Hydrogen Production by Steam Reforming of Ethanol on Rh-Pt Catalysts: Influence of CeO2, ZrO2, and La2O3 as Supports

CeO2-, ZrO2-, and La2O3-supported Rh-Pt catalysts were tested to assess their ability to catalyze the steam reforming of ethanol (SRE) for H2 production. SRE activity tests were performed using EtOH:H2O:N2 (molar ratio 1:3:51) at a gaseous space velocity of 70,600 h−1 between 400 and 700 °C at atmospheric pressure. The SRE stability of the catalysts was tested at 700 °C for 27 h time on stream under the same conditions. RhPt/CeO2, which showed the best performance in the stability test, also produced the highest H2 yield above 600 °C, followed by RhPt/La2O3 and RhPt/ZrO2. The fresh and aged catalysts were characterized by TEM, XPS, and TGA. The higher H2 selectivity of RhPt/CeO2 was ascribed to the formation of small (~5 nm) and stable particles probably consistent of Rh-Pt alloys with a Pt surface enrichment. Both metals were oxidized and acted as an almost constant active phase during the stability test owing to strong metal-support interactions, as well as the superior oxygen mobility of the support. The TGA results confirmed the absence of carbonaceous residues in all the aged catalysts.

The steam reforming of hydrocarbons with special reference to methane

From an examination of the literature relating to the catalytic steam reforming of hydrocarbons, it is concluded that the kinetics of high pressure reforming, particularly steam-methane reforming, has received relatively little attention. Therefore because of the increasing availability of natural gas in the U.K., this system was considered worthy of investigation. An examination of the thermodynamics relating to the equilibria of steam-hydrocarbon reforming is described. The reactions most likely to have influence over the process are established and from these a computer program was written to calculate equilibrium compositions. A means of presenting such data in a graphica1 form for ranges of the operating variables is given, and also an operating chart which may be used to quickly check feed ratios employed on a working naphtha reforming plant is presented. For the experimental kinetic study of the steam-methane system, cylindrical pellets of ICI 46-1 nickel catalyst were used in the form of a rod catalyst. The reactor was of the integral type and a description is given with the operating procedures and analytical method used. The experimental work was divided into two parts, qualitative and quantitative. In the qualitative study the various reaction steps are examined in order to establish which one is rate controlling. It is concluded that the effects of film diffusion resistance within the conditions employed are negligible. In the quantitative study it was found that at 250 psig and 6500C the steam-methane reaction is much slower than the CO shift reaction and is rate controlling. Two rate mechanisms and accompanying kinetic rate equations are derived, both of which represent 'chemical' steps in the reaction and are considered of equal merit. However the possibility of a dual control involving 'chemical' and pore diffusion resistances is also expressed.

Zirconia and alumina based catalysts for steam reforming of naphthalene

The present paper deals with experimentation of ZrO2 and Al2O3-supported catalysts for conversion of naphthalene, chosen as tar model compound of pyrolysis or gasification syngas. In particular, the reforming capacity of active metals and promoters such as Co, Ni, Fe, Cr, Ce and Pt was tested in a fixed bed reactor at temperature from 400 to 900 °C. As regards ZrO2-supported catalysts, the best results were achieved by the Ni/Fe/Pt catalyst with 96% naphthalene conversion, 78% and 280% as CO and H2 production yield at 800 °C. Regarding Al2O3-supported catalysts, they were more active on average than the zirconia ones, achieving a very good performance even at 500 °C (90–100% naphthalene conversion, 30–40% CO yield and 300–350% H2 yield at 550 °C). Influence of different amounts of alumina, montmorillonite and carbon on carrier composition as well as pellets’ size were also studied. Both zirconia and alumina catalysts showed deactivation at higher temperatures due to coke deposition, resulting in a strong H2 production drop. Regeneration of catalysts by O2 and steam as well as activation by H2 were also studied. The activated catalyst was able to convert more than 99% naphthalene at 450 °C with a CO and H2 production yield of 26% and 420%, respectively.

