TiO2/Al2O3 membrane reactor equipped with a methanol recovery unit to produce palm oil biodiesel

In this study, the central composite design of the response surface methodology was employed to investigate the effects of reaction temperature, catalyst concentration and cross flow circulation velocity on the production of biodiesel in a TiO₂/Al₂O₃ membrane reactor. High‐quality palm oil biodiesel was produced by combination of alkali transesterification and separation processes in the ceramic membrane reactor. The optimum conditions for the conversion of palm oil to biodiesel in the ceramic membrane reactor were as follows: 70°C reaction temperature, 1.12 wt% catalyst concentration and 0.211 cm s^{? 1} cross flow circulation velocity. The physical and chemical properties of the produced biodiesel were determined and compared with the standard specifications. Copyright © 2010 John Wiley & Sons, Ltd.     

Methanol steam reforming in an Al2O3 supported thin Pd-layer membrane reactor over Cu/ZnO/Al2O3 catalyst

In this experimental study, a membrane reactor housing a composite membrane constituted by a thin Pd-layer supported onto Al₂O₃ is utilized to perform methanol steam reforming reaction to produce high-grade hydrogen for PEM fuel cell applications. The influence of various parameters such as temperature, from 280 to 330 °C, and pressure, from 1.5 to 2.5 bar, is analyzed. A commercial Cu/Zn-based catalyst is packed in the annulus of the membrane reactor and the experimental tests are performed at space velocity equal to 18,500 h⁻¹ and H₂O:CH₃OH feed molar ratio equal to 2.5:1. Results in terms of methanol conversion, hydrogen recovery, hydrogen yield and products selectivities are given. As a best result of this work, 85% of methanol conversion and a highly pure hydrogen stream permeated through the membrane with a CO content lower than 10 ppm were reached at 330 °C and 2.5 bar. Furthermore, a comparison between the experimental results obtained in this work and literature data is proposed and discussed.     

Optimization of a fluidized bed reactor for methane decomposition over Fe/Al2O3 catalysts: Activity and regeneration studies

Catalytic methane decomposition was investigated over 40 wt% Fe/Al₂O₃ catalyst in fluidized bed reactor (FLBR). After optimization of FLBR conditions in terms of catalyst bulk density, particle size, minimum fluidization velocity, and the catalyst bed height, the catalyst activity and stability tests were conducted by comparison with a fixed bed reactor (FBR). Although a similar stable methane conversion was obtained over both reactors, the pressure drop during 35 min operation of FBR was 9 times higher than that of FLBR, which indicated the possibility of continuous operation of methane decomposition process over FLBR. Further, the influence of the space velocity, feed dilution and regeneration on catalysts reactivity was studied in FLBR to conclude that a reaction condition of 12 L/g_cat∙h, feed of 20%H₂–80%CH₄ and CO₂-regeneration of deactivated catalysts may be favourable for operating methane decomposition in FLBR continually and effectively to provide stable hydrogen.     

A CFD study on H2-permeable membrane reactor for methane CO2 reforming: Effect of catalyst bed volume

A 2D axisymmetric model is developed for a H₂-permeable membrane reactor for methane CO₂ reforming. The effect of catalyst bed volume on CH₄ conversion and H₂ permeation rate is investigated. The simulation results indicate that catalyst bed volume with a shell radius of 9 mm is optimal for a tubular Vycor glass membrane with a diameter of 10 mm and H₂ permeance of 2x10⁻⁶ mol/m²/Pa/s. The concentration polarization at the retentate side and the accumulation of H₂ at permeate side make it hard to extract the H₂ production at the zone far from the membrane surface. Though increasing pressure at the retentate side enhances H₂ permeation, CH₄ conversion is even decreased due to unfavorable thermodynamics. And increasing sweep gas flow rate at permeate side benefits to both CH₄ conversion and H₂ permeation. This work highlights the importance of determining the optimal catalyst bed volume to match the membrane in the design of membrane reactors.     

