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A series of multifunctional catalysts were derived from lamellar montmorillonite (MMT) via ultrasound-assisted cation-exchange method. They were characterized by N 2 adsorption-desorption, X-ray diffraction (XRD), H 2 temperature-programmed reduction (H 2 -TPR), H 2 pulse chemisorption, inductively coupled plasma optical emission spectrometry (ICP-OES), and transmission electron microscopy (TEM). The characterization results show that metal-support interaction (MSI) together with Ni and Ca dispersion interrelates with confinement effect of montmorillonite. The CO 2 absorption capacity of CAT-5 (Ca/MMT molar ratio is 5) was still above 20.0% at the tenth cycle. The steam to glycerol molar ratio (S/G) and reaction temperature were investigated, and an S/G = 3 and a temperature of 600 °C were optimized. The hydrogen purity was significantly enhanced by the equilibrium shift of insitu CO 2 removal at 600 °C. CAT-5 presents the best performance considering the synchronized absorption capacity and catalytic activity. Compared with CAT-M, CAT-5 shows higher stability in the multiple reaction-decarbonation cycles, which is due to the elevated sintering resistance of CaO derived from the confinement effect of lamellar structure. [ABSTRACT FROM AUTHOR]

This paper describes the synthesis of a series of Ni based Al-MCM-41 oxygen carriers with and without Ce promoter and their application in chemical looping steam reforming of glycerol. The Al-MCM-41 is derived from montmorillonite. The oxygen carriers were prepared by direct-synthesis and post-synthesis method. A variety of technologies including N 2 adsorption-desorption, X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), H 2 temperature-programmed reduction (H 2 -TPR), and transmission electron microscopy (TEM) were conducted to characterize the fresh and used oxygen carriers. The results show the direct-synthesis oxygen carrier possesses excellent textual properties, such as high Ni loading, small particle size, large pore volume, and uniform pore size. The incorporation of Ce could effectively control particle size via strong metal support interaction, promote the homogeneous distribution of Ni, and enhance oxygen mobility capability and water gas shift reaction. And thus shorten ‘dead time’ during the fuel feed step. The CeNi/Al-MCM-41 displayed the superior activity and excellent long-term stability, which could be due to the strengthened anti-sintering and coke capability. [ABSTRACT FROM AUTHOR]

For the fixed-bed reactor configuration in the sorption-enhanced steam reforming process (SERP), solid mixture of catalyst and sorbent is stationary and alternatively exposed to reaction and regeneration conditions for multi-cycles by periodically switching the feed gases for enhanced hydrogen production with in-situ CO 2 removal. A NiO/NiAl 2 O 4 catalyst was synthesized by the co-precipitation method with rising pH technique and the crystalline spinel phase of NiAl 2 O 4 was formed under the calcination temperature of 900 °C. The catalyst was characterized by X-ray powder diffraction (XRD), scanning electron microscope (SEM), thermo-gravimetric analysis (TGA), and N 2 adsorption–desorption. The non-stoichiometric thermodynamic calculation was carried out to determine the effects of temperature and in-situ CO 2 removal on the enhancement of hydrogen production by SERP from glycerol at 425–700 °C. The multi-cycles on reaction and regeneration for hydrogen production by SERP from glycerol were performed by NiO/NiAl 2 O 4 catalyst and CaO based sorbent in a fixed-bed reactor. The results showed that hydrogen production by SERP can be clearly divided into three periods, and the experimental gaseous products were compared with non-stoichiometric thermodynamic calculations. It is obvious that H 2 purity was greatly increased, and CO 2 , CO and CH 4 concentrations were reduced by in-situ CO 2 removal during the pre-breakthrough period. It is found that enhanced hydrogen production was mainly depended on in-situ CO 2 removal. The operation durations for producing high-purity hydrogen of more than 90% were decreased with the increase of the cycles. It may due to the decrease in the reactivity of CaO based sorbent after multi-cycles reaction and regeneration. [ABSTRACT FROM AUTHOR]

In this study, renewable hydrogen production was achieved by coupling of water splitting and glycerol oxidation reforming by chemical looping technology (CLWS-GOR) using the novel Ce–Ni modified Fe-based oxygen carriers (OCs). The OCs were developed by combining metal chelating sol-gel and isometric impregnation method, which exhibited anti-sintering characteristic and lattice oxygen migration ability in CLWS-GOR. The amount of hydrogen between 12.49 and 12.96 mmol in the steam stage was produced from all the OCs with different ratios of Fe, Ce and Ni. However, with the increase of Ce and Ni doping, the production of H 2 and CO in the fuel stage increased, as well as the probability of carbon deposits released in the subsequent steam stage. The H 2 /CO ratio in syngas were easily adjusted by steam to carbon molar ratio (S/C) in chemical looping steam reforming (CLSR), but the effects of steam introducing led to gradual deterioration of OCs. The results proved the OCs prepared by the combination method has high activity and stability for renewable hydrogen production from coupling of CLWS-GOR. [Display omitted] • Coupling of water splitting and glycerol oxidation reforming by chemical looping. • Ce–Ni modified Fe-based OCs were synthesized by combined method. • Pure H 2 was achieved from CLWS-GOR by reduced OCs. • WGS enhancement and the H 2 /CO ratio adjustment were achieved. [ABSTRACT FROM AUTHOR]

Highlights: [•] Ni–Cu–Al catalyst for hydrogen production was synthesized by rising pH technique. [•] Experimental data were analyzed with non-stoichiometric thermodynamic calculation. [•] Catalyst deactivation due to carbon deposits in glycerol steam reforming was found. [•] Carbon removal was analyzed by TGA experiment during medium temperature oxidation. [•] Reforming was tested by separability kinetics of rate law and catalyst deactivation. [Copyright &y& Elsevier]

Abstract: The objective of this review is to analyze potential technologies and their baseline performance of producing hydrogen from catalytic steam reforming of biodiesel byproduct glycerol. High oxygen content and high impurity level of biodiesel byproduct glycerol, as well as the complex intermediates and high coking potential in its thermal degradation, make the modeling, design, and operation of glycerol steam reforming a challenge. Thermal decomposition characterization of biodiesel byproduct glycerol was covered, and the recent developments and methods for high-purity hydrogen production from glycerol steam reforming were illustrated. The thermodynamics constraint of water gas shift reaction can be overcome by the sorption-enhanced steam reforming process, which integrated catalytic steam reforming, water gas shift reaction and in-situ CO2 removal at high temperatures in a single stage reactor. The effectiveness of both the enhanced H2 production and the use of CO2 sorbents have been demonstrated and discussed. The technical challenges to achieve a stable high-purity hydrogen production by the sorption-enhanced steam reforming process included extending operation time, selecting suitable sorbents, finding a way for continuous reaction-regeneration of catalyst and sorbent mixture and improving process efficiencies. The continuous sorption-enhanced steam reforming of glycerol was designed by a simultaneous flow concept of catalyst and sorbent for continuous reaction-regeneration using two slow moving-bed reactors for high-purity hydrogen production and CO2 capture, and in this process, catalyst and sorbent were run in nearly fresh state for H2 production. The sorption-enhanced chemical-looping reforming was also demonstrated. The paper discusses some issues and challenges, along with the possible solutions in order to help in efficient production of hydrogen from catalytic steam reforming of biodiesel byproduct glycerol. [Copyright &y& Elsevier]

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

Abstract: About 10wt.% of glycerol can be produced during the conversion of vegetable oils or animal fats into biodiesel fuel by the transesterification process. To make use of glycerol and increase its values, H2 production from catalytic steam reforming of glycerol by Ni–Mg–Al based catalysts was evaluated experimentally in a fixed-bed reactor under atmospheric pressure within a temperature range of 450–650°C. The thermodynamic analysis was conducted by using a non-stoichiometric methodology based on the minimization of Gibbs free energy. The Ni–Mg–Al based catalysts were synthesized by the co-precipitation method with rising pH technique. The synthesized catalysts were characterized by the elemental analysis, BET, XRD and SEM methods. All the metals in the catalyst remained in oxide forms and the catalysts had the specific surface areas from 98.542 to 126.777m2/g for different compositions. The results showed that glycerol conversion and H2 selectivity were increased with increasing temperatures from 450 to 650°C. The formations of CH4 and CO in the glycerol steam reforming were almost negligible. Carbon formation in glycerol steam reforming was serious in low temperatures. The catalyst containing NiO of 24.1wt.%, MgO of 26.1wt.% and Al2O3 of 49.8wt.% performed appreciable catalytic activity, and the H2 selectivity was found to be 78.5% and conversion of glycerol was up to 88.0% at 650°C. The effects of the operating conditions including temperature, the ratio of steam to carbon (S/C), glycerol inlet concentration and flow rate of carrier gas on glycerol steam reforming by the optimized catalyst were tested. Based on a kinetic model assuming the power law with a first reaction order, the activation energy and the frequency factor for glycerol steam reforming by the Ni–Mg–Al based catalysts were calculated. [Copyright &y& Elsevier]