Computationsl modelling of dimethyl ether separation and steam reforming in fluidized bed reactors

This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether (DME) gas adsorptive separation and steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian-Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). Hydrogen is currently receiving increasing interest as an alternative source of clean energy and has high potential applications, including the transportation sector and power generation. Computational fluid dynamic (CFD) modelling has attracted considerable recognition in the engineering sector consequently leading to using it as a tool for process design and optimisation in many industrial processes. In most cases, these processes are difficult or expensive to conduct in lab scale experiments. The CFD provides a cost effective methodology to gain detailed information up to the microscopic level. The main objectives in this project are to: (i) develop a predictive model using ANSYS FLUENT (CFD) commercial code to simulate the flow hydrodynamics, mass transfer, reactions and heat transfer in a large scale dual fluidized bed system for combined gas separation and steam reforming processes (ii) implement a suitable adsorption models in the CFD code, through a user defined function, to predict selective separation of a gas from a mixture (iii) develop a model for dimethyl ether steam reforming (DME-SR) to predict hydrogen production (iv) carry out detailed parametric analysis in order to establish ideal operating conditions for future industrial application. The project has originated from a real industrial case problem in collaboration with the industrial partner Dow Corning (UK) and jointly funded by the Engineering and Physical Research Council (UK) and Dow Corning. The research examined gas separation by adsorption in a bubbling bed, as part of a dual fluidized bed system. The adsorption process was simulated based on the kinetics derived from the experimental data produced as part of a separate PhD project completed under the same fund. The kinetic model was incorporated in FLUENT CFD tool as a pseudo-first order rate equation; some of the parameters for the pseudo-first order kinetics were obtained using MATLAB. The modelling of the DME adsorption in the designed bubbling bed was performed for the first time in this project and highlights the novelty in the investigations. The simulation results were analysed to provide understanding of the flow hydrodynamic, reactor design and optimum operating condition for efficient separation. Bubbling bed validation by estimation of bed expansion and the solid and gas distribution from simulation agreed well with trends seen in the literatures. Parametric analysis on the adsorption process demonstrated that increasing fluidizing velocity reduced adsorption of DME. This is as a result of reduction in the gas residence time which appears to have much effect compared to the solid residence time. The removal efficiency of DME from the bed was found to be more than 88%. Simulation of the DME-SR in FLUENT CFD was conducted using selected kinetics from literature and implemented in the model using an in-house developed user defined function. The validation of the kinetics was achieved by simulating a case to replicate an experimental study of a laboratory scale bubbling bed by Vicente et al [1]. Good agreement was achieved for the validation of the models, which was then applied in the DME-SR in the large scale riser section of the dual fluidized bed system. This is the first study to use the selected DME-SR kinetics in a circulating fluidized bed (CFB) system and for the geometry size proposed for the project. As a result, the simulation produced the first detailed data on the spatial variation and final gas product in such an industrial scale fluidized bed system. The simulation results provided insight in the flow hydrodynamic, reactor design and optimum operating condition. The solid and gas distribution in the CFB was observed to show good agreement with literatures. The parametric analysis showed that the increase in temperature and steam to DME molar ratio increased the production of hydrogen due to the increased DME conversions, whereas the increase in the space velocity has been found to have an adverse effect. Increasing temperature between 200 oC to 350 oC increased DME conversion from 47% to 99% while hydrogen yield increased substantially from 11% to 100%. The CO2 selectivity decreased from 100% to 91% due to the water gas shift reaction favouring CO at higher temperatures. The higher conversions observed as the temperature increased was reflected on the quantity of unreacted DME and methanol concentrations in the product gas, where both decreased to very low values of 0.27 mol% and 0.46 mol% respectively at 350 °C. Increasing the steam to DME molar ratio from 4 to 7.68 increased the DME conversion from 69% to 87%, while the hydrogen yield increased from 40% to 59%. The CO2 selectivity decreased from 100% to 97%. The decrease in the space velocity from 37104 ml/g/h to 15394 ml/g/h increased the DME conversion from 87% to 100% while increasing the hydrogen yield from 59% to 87%. The parametric analysis suggests an operating condition for maximum hydrogen yield is in the region of 300 oC temperatures and Steam/DME molar ratio of 5. The analysis of the industrial sponsor’s case for the given flow and composition of the gas to be treated suggests that 88% of DME can be adsorbed from the bubbling and consequently producing 224.4t/y of hydrogen in the riser section of the dual fluidized bed system. The process also produces 1458.4t/y of CO2 and 127.9t/y of CO as part of the product gas. The developed models and parametric analysis carried out in this study provided essential guideline for future design of DME-SR at industrial level and in particular this work has been of tremendous importance for the industrial collaborator in order to draw conclusions and plan for future potential implementation of the process at an industrial scale.