Real-time sensing of methane steam reforming by YSZ oxygen sensor

In this study, a new and convenient technique for the in-situ analyisis of methane steam reforming in the chamber was proposed. The YSZ oxygen sensor was used as the sensing device, which provided the partial pressure of oxygen in the reactor. The oxygen sensors were set in the catalytic bed of 1 wt.% Ni/Al₂O₃ along the gas flow direction and the progress of catalytic reforming was monitored at each position. The methane conversion derived from the oxygen sensor agreed well with that from the gas chromatograph set at the outlet part of the catalyst layer. Along the gas flow direction in the reactor, the change in the gas composition was clearly observed; the methane conversion changed significantly depending on the reaction temperature and space velocity of reactant gas. Furthermore, the deterioration behavior of catalytic activity was successfully monitiored when a highly humidified methane with a steam to carbon ratio of 4.0 was supplied with a high space velocity of 6250 l kg⁻¹ h⁻¹.     

Catalytic conversion of CO2 to biofuel (methanol) and downstream separation in membrane-integrated photoreactor system under suitable conditions

A heterogeneous photocatalyst has been developed using sono-chemical assisted sol-gel method by maintaining aweight ratio of 1:2:3 for hydrogen exfoliation graphene, titanium oxide andcopper sulphateand exhaustively characterized. Rigorous experimentations have been done using newly developed heterogeneous photocatalyst for efficient capturing and maximum conversion of carbon di oxide to methanol by mutual effects of governing conditions, like as catalyst dose, pH, CO₂ flow rate and temperature. Optimization study has been carried out employing a statistical approach of response surface methodology which reveals the maximum methanol productivity and yield. Approximately, 134 g/Lh of productivity and 40 mg/g_catof yield were found after 3 h of illumination under UV in an annular type Pyrex reactor at an optimum catalyst dosage of 10 g/L, CO₂ flow rate of 3 L/m, pH of 3, and process temperature of 50 °C. By the judicial integration of flat-sheet cross flow microfiltration membrane module for catalyst separation and recycle, a steady state permeate flux 145 L/m²h was achieved at an applied pressure of 3 bar and cross-flow feed rate of 700 L/h.     

Water–gas shift reaction in a Pd membrane reactor over Pt/Ce0.6Zr0.4O2 catalyst

A water–gas shift (WGS) Pt/Ce_0.6Zr_0.4O₂ catalyst has been prepared, which exhibits much faster kinetics than conventional high-temperature ferrochrome catalysts in the temperature range most suitable for operation of WGS Pd membrane reactors, i.e. above 623 K. The performance of the Pt catalyst was tested in a reactor furnished with a supported, 1.4 μm thick high-flux Pd membrane using feeds obtained by autothermal reforming of natural gas. CO conversion remained above thermodynamic equilibrium up to feed space velocities of 9100 l kg⁻¹ h⁻¹ at 623 K, P_total = 1.2 MPa and steam-to-carbon ratio S/C = 3, but H₂ recovery decreased from 84.8% at GHSV = 4050 l kg⁻¹ h⁻¹ to 48.7% at the highest space velocity. This rapid decline of separation performance is attributed to slow H₂ diffusion through the catalyst bed, suggesting that external mass flow resistance has a significant impact on the H₂ permeation rate in such membrane reactors. This could be minimized by the development of WGS catalysts with even faster kinetics which would allow further reduction of the catalyst bed height.     

Reforming of methanol with steam in a micro-reactor with Cu–SiO2 porous catalyst

In the present work, we report the results of a series of experiments for the hydrogen production via steam reforming of methanol with Cu–SiO₂ porous catalyst coated on the internal walls of a micro-reactor with parallel micro-passages. The catalyst was prepared by coating copper and silica nanoparticles on the internal surface of the microchannel via convective flow boiling heat transfer, followed by a calcination procedure at 973 K and therefore, the catalyst does not require any supportive material, which in turn reduced the complexity and cost of the preparation. The experiments were conducted at reactant flow rates of 0.1–0.9 lit/min, operating temperatures of 523–673 K, catalyst loading of 0.25 gr to 1.25 gr and at heat flux value of 500 kW/m². Results of the experiments showed that the methanol conversion can reach 97% at catalyst loading of 1.25 gr. It was also found that with an increase in the gas hourly space velocity (GHSV) of the reactants, the methanol conversion decreases, which was attributed to the decrease in the residence time, the suppression in diffusion of reactants into the pores of the catalyst, and also the decrease in the average film temperature of the reactor. The highest methanol conversion was obtained at gas hourly space velocity of 24,000 ml/(gr.hr) and T = 773 K and for molar ratio of methanol to water of 0.1. The molar ratio of methanol to water also influenced the thermal response of the reactor such that the surface temperature profile of the micro-reactor was more decreased at low methanol/water molar ratios.     