Abstract: Hydrogen production from steam reforming of glycerol in a fluidized bed reactor has been simulated using a CFD method by an additional transport equation with a kinetic term. The Eulerian–Eulerian two-fluid approach was adopted to simulate hydrodynamics of fluidization, and chemical reactions were modelled by laminar finite-rate model. The bed expansion and pressure drop were predicted for different inlet gas velocities. The results showed that the flow system exhibited a more heterogeneous structure, and the core-annulus structure of gas–solid flow led to back-mixing and internal circulation behaviour, and thus gave a poor velocity distribution. This suggests the bed should be agitated to maintain satisfactory fluidizing conditions. Glycerol conversion and H2 production were decreased with increasing inlet gas velocity. The increase in the value of steam to carbon molar ratio increases the conversion of glycerol and H2 selectivity. H2 concentrations in the bed were uneven and increased downstream and high concentrations of H2 production were also found on walls. The model demonstrated a relationship between hydrodynamics and hydrogen production, implying that the residence time and steam to carbon molar ratio are important parameters. The CFD simulation will provide helpful data to design and operate a bench scale catalytic fluidized bed reactor. [ABSTRACT FROM AUTHOR]

Abstract: Steam reforming of the crude glycerol by-product of a biodiesel production plant has been evaluated experimentally at atmospheric pressure, with and without in situ CO2 sorption, in a continuous flow fixed-bed reactor between 400°C and 700°C. The process outputs were compared to those using pure glycerol. Thermodynamic equilibrium calculations were used to assess the effect on the steam reforming process of the main crude impurities (methanol and four fatty acid methyl esters). The crude glycerol and steam conversions and the H2 purity reached 100%, 11% and 68%, respectively at 600°C. No CH4 was found at and above 600°C. Steam reforming of crude glycerol with in situ CO2 removal is shown to be an effective means of achieving hydrogen purity above 88% in pre-CO2 breakthrough conditions. [Copyright &y& Elsevier]

[Display omitted] • Hydrogen was efficiently produced from CLSR of biodiesel byproduct glycerol. • Well-order mesoporous CeNiO/MCM-41 and CeNiO/SBA-15 were synthesized for CLSR. • High feeding conversion and H 2 selectivity was achieved by mesoporous OCs. • High loading NiO and CeO 2 on mesoporous OCs achieved excellent CLSR redox cycles. The selection of metal oxides and supports to improve catalytic activity and stability of oxygen carriers (OCs) is crucial for chemical looping steam reforming (CLSR) to hydrogen production. In this study, the Ni-based MCM-41 and SBA-15 OCs with and without CeO 2 promoter were prepared by direct synthesis and impregnation methods. The BET, XRD, TEM, ICP-AES, H 2 -TPR and DSC-TGA were used to analyze the synthesized OCs. Hydrogen production by CLSR using biodiesel byproduct glycerol was studied in a fixed-bed reactor with fuel and air stages. The DSC-TGA experiments were carried out to determine the thermal decomposition of biodiesel byproduct glycerol and the results indicated the exothermic and/or endothermic reactions as a result of secondary reactions and, the main degradation with the mass loss of 85.5 wt% occurred in the stages of 150–500 °C. The mesoporous OCs presented high specific surface area, large pore volume, and uniform pore size. It was found that the NiO and CeO 2 in the mesoporous OCs were first reduced by fuels and the reduced OCs was responsible of steam reforming and water gas shift (WGS) to hydrogen production, and hydrogen selectivity was up to 90% using CeNiO/SBA-15. The mesoporous OCs with Ce promoter greatly shortened 'dead time' (the reduce time of OCs), and effectively suppressed carbon deposited on OCs. High loading of NiO and CeO 2 on SBA-15 improved oxygen transfer and achieved excellent cyclic stability. These findings provide the fundamental understanding and principle of design on the conventional Ni-based OCs with room for further developments in chemical looping process. [ABSTRACT FROM AUTHOR]