The intermediate pyrolysis and catalytic steam reforming of brewers spent grain

Brewers spent grain (BSG) is a widely available feedstock representing approximately 85% of the total by-products generated in the brewing industry. This is currently either disposed of to landfill or used as cattle feed due to its high protein content. BSG has received little or no attention as a potential energy resource, but increasing disposal costs and environmental constraints are now prompting the consideration of this. One possibility for the utilisation of BSG for energy is via intermediate pyrolysis to produce gases, vapours and chars. Intermediate pyrolysis is characterised by indirect heating in the absence of oxygen for short solids residence times of a few minutes, at temperatures of 350-450 °C. In the present work BSG has been characterised by chemical, proximate, ultimate and thermo-gravimetric analysis. Intermediate pyrolysis of BSG at 450 °C was carried out using a twin coaxial screw reactor known as Pyroformer to give yields of char 29%, 51% of bio-oil and 19% of permanent gases. The bio-oil liquid was found to separate in to an aqueous phase and organic phase. The organic phase contained viscous compounds that could age over time leading to solid tars that can present problems in CHP application. The quality of the pyrolysis vapour products before quenching can be upgraded to achieve much improved suitability as a fuel by downstream catalytic reforming. A Bench Scale batch pyrolysis reactor has then been used to pyrolyse small samples of BSG under a range of conditions of heating rate and temperature simulating the Pyroformer. A small catalytic reformer has been added downstream of the reactor in which the pyrolysis vapours can be further cracked and reformed. A commercial reforming nickel catalyst was used at 500, 750 and 850 °C at a space velocity about 10,000 L/h with and without the addition of steam. Results are presented for the properties of BSG, and the products of the pyrolysis process both with and without catalytic post-processing. Results indicate that catalytic reforming produced a significant increase in permanent gases mainly (H2 and CO) with H2 content exceeding 50 vol% at higher reforming temperatures. Bio-oil yield decreased significantly as reforming temperature increased with char remaining the same as pyrolysis condition remained unchanged. The process shows an increase in heating value for the product gas ranging between 10.8-25.2 MJ/m as reforming temperature increased. © 2012 Elsevier B.V. All rights reserved.

Hydrogen production by steam reforming of DME in a large scale CFB reactor. Part I:computational model and predictions

This study presents a computational fluid dynamic (CFD) study of Dimethyl Ether steam reforming (DME-SR) in a large scale Circulating Fluidized Bed (CFB) reactor. The CFD model is based on Eulerian-Eulerian dispersed flow and solved using commercial software (ANSYS FLUENT). The DME-SR reactions scheme and kinetics in the presence of a bifunctional catalyst of CuO/ZnO/Al2O3+ZSM-5 were incorporated in the model using in-house developed user-defined function. The model was validated by comparing the predictions with experimental data from the literature. The results revealed for the first time detailed CFB reactor hydrodynamics, gas residence time, temperature distribution and product gas composition at a selected operating condition of 300 °C and steam to DME mass ratio of 3 (molar ratio of 7.62). The spatial variation in the gas species concentrations suggests the existence of three distinct reaction zones but limited temperature variations. The DME conversion and hydrogen yield were found to be 87% and 59% respectively, resulting in a product gas consisting of 72 mol% hydrogen. In part II of this study, the model presented here will be used to optimize the reactor design and study the effect of operating conditions on the reactor performance and products.

A hydrothermally stable transition alumina by condensation-enhanced self-assembly and pyrolysis crystallization:application in the steam reforming of methane

The preparation of a steam-based hydrothermally stable transition alumina is reported. The gel was derived from a synthetic sol-gel route where Al-tri-sec-butoxide is hydrolysed in the presence of a non-ionic surfactant (EO20PO70EO20), HCl as the catalyst and water (H2O/Al = 6); the condensation was enhanced by treating the hydrolysed gel with tetrabutylammonium hydroxide (TBAOH), after which it was dried at 60 °C by solvent evaporation. The so-obtained mesophase was crystallized under argon at 1200 °C (1 h) producing a transition alumina containing δ/α, and possibly θ, alumina phases. Due to its surface acidity, the pyrolysis conditions transform the block copolymer into a cross-linked char structure that embeds the alumina crystallites. Calcination at 650 °C generates a fully porous material by burning the char; a residual carbon of 0.2 wt.% was found, attributed to the formation of surface (oxy)carbides. As a result, this route produces a transition alumina formed by nanoparticles of about 30 nm in size on average, having surface areas in the range of 59-76 m2 g-1 with well-defined mesopores centered at 14 nm. The material withstands steam at 900 °C with a relative surface area rate loss lower than those reported for δ-aluminas, the state-of-the-art MSU-X γ-alumina and other pure γ-aluminas. The hydrothermal stability was confirmed under relevant CH4 steam reforming conditions after adding Ni; a much lower surface area decay and higher CH4 conversion compared to a state-of-the-art MSU-X based Ni catalyst were observed. Two effects are important in explaining the properties of such an alumina: the char protects the particles against sintering, however, the dominant effect is provided by the TBAOH treatment that makes the mesophase more resistant to coarsening and sintering. This journal is © the Partner Organisations 2014.

Bimetallic PtSn/C catalysts obtained via SOMC/M for glycerol steam reforming

A detailed study on the preparation of bimetallic PtSn/C catalysts using surface-controlled synthesis methods, and on their catalytic performance in the glycerol steam reforming reaction has been carried out. In order to obtain these well-defined bimetallic phases, techniques derived from Surface Organometallic Chemistry on Metals (SOMC/M) were used. The preparation process involved the reaction between an organometallic compound ((C4H9)4Sn) and a supported transition metal (Pt) in a H2 atmosphere. Catalysts with Sn/Pt atomic ratios of 0.2, 0.3, 0.5, and 0.7 were obtained, and characterized using several techniques: ICP, H2 chemisorption, TEM and XPS. These systems were tested in the glycerol steam reforming varying the reaction conditions (glycerol concentration and reaction temperature). The best performance was observed for the catalysts with the lowest tin contents (PtSn0.2/C and PtSn0.3/C). It was observed that the presence of tin increased the catalysts’ stability when working under more severe reaction conditions.

A computational model of hydrogen production by steam reforming of dimethyl ether in a large scale CFB reactor. Part II:parametric analysis

This study presents a computational parametric analysis of DME steam reforming in a large scale Circulating Fluidized Bed (CFB) reactor. The Computational Fluid Dynamic (CFD) model used, which is based on Eulerian-Eulerian dispersed flow, has been developed and validated in Part I of this study [1]. The effect of the reactor inlet configuration, gas residence time, inlet temperature and steam to DME ratio on the overall reactor performance and products have all been investigated. The results have shown that the use of double sided solid feeding system remarkable improvement in the flow uniformity, but with limited effect on the reactions and products. The temperature has been found to play a dominant role in increasing the DME conversion and the hydrogen yield. According to the parametric analysis, it is recommended to run the CFB reactor at around 300 °C inlet temperature, 5.5 steam to DME molar ratio, 4 s gas residence time and 37,104 ml gcat -1 h-1 space velocity. At these conditions, the DME conversion and hydrogen molar concentration in the product gas were both found to be around 80%.

Tailored mesoporous silica supports for Ni catalysed hydrogen production from ethanol steam reforming

Mesoporous silica supported Ni nanoparticles have been investigated for hydrogen production from ethanol steam reforming. Ethanol reforming is structure-sensitive over Ni, and also dependent on support mesostructure; three-dimensional KIT-6 possessing interconnected mesopores offers superior metal dispersion, steam reforming activity, and on-stream stability against deactivation compared with a two-dimensional SBA-15 support.

Synthesis Gas Generation by Chemical-Looping Reforming Using Ce-Based Oxygen Carriers Modified with Fe, Cu, and Mn Oxides

Chemical-looping reforming (CLR) is a technology that can be used for partial oxidation and steam reforming of hydrocarbon fuels. It involves the use of a metal oxide as an oxygen carrier, which transfers oxygen from combustion air to the fuel. Composite oxygen carriers of cerium oxide added with Fe, Cu, and Mn oxides were prepared by co-precipitation and investigated in a thermogravimetric analyzer and a fixed-bed reactor using methane as fuel and air as oxidizing gas. It was revealed that the addition of transition-metal oxides into cerium oxide can improve the reactivity of the Ce-based oxygen carrier. The three kinds of mixed oxides showed high CO and H-2 selectivity at above 800 degrees C. As for the Ce-Fe-O oxygen carrier, methane was converted to synthesis gas at a H-2/CO molar ratio close to 2:1 at a temperature of 800-900 degrees C; however, the methane thermolysis reaction was found on Ce-Cu-O and Ce-Mn-O oxygen carriers at 850-900 degrees C. Among the three kinds of oxygen carriers, Ce-Fe-O presented the best performance for methane CLR. On Ce-Fe-O oxygen carriers, the CO and H-2 selectivity decreased as the Fe content increased in the carrier particles. An optimal range of the Ce/Fe molar ratio is Ce/Fe > 1 for Ce-Fe-O oxygen carriers. Scanning electron microscopy (SEM) analysis revealed that the microstructure of the Ce-Fe-O oxides was not dramatically changed before and after 20 cyclic reactions. A small amount of Fe3C was found in the reacted Ce-Fe-O oxides by X-ray diffraction (XRD) analysis.

Mixed reforming of heptane to syngas in the Ba0.5Sr0.5Co0.8Fe0.2O3 membrane reactor

Fuel cells are recognized as the most promising new power generation technology, but hydrogen supply is still a problem. In our previous work, we have developed a LiLaNiO/gamma-Al2O3 catalyst, which is excellent not only for partial oxidation of hydrocarbons, but also for steam reforming and autothermal reforming. However, the reaction needs pure oxygen or air as oxidant. We have developed a dense oxygen permeable membrane Ba0.5Sr0.5Co0.8Fe0.2O3 which has an oxygen permeation flux around 11.5 ml/cm(2) min at reaction conditions. Therefore, this work is to combine the oxygen permeable membrane with the catalyst LiLaNiO/gamma-Al2O3 in a membrane reactor for hydrogen production by mixed reforming of heptane. Under optimized reaction conditions, a heptane conversion of 100%, a CO selectivity of 91-93% and a H-2 selectivity of 95-97% have been achieved. (c) 2005 Elsevier B.V. All rights reserved.

Autothermal reforming of n-octane on Ru-based catalysts

In an attempt to effectively integrate catalytic partial oxidation (CPO) and steam reforming (SR) reactions on the same catalyst, autothermal reforming (ATR) of n-octane was addressed based on thermodynamic analysis and carried out on a non-pyrophoric catalyst 0.3 wt.% Ru/K2O-CeO2/gamma-Al2O3. The ATR of n-octane was more efficient at the molar ratio Of O-2/C 0.35-0.45 and H2O/C 1.6-2.2 (independent parameters), respectively, and reforming temperature of 750-800 degrees C (dependent parameter). Among the sophisticated reaction network, the main reaction thread was deducted as: long-chain hydrocarbon -> CH4, short-chain hydrocarbon -> CO2, CO and H-2 formation by steam reforming, although the parallel CPO, decomposition and reverse water gas shift reaction took place on the same catalyst. Low temperature and high steam partial pressure had more positive effect on CH4 SR to produce CO2 other than CO. This was verified by the tendency of the outlet reformate to the equilibrium at different operation conditions. Furthermore, the loss of active components and the formation of stable but less active components in the catalyst in the harsh ATR atmosphere firstly make the CO inhibition capability suffer, then eventually aggravated the ATR performance, which was verified by the characterizations of X-ray fluorescence, BET specific surface areas and temperature programmed reduction. (c) 2005 Elsevier B.V. All rights reserved.

Biogas reforming using renewable wind energy and induction heating

While the benefits of renewable energy are well known and used to influence government policy there are a number of problems which arise from having significant quantities of renewable energies on an electricity grid. The most notable problem stems from their intermittent nature which is often out of phase with the demands of the end users. This requires the development of either efficient energy storage systems, e.g. battery technology, compressed air storage etc. or through the creation of demand side management units which can utilise power quickly for manufacturing operations. Herein a system performing the conversion of synthetic biogas to synthesis gas using wind power and an induction heating system is shown. This approach demonstrates the feasibility of such techniques for stabilising the electricity grid while also providing a robust means of energy storage. This exemplar is also applicable to the production of hydrogen from the steam reforming of natural gas.