Utilization of CO2 for syngas production by CH4 partial oxidation using a catalytic membrane reactor

In this research, a synthetic flue gas mixture with added methane was used as the feed gas in the process of dry reforming with partial oxidation of methane using a laboratory scale catalytic membrane reactor to produce hydrogen and carbon monoxide that can present the starting point for methanol or ammonia synthesis and Fischer-Tropsch reactions. 0.5% wt% Rh catalyst was deposited on a γ-alumina support using rhodium (III) chloride precursor and incorporated into a shell and tube membrane reactor to measure the yield of synthesis gas (CO and H₂) and conversion of CH₄, O₂ and CO₂ respectively. These measurements were used to determine the reaction order and rate of CO₂. The conversion of CO₂ and CH₄ were determined at different gas hourly space velocities. The reaction order was determined to be a first-order with respect to CO₂. The rate of reaction for CO₂ was found to follow an Arrhenius equation having an activation energy of 49.88 × 10⁻¹ kJ mol⁻¹. Experiments were conducted at 2.5, 5 and 8 ml h⁻¹ g⁻¹ gas hourly space velocities and it was observed that increasing the hourly gas velocities resulted in a higher CO₂ and CH₄ conversions while O₂ conversion remained fairly constant. CO₂ had a high conversion rate of 96% at 8 ml h⁻¹ g⁻¹. The synthesized catalytic membrane was characterized by Scanning Electron Microscopy (SEM) and the Energy Dispersive X-ray Analysis (EDXA) respectively. The micrographs showed the Rh particles deposited on the alumina support. Single gas permeation of CH₄, CO₂ and H₂ through the alumina support showed that the permeance of H₂ increased as the pressure was increased to 1 × 10⁵ Pa. The order of gas permeance was H₂ (2.00 g/mol) > CH₄ (16.04 g/mol) > N₂ (28.01 g/mol) > O₂ (32 g/mol) > CO₂ (44.00 g/mol) which is indicative of Knudsen flow mechanism. The novelty of the work lies in the combination of exothermic partial oxidation and endothermic CO₂ and steam reforming in a single step in the membrane reactor to achieve near thermoneutrality while simultaneously consuming almost all the greenhouse gases in the feed gas stream.     

Experimental investigation on hydrogen production by methanol steam reforming in a novel multichannel micro packed bed reformer

A novel multichannel micro packed bed reactor with bifurcation inlet manifold and rectangular outlet manifold was developed to improve the methanol steam reforming performance in this study. The commercial CuO/ZnO/Al₂O₃ catalyst particles were directly packed in the reactor. The flow distribution uniformity in the reactor was optimized numerically. Experiments were conducted to study the influences of steam to carbon molar ratio (S/C), weight hourly space velocity (WHSV), reactor operating temperature (T) and catalyst particle size on the methanol conversion rate, H₂ production rate, CO concentration in the reformate, and CO₂ selectivity. The results show that increase of the S/C and T, as well as decrease of the WHSV and catalyst particle size, both enhance the methanol conversion. The CO concentration decreases as the S/C and WHSV increase as well as the T and catalyst particle size decrease. Moreover, T plays a more important role on the methanol steam reforming performance than WHSV and S/C. The impacts on CO concentration become insignificant when the S/C is higher than 1.3, WHSV is larger than 1.34 h⁻¹ and T is lower than 275 °C. A long term stability test of this reactor was also performed for 36 h and achieved high methanol conversion rate above 94.04% and low CO concentration less than 1.05% under specific operating conditions.     

Developing a mathematical model for reforming of glycerol towards a comparative evaluation of the liquid vs. gas phase medium

Glycerol might be converted into hydrogen through a catalytic reforming process. In order to design an effective route, the choice of reaction conditions and in particular its medium considered yet a crucial issue still needing further investigations. In this research, a mathematical model of reforming processes in vapor (i.e., steam reforming (SR) and liquid phase (i.e.; aqueous phase reforming (APR)) were developed. This was performed in terms of understudying effects of parameters including the reactor diameter, catalyst morphology (i.e., particle size) and mass flow rate on the glycerol conversion. Then, a superior reaction medium in terms of these variables was determined. For data validation, experimental values were adopted from glycerol reforming over Pt/CeZrO₂ catalyst with BET surface area of 81–102 m² g⁻¹, mean particle size of 5.29–7.18 nm and crystallinity of 40–53%. It was revealed that, for the same WHSV and reactor length, conversion of the APR was considerably more than that of the SR process. Moreover, it was demonstrated that, if the SR had to have the same conversion as that of the APR, the utilized reactor length should have approximately increased by about 80 folds for the liquid phase. Overall, this study provided a simple pathway through the developed model to comparatively evaluate the medium (i.e.; gaseous as in the SR vs. liquid as in the APR) for the glycerol conversion aiming at reducing experimental costs a head of going to the laboratory.     

Hydrogen production by reforming of liquid hydrocarbons in a membrane reactor for portable power generation—Experimental studies

One of the most promising technologies for lightweight, compact, portable power generation is proton exchange membrane (PEM) fuel cells. PEM fuel cells, however, require a source of pure hydrogen. Steam reforming of hydrocarbons in an integrated membrane reactor has potential to provide pure hydrogen in a compact system. Continuous separation of product hydrogen from the reforming gas mixture is expected to increase the yield of hydrogen significantly as predicted by model simulations. In the laboratory-scale experimental studies reported here steam reforming of liquid hydrocarbon fuels, butane, methanol and Clearlite^® was conducted to produce pure hydrogen in a single step membrane reformer using commercially available Pd–Ag foil membranes and reforming/WGS catalysts. All of the experimental results demonstrated increase in hydrocarbon conversion due to hydrogen separation when compared with the hydrocarbon conversion without any hydrogen separation. Increase in hydrogen recovery was also shown to result in corresponding increase in hydrocarbon conversion in these studies demonstrating the basic concept. The experiments also provided insight into the effect of individual variables such as pressure, temperature, gas space velocity, and steam to carbon ratio. Steam reforming of butane was found to be limited by reaction kinetics for the experimental conditions used: catalysts used, average gas space velocity, and the reactor characteristics of surface area to volume ratio. Steam reforming of methanol in the presence of only WGS catalyst on the other hand indicated that the membrane reactor performance was limited by membrane permeation, especially at lower temperatures and lower feed pressures due to slower reconstitution of CO and H₂ into methane thus maintaining high hydrogen partial pressures in the reacting gas mixture. The limited amount of data collected with steam reforming of Clearlite^® indicated very good match between theoretical predictions and experimental results indicating that the underlying assumption of the simple model of conversion of hydrocarbons to CO and H₂ followed by equilibrium reconstitution to methane appears to be reasonable one.     

Hydrogen production by steam methane reforming in a membrane reactor equipped with a Pd composite membrane deposited on a porous stainless steel

With the aim of producing hydrogen at low cost and with a high conversion efficiency, steam methane reforming (SMR) was carried out under moderate operating conditions in a Pd-based composite membrane reactor packed with a commercial Ru/Al₂O₃ catalyst. A Pd-based composite membrane with a thickness of 4–5 μm was prepared on a tubular stainless steel support (diameter of 12.7 mm, length of 450 mm) using electroless plating (ELP). The Pd-based composite membrane had a hydrogen permeance of 2.4 × 10^?3 mol m^?1 s^?1 Pa^?0.5 and an H₂/N₂ selectivity of 618 at a temperature of 823 K and a pressure difference of 10.1 kPa. The SMR test was conducted at 823 K with a steam-to-carbon ratio of 3.0 and gas hourly space velocity of 1000 h^?1; increasing the pressure difference resulted in enhanced methane conversion, which reached 82% at a pressure difference of 912 kPa. To propose a guideline for membrane design, a process simulation was conducted for conversion enhancement as a function of pressure difference using Aspen HYSYS^®. A stability test for SMR was conducted for ～120 h; the methane conversion, hydrogen production rate, and gas composition were monitored. During the SMR test, the carbon monoxide concentration in the total reformed stream was <1%, indicating that a series of water gas shift reactors was not needed in our membrane reactor system.     

Design of a methane processing system producing high-purity hydrogen

Design of a catalytic methane-to-proton exchange membrane fuel cell (PEMFC) grade hydrogen conversion system consisting of indirect partial oxidation (IPOX), water–gas shift (WGS) and preferential carbon monoxide oxidation (PROX) reactors is investigated using modeling and simulation techniques. Steady-state simulation, design and sizing of reactors, which are considered to be packed-bed tubular type, are carried out for twelve different feed composition and PEMFC power output configurations, namely (CH₄/O₂, H₂O/CH₄) = (2.24, 1.17), (1.89, 1.56) and (10, 50, 100, 500, 1000, 1500 W). For every configuration, material balance calculations are executed to obtain the flow rates of each species at each stream. These results are then used as boundary conditions to estimate the catalyst weights in each reactor via simulations conducted using a one-dimensional pseudo-homogeneous reactor model. Finally, reactor and catalyst particle dimensions are estimated by considering pressure drop and a set of criteria to quantify interfacial heat and intraparticle mass transfer resistances and fluid flow characteristics in packed beds. The total catalyst quantity is found to increase almost linearly with the PEMFC power output at both feed compositions. Total system volume, excluding piping, pumping, heat exchange and other peripheral units, is estimated to be 6.3, 40.3, 83.4, 488, 985 and 1527 cm³ for 10, 50, 100, 500, 1000 and 1500 W operations, respectively. WGS unit requires the highest space corresponding to ca. 50% of the total reactor volume, followed by IPOX (ca. 39%) and PROX (ca. 11%) reactors. Power densities, based on the weight and volume of the reactors are estimated as 1.1 kW/kg and 1.2 kW/l, respectively.     

Evaluation of a micro-channel reactor for steam reforming of ethylene glycol: A comparative study of catalytic activity of Pt or/and Ni supported γ-alumina catalysts

Steam reforming of ethylene glycol (EG) was studied using γ-alumina supported 12%Ni, 3%Pt and 3%Pt12%Ni catalysts, in a micro-channel reactor. The parallel micro-channels were etched on a stainless steel plate using micro-milling technique with high speed CNC machine. The catalysts were prepared by the incipient wetness impregnation method and were characterized by using XRD, BET, FE-SEM, H₂-TPR and TGA analyses. The effects of reaction temperature and feed flow rate on the EG conversion, hydrogen yield and selectivities of the gaseous products were investigated. Experimental findings revealed that 3%Pt12%Ni/γ-alumina catalyst can provide the highest EG conversion (96.1%) with 76.6% hydrogen yield and 5.3% CO selectivity at 450 °C temperature and 4 mL h^?1 feed flow rate. Furthermore, continuous EG steam reforming identified 3%Pt12%Ni/γ-alumina as the most stable catalyst. This catalyst can remain stable after being on stream for more than 20 h.     

An investigation on the performance of a FTS fixed-bed reactor using CFD methods

In the present work, a numerical model was developed and validated in order to simulate and improve the conversion of synthesis gas (CO + H₂) to higher hydrocarbons in a Fischer–Tropsch Synthesis (FTS) fixed-bed reactor. The reactor was a 3.1 cm diameter and 2.75 m length steel tube in which saturated water was employed to control the peak temperature within the catalyst bed. A 2-D CFD model with an optimized mesh of 22,016 square cells was developed to model hydrodynamics, chemical reaction, non-ideality of the mixture, heat and mass transfer in the reactor. Good agreement was achieved between pilot experimental data and the model. The result showed that adjusting the boiling water flow rate in the range of 25–250 g.min^{– 1} allows maintaining the FTS temperature at suitable values. An optimum value of 573 K was obtained for feed temperature.     

Parametric study of the decomposition of methane using a NiCu/Al2O3 catalyst in a fluidized bed reactor

CO₂-free production of hydrogen via catalytic decomposition of methane (CDM) was studied in a fluidized bed reactor (FBR) using a NiCu/Al₂O₃ catalyst. A parametric study of the effects of some process variables, including catalyst particle size, reaction temperature, space velocity and the ratio of gas flow velocity to the minimum fluidization velocity (u_o/u_mf), was undertaken. A mean particle size of 150 μm allows optimization of results in terms of hydrogen production without agglomeration problems. The operating conditions strongly affect the catalyst performance: hydrogen production was enhanced by increasing operating temperature and lowering space velocity. However, increases in operating temperature, space velocity and the ratio u_o/u_mf provoked increases in the catalyst deactivation rate. At 700 °C, carbon was deposited as carbon nanofibers, while higher temperatures promoted the formation of encapsulating carbon, which led to rapid catalyst deactivation.     

Performance of a miniaturized silicon reformer-PrOx-fuel cell system

A fuel cell made with silicon is operated with hydrogen supplied by a reformer and a preferential oxidation (PrOx) reactor those are also made with silicon. The performance and durability of the fuel cell is analyzed and tested, then compared with the results obtained with pure hydrogen. Three components of the system are made using silicon technologies and micro electro-mechanical system (MEMS) technology. The commercial Cu-ZnO-Al₂O₃ catalyst for the reformer and the Pt-Al₂O₃ catalyst for the PrOx reactor are coated by means of a fill-and-dry method. A conventional membrane electrode assembly composed of a 0.375 mg cm⁻² PtRu/C catalyst for the anode, a 0.4 mg cm⁻² Pt/C catalyst for the cathode, and a Nafion™ 112 membrane is introduced to the fuel cell. The reformer gives a 27 cm³ min⁻¹ gas production rate with 3177 ppm CO concentration at a 1 cm³ h⁻¹ methanol feed rate and the PrOx reactor shows almost 100% CO conversion under the experimental conditions. Fuel cells operated with this fuel-processing system produce 230 mW cm⁻² at 0.6 V, which is similar to that obtained with pure hydrogen.     

H2 production via water gas shift in a composite Pd membrane reactor prepared by the pore-plating method

In this work, H₂ production via catalytic water gas shift reaction in a composite Pd membrane reactor prepared by the ELP “pore-plating” method has been carried out. A completely dense membrane with a Pd thickness of about 10.2 μm over oxidized porous stainless steel support has been prepared. Firstly, permeation measurements with pure gases (H₂ and N₂) and mixtures (H₂ with N_2, CO or CO₂) at four different temperatures (ranging from 350 to 450 °C) and trans-membrane pressure differences up to 2.5 bar have been carried out. The hydrogen permeance when feeding pure hydrogen is within the range 2.68–3.96·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5, while it decreases until 0.66–1.35·10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 for gas mixtures. Furthermore, the membrane has been also tested in a WGS membrane reactor packed with a commercial oxide Fe–Cr catalyst by using a typical methane reformer outlet (dry basis: 70%H₂–18%CO–12%CO₂) and a stoichiometric H₂O/CO ratio. The performance of the reactor was evaluated in terms of CO conversion at different temperatures (ranging from 350 °C to 400 °C) and trans-membrane pressures (from 2.0 to 3.0 bar), at fixed gas hourly space velocity (GHSV) of 5000 h⁻¹. At these conditions, the membrane maintained its integrity and the membrane reactor was able to achieve up to the 59% of CO conversion as compared with 32% of CO conversion reached with conventional packed-bed reactor at the same operating conditions.     

Hydrogen-rich gas production from oxygen pressurized gasification of biomass using a Fe–Cr Water Gas Shift catalyst

In this paper the catalytic activity of a Fe–Cr WGS catalyst is evaluated in terms of CO conversion and H₂ production. The experimental study has been carried out under realistic conditions typical of oxygen pressurized gasification of biomass. The influence of temperature, excess steam, feed gas composition and space velocity on the activity and selectivity of the catalyst for the WGS reaction is investigated. The experimental work was carried out in a micro reactor testing unit using synthetic gas feed mixtures.