Comparison of experimental and simulation results on catalytic HI decomposition in a silica-based ceramic membrane reactor

In this study, the catalytic decomposition of hydrogen iodide was theoretically and experimentally investigated in a silica-based ceramic membrane reactor to assess the reactor's suitability for thermochemical hydrogen production. The silica membranes were fabricated by depositing a thin silica layer onto the surface of porous alumina ceramic support tubes via counter-diffusion chemical vapor deposition of hexyltrimethoxysilane. The performance of the silica-based ceramic membrane reactor was evaluated by exploring important operating parameters such as the flow rates of the hydrogen iodide feed and the nitrogen sweep gas. The influence of the flow rates on the hydrogen iodide decomposition conversion was investigated in the lower range of the investigated feed flow rates and in the higher range of the sweep-gas flow rates. The experimental data agreed with the simulation results reasonably well, and both highlighted the possibility of achieving a conversion greater than 0.70 at decomposition temperature of 400 °C. Therefore, the developed silica-based ceramic membrane reactor could enhance the total thermal efficiency of the thermochemical process.     

Experimental study on sulfur trioxide decomposition in a volumetric solar receiver–reactor

Process conditions for the direct solar decomposition of sulfur trioxide have been investigated and optimized by using a receiver–reactor in a solar furnace. This decomposition reaction is a key step to couple concentrated solar radiation or solar high‐temperature heat into promising sulfur‐based thermochemical cycles for solar production of hydrogen from water. After proof‐of‐principle a modified design of the reactor was applied. A separated chamber for the evaporation of the sulfuric acid, which is the precursor of sulfur trioxide in the mentioned thermochemical cycles, a higher mass flow of reactants, an independent control and optimization of the decomposition reactor were possible. Higher mass flows of the reactants improve the reactor efficiency because energy losses are almost independent of the mass flow due to the predominant contribution of re‐radiation losses. The influence of absorber temperature, mass flow, reactant initial concentration, acid concentration, and residence time on sulfur trioxide conversion and reactor efficiency has been investigated systematically. The experimental investigation was accompanied by energy balancing of the reactor for typical operational points. The absorber temperature turned out to be the most important parameter with respect to both conversion and efficiency. When the reactor was applied for solar sulfur trioxide decomposition only, reactor efficiencies of up to 40% were achieved at average absorber temperature well below 1000°C. High conversions almost up to the maximum achievable conversion determined by thermodynamic equilibrium were achieved. As the re‐radiation of the absorber is the main contribution to energy losses of the reactor, a cavity design is predicted to be the preferable way to further raise the efficiency. Copyright © 2009 John Wiley & Sons, Ltd.     

Module design of silica membrane reactor for hydrogen production via thermochemical IS process

The potential of the silica membrane reactors for use in the decomposition of hydrogen iodide (HI) was investigated by simulation with the aim of producing CO₂-free hydrogen via the thermochemical water-splitting iodine-sulfur process. Simulation model validation was done using the data derived from an experimental membrane reactor. The simulated results showed good agreement with the experimental findings. The important process parameters determining the performance of the membrane reactor used for HI decomposition, namely, reaction temperature, total pressures on both the feed side and the permeate side, and HI feed flow rate were investigated theoritically by means of a simulation. It was found that the conversion of HI decomposition can be improved by up to four times (80%) or greater than the equilibrium conversion (20%) at 400 °C by employing a membrane reactor equipped with a tubular silica membrane. The features to design the membrane reactor module for HI decomposition of the thermochemical iodine-sulfur process were discussed under a wide range of operation conditions by evaluating the relationship between HI conversion and number of membrane tubes.     

A novel tubular membrane reactor for pure hydrogen production in the synthesis of formaldehyde by the silver catalyst process

Formaldehyde-based chemistry plays a significant role in the production of different materials. In this work, attempts have been made to revamp a silver catalyzed formaldehyde plant by applying membrane technology. The conventional silver catalyst packed bed reactor was replaced by a shell and tube membrane reactor. A steady-state one-dimensional model was applied to evaluate the performance of the proposed membrane process. The model was validated with experimental results from the plant.The effects of various parameters including reactor pressure, feed temperature, and membrane thickness on the membrane reactor were investigated. Results showed that the effect of feed temperature on production rates was negligible. The increase in pressure and decrease in membrane thickness, however, leads to increase products. The simultaneous production of 100 tonnes/day of formalin 37% (37 wt% formaldehyde in water) and 500 kg/day pure hydrogen achieved by the proposed process. Furthermore, the exiting reactor temperature can be reduced to 420 °C which is significantly lower than the conventional method (650 °C).     

Application of catalytic membrane reactor for pure hydrogen production by flare gas recovery as a novel approach

In the present study, application of catalytic membrane reactor as a novel approach for the flare gas recovery is proposed. A comprehensive two-dimensional non-isothermal model has been constructed to evaluate the performance of flare gas recovery process in the membrane reactor. The model is developed by taking into accounts the main chemical kinetics, heat and mass transfer phenomena and hydrogen permeation in the radial direction across a Pd–Ag membrane. The model predictions are validated based on different experimental results reported in literature. The impact of reactor operating conditions on the recovery process such as temperature and pressure, feed molar ratio and sweep gas ratio are investigated and discussed. The modeling results confirm that the flare gas conversion and hydrogen recovery improves with increasing the operating temperature, pressure and sweep ratio as a consequence of increasing the driving force for H₂ permeation through membrane. The environmental consideration revealed that by application of catalytic membrane reactor for the flare gas recovery of Asalouyeh gas processing plant (Iran), not only the equivalent mass of greenhouse gases emission reduces from 2179 kg/s to 36 kg/s, but also, 12.7 kg/s pure hydrogen will be produced by flare gas recovery at 750 K, 5 bar, sweep ratio of 5 and feed molar ratio of 4.     

Tube-wall catalytic membrane reactor for hydrogen production by low-temperature ammonia decomposition

Ammonia has attracted great interest as a chemical hydrogen carrier. However, ammonia decomposition is limited kinetically rather than thermodynamically below 400 °C. We developed a tube-wall catalytic membrane reactor that could decompose ammonia with high conversion even at temperatures below 400 °C. The reactor had excellent heat transfer characteristics, and thus nearly 100% conversion for an NH3 feed of 10 mL/min at 375 °C was achieved with a 2-μm-thick palladium composite membrane, and hydrogen removal from the decomposition side resulted in a large kinetic acceleration.     

Application of aspen plus to renewable hydrogen production from glycerol by steam reforming

Steam reforming is the most favored method for the production of hydrogen. Hydrogen is mostly manufactured by using steam reforming of natural gas. Due to the negative environmental impact and energy politics, alternative hydrogen production methods are being explored. Glycerol is one of the bio-based alternative feedstock for hydrogen production. This study is aimed to simulate hydrogen production from glycerol by using Aspen Plus. First of all, the convenient reactor type was determined. RPlug reactor exhibited the highest performance for the hydrogen production. A thermodynamic model was determined according to the formation of byproduct. The reaction temperature, water/glycerol molar feed ratio as reaction parameters and reactor pressure were investigated on the conversion of glycerol and yield of hydrogen. Optimum reaction parameters are determined as 500 °C of reaction temperature, 9:1 of water to glycerol ratio and 1 atm of pressure. Reactor design was also examined. Optimum reactor diameter and reactor length values were determined as 5 m and 50 m, respectively. Hydrogen purification was studied and 99.9% purity of H₂was obtained at 25 bar and 40 °C. The obtained results were shown that Aspen Plus has been successfully applied to investigate the effects of reaction parameters and reactor sizing for hydrogen production from glycerol steam reforming.     

Differential evolution (DE) strategy for optimization of methane steam reforming and hydrogenation of nitrobenzene in a hydrogen perm‐selective membrane thermally coupled reactor

In this work, a thermally coupled membrane reactor is proposed for methane steam reforming and hydrogenation of nitrobenzene. The steam reforming process is carried out in the assisted membrane surface of the endothermic side, