Cu/Mg/Al catalysts in the steam reforming of tar in terms of activity and coke resistance. The catalyst gave almost total conversion of tar even at temperature as low as 823 K. This high performance was related to the higher metal dispersion, larger amount of surface active sites, higher oxygen affinity, and surface modification caused by the formation of small Ni–Cu alloy particles. In addition, the Ni–Cu/Mg/Al catalyst showed better long-term stability than the Ni/Mg/Al catalyst. No obvious aggregation and structural change of the Ni–Cu alloy particles were observed. The coke deposition on the Ni–Cu/Mg/Al catalyst was approximately ten times smaller than that on the Ni/Mg/Al catalyst, indicating good coke-resistance of the Ni–Cu alloy particles.     

Ordered mesoporous Ni–Mg–Al2O3 as an effective catalyst for CO2 reforming of CH4

The Ni based catalysts have been considered as promising candidates for the CO₂ reforming of CH₄ (CRM). However, they have suffered from two challenging issues of sintering and carbon accumulation. In order to overcome these drawbacks, a series of ordered mesoporous Ni-xMg-Al₂O₃ catalysts (x was the mole ratio of Mg/(Mg + Al)) with different Mg contents were synthesized by an improved one-pot evaporation-induced self-assembly method. The effect of Mg on the physicochemical property and catalytic performance of Ni-xMg-Al₂O₃ catalysts for CRM was investigated. The catalysts were characterized by XRD, H₂-TPR, XPS, TEM, NH₃-TPD, and N₂ adsorption-desorption at low temperature. The results showed that the introduction of Mg into the Ni–Al₂O₃ maintained well the ordered mesoporous structure and enhanced the interaction between Ni and Al₂O₃, which could effectively restrict the thermal agglomeration of Ni nanoparticles. In addition, the acid sites were decreased with the introduction of Mg, which was beneficial for resistance to carbon accumulation, and then improving the CRM performance. Among Ni-xMg-Al₂O₃ catalysts, Ni–3Mg–Al₂O₃ presented the highest catalytic activity and stability. Under the conditions of 750 °C and GHSV = 32000 mL g^?1 h^?1, the conversion of CH₄ and CO₂ could reach 81.97% and 89.11% without deactivation for 20 h.     

Hydrogen production from catalytic reforming of the aqueous fraction of pyrolysis bio-oil with modified Ni–Al catalysts

Hydrogen production from renewable resources has received extensive attention recently for a sustainable and renewable future. In this study, hydrogen was produced from catalytic steam reforming of the aqueous fraction of crude bio-oil, which was obtained from pyrolysis of biomass. Five Ni–Al catalysts modified with Ca, Ce, Mg, Mn and Zn were investigated using a fixed-bed reactor. Optimized process conditions were obtained with a steam reforming temperature of 800 °C and a steam to carbon ratio of 3.54. The life time of the catalysts in terms of stability of hydrogen production and prohibition of coke formation on the surface of the catalyst were carried out with continuous feeding of raw materials for 4 h. The results showed that the Ni–Mg–Al catalyst exhibited the highest stability of hydrogen production (56.46%) among the studied catalysts. In addition, the life-time test of catalytic experiments showed that all the catalysts suffered deactivation at the beginning of the experiment (reduction of hydrogen production), except for the Ni–Mg–Al catalyst; it is suggested that the observation of abundant amorphous carbon formed on the surface of reacted catalysts (temperature programmed oxidation results) may be responsible for the initial reduction of hydrogen production. In addition, the Ni–Ca–Al catalyst showed the lowest hydrogen production (46.58%) at both the early and stabilized stage of catalytic steam reforming of bio-oil.     

Synthetic gas production by dry reforming of methane over Ni/Al2O3–ZrO2 catalysts: High H2/CO ratio

Alumina prepared by the sol-gel method, was impregnated with zirconia (5, 15 and 30 wt.%). Subsequently, the resulting Al₂O₃–ZrO₂ supports were impregnated with 15% Ni to obtain the Ni/Al₂O₃–ZrO₂ catalysts. The obtained catalysts were characterized by BET, SEM, XRD, H₂-TPR and TPD- CO₂. The catalytic activity was studied by means of dry reforming of methane (DRM) for syngas production. The catalysts displayed different physicochemical properties and trends of their catalytic activity as a function of the ZrO₂ content in the mixed oxide supports. For instance, ZrO₂ (5 wt %) in the catalyst, led to enhanced concentration of the medium strength basic sites and increased specific surface area, yielding thus the best performance in the DRM, with low carbon deposition after 36 h of reaction, compared with the other catalysts. This indicates that during the DRM reaction, this catalyst can provide more surface oxygen to prevent carbon deposits that could deactivate the catalyst.     

Study of Ni/CeO2–ZnO catalysts in the production of H2 from acetone steam reforming

This paper reports the study of new Ni/ZnO-based catalysts for hydrogen production from substoichiometric acetone steam reforming (ASR). The effect of CeO₂ introduction is analyzed regarding the catalytic behavior and carbon deposits formation. ASR was studied at 600 °C using a steam/carbon ratio S/C = 1. Ni/xCeZnO (x = 10, 20, 30 CeO₂ wt %) catalysts showed a better performance than the bare Ni/ZnO. Ni/xCeZnO generated a lower amount and less ordered carbon deposits than Ni/ZnO. The higher the CeO₂ content in Ni/xCeZnO, the lower the amount of carbon deposits in the post-reaction catalyst. The highest H₂ production under ASR at the experimental conditions used was achieved for the Ni/xCeZnO catalysts. In-situ DRIFTS-MS experiments under ESR conditions showed different reaction pathways over Ni/20CeZnO and Ni/ZnO catalysts.     

Co-precipitated Ni–Mg–Al catalysts for hydrogen production by supercritical water gasification of glucose

Supercritical water gasification (SCWG) is a promising process for hydrogen production from biomass. In this study, a series of Ni–Mg–Al catalysts with different Mg/Al molar ratios has been synthesized by a co-precipitation method for hydrogen production by SCWG of glucose. Effects of Mg addition on the catalytic activity, hydrothermal stability and anti-carbon performance of alumina supported nickel catalyst were investigated. The highly dispersed nickel catalysts prepared by co-precipitation could greatly enhance the gasification efficiency of glucose in supercritical water. Among the tested Ni–Mg–Al catalysts, NiMg_0.6Al_1.9 showed the highest catalytic activity with the hydrogen yield of 11.77 mmol/g (912% as that of non-catalytic test). NiMg_0.6Al_1.9 also showed the best hydrothermal stability probably due to the formation of MgAl₂O₄. Mg could efficiently improve the anti-carbon ability of Ni–Al catalyst by inhibiting the formation of graphite carbon. It is also confirmed that MgO supported nickel catalyst is not suitable for SCWG process owing to the difficulty on nickel oxides reduction in the precursors and the phase change of MgO to Mg(OH)₂ under the hydrothermal condition.     

Ni–Co bimetallic MgO-based catalysts for hydrogen production via steam reforming of acetic acid from bio-oil

Acetic acid (AC) is a representative compound of bio-oil via fast pyrolysis of biomass, and can be processed for hydrogen production via steam reforming (SR). In the current work, the Ni_xCo_1−xMg₆O_7±δ (x = 0–1) bimetallic catalysts were prepared via co-precipitation and impregnation, and tested in SR of AC. The reaction results indicate that the monometallic catalysts were deactivated obviously in SR, while the Ni_0.2Co_0.8Mg₆O_7±δ bimetallic catalyst performed better in both activity and stability: not only the conversion of AC remained stable near 100%, but also the H₂ yield maintained stable near 3.1 mol-H₂/mol-AC. The results of XRD, BET, XPS, TG and TEM indicate that the high catalytic performance of the Ni_0.2Co_0.8Mg₆O_7±δ catalyst can be attributed to 1) resistance to oxidation of active metals, 2) resistance to coking, and 3) stability of structure and electronic properties.     

Natural gas reforming of carbon dioxide for syngas over Ni–Ce–Al catalysts

A series of Ni–Ce–Al composite oxides with various Ni molar contents were synthesized via the refluxed co-precipitation method and used for natural gas reforming of CO₂ (NGRC) for syngas production. The effect of Ni molar content, reaction temperature, feed gas ratio and gas hourly space velocity (GHSV) on the Ni–Ce–Al catalytic performance was investigated. The Ni₁₀CeAl catalyst was selected to undergo 30 h stability test and the conversion of CH₄ and CO₂ decreased by 2.8% and 2.6%, respectively. The characterization of the reduced and used Ni₁₀CeAl catalyst was performed using BET, H₂-TPR, in-situ XRD, TEM, and TGA-DTG techniques. The in-situ XRD results revealed that Ce₂O₃, CeO₂ and CeAlO₃ coexisted in the Ni₁₀CeAl catalyst after reduction at 850 °C for 2 h. The results of the TEM analysis revealed that the Ni particle size increased after the NGRC reaction, which mainly caused the catalyst deactivation.     

Experimental investigation of hydrogen production by CH4–CO2 reforming using rotating gliding arc discharge plasma

Hydrogen produced from CH₄–CO₂ reforming by an optimized rotating gliding arc discharge plasma reactor is investigated in this study. The effect of CH₄/CO₂ ratio (mole ratio), total input flow rate, discharge gap, voltage, and discharge frequency are analyzed. The results show that H₂ yield increases with the increase of CH₄/CO₂ ratio. Arc can be stretched effectively by increasing total input flow rate, then the discharge region is enlarged. Increasing discharge gap can enlarge the discharge region, but the reaction of the gas mixture would be suppressed if the discharge region was excessively large. The discharge region decreases with the increased discharge frequency to a certain degree. Based on the experimental results, the optimal experimental condition is concluded as applied voltage 60 V, discharge frequency 20 kHz, and minimum discharge gap 3 mm. It is anticipated that the results would serve as a good guideline to the application of hydrogen production from hydrocarbon fuels by plasma reforming onboard.     

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.     

Coke resistance of Ni-based catalysts enhanced by cold plasma treatment for CH4–CO2 reforming: Review

Carbon dioxide reforming of methane can reduce emissions of greenhouse gases, and has been extensively studied. The conventional Ni-based catalysts easily coke, sinter, and deactivate in the CRM reaction. The studies suggested that the cold plasma treatment can improve the structure of Ni-based catalysts, and so enhance coke resistance of the catalysts. The review summarized the effect of cold plasma treatment on the coke resistance of Ni-based catalysts for the CRM reaction. The main goal of the paper was to illuminate: the structure change of catalysts treated by cold plasma, such as crystal planes of Ni particles, the particles size of Ni, the Ni dispersion, the metal-support interaction, and CO₂ absorption capacity; the correlation between plasma treatment conditions (treatment way and parameters) and coke resistance of the catalyst treated by cold plasma; and the mechanism of plasma treatment to improve the coke resistance of the catalysts.     

Hydrogen production from ethanol steam reforming over Co–Ce/sepiolite catalysts prepared by a surfactant assisted coprecipitation method

A series of Co–Ce/Sepiolite (SEP) catalysts were prepared by surfactant-assisted coprecipitation route and subsequently evaluated for hydrogen production from ethanol steam reforming. The effects of the types and quantities of surfactants such as Cetyltrimethyl Ammonium Bromide (CTAB) and Polyvinyl Pyrrolidone (PVP) on catalysts microstructures were investigated by means of N₂ adsorption-desorption, XRD, H₂-TPR, Raman, XPS, SEM, and TEM. The results demonstrated that the function of surfactants complexation with Co/Ce precursors enlarged the metal interparticle distance, led to the surface enrichment of Co/Ce atoms and provoked diverse Co–Ce interfaces, which could both enhance the reforming behavior and restrain the amorphous coke during reaction. Meanwhile, the optimal complexation effect of CTAB on Co–Ce/SEP-C0.4 (CTAB:M^δ+ = 0.4) gave it superior reducibility, surface content of Co/Ce atoms and relative abundance of oxygen vacancies. Consequently, Co–Ce/SEP-C0.4 presented the best ethanol conversion (96.2%), hydrogen yield (77.9%) and the uppermost catalytic stability (100 h) during ESR reaction. In addition, the scatter modes of surface Co/Ce particles and forms of Co–Ce interfaces significantly depended on surfactant types.     

Promoted Ni–Co–Al2O3 nanostructured catalysts for CO2 methanation

15 wt.%Ni-12.5 wt.%Co–Al₂O₃ catalysts promoted with Fe, Mn, Cu, Zr, La, Ce, and Ba were prepared by a novel solid-state synthesis method and employed in CO₂ methanation reaction. BET, XRD, EDS, SEM, TPR, TGA, and FTIR analyses were conducted to identify the chemicophysical characteristics of the prepared samples. The addition of Fe, Mn, La, Ce, and Ba was effective to improve the catalytic performance of the 15 wt%Ni-12.5 wt%Co–Al₂O₃ due to the higher CO₂ adsorption capacity of the promoted catalysts. Among the studied promoters, the Fe-promoted catalyst possessed the highest catalytic activity (X_CO2 = 61.2% and S_CH4 = 98.87% at 300 °C). Also, the effect of calcination temperature, feed composition, and GHSV on the performance of the 15 wt%Ni-12.5 wt%Co-5wt%Fe–Al₂O₃ catalyst in CO₂ methanation reaction was assessed. The outcomes confirmed that the 15 wt%Ni-12.5 wt%Co-5wt%Fe–Al₂O₃ catalyst with the BET area of 122.4 m²/g and the highest pore volume and largest pore diameter had the highest catalytic activity. Also, the catalytic performance in the methanation of carbon monoxide was studied, and 100% conversion of carbon monoxide was observed at 250 °C.     

One-step synthesis of metallic Ni–C/Al2O3 directly applied for CO2 reforming of CH4

In this work, the vacuum co-impregnation of glucose and nickel precursor followed by the carbonization in an inert gas was developed as a new method for the preparation of the directly reduced Ni-based catalysts (Ni–C/Al₂O₃), which can be directly applied for CO₂ reforming of CH₄ (CRM) without any reduction. The materials were characterized by XRD, TEM, and N₂ adsorption-desorption at low temperature. The results showed that H₂ and CH₄ derived from the decomposition of the glucose acted as the reducing agents for synthesizing metallic Ni from Ni precursors, and the reduction content of nickel was strongly dependent on the amount the glucose. The introduction of carbon derived from decomposition of glucose decreased the interaction between Ni and Al₂O₃ and then resulting in bigger Ni particle. Under the same CRM reaction conditions, the as-prepared Ni-0.35C/Al₂O₃ catalyst without further reduction showed highest catalytic activity and stability. The use of the directly reduced Ni-based catalyst without further high-temperature reduction is promising for the development of a more efficient CRM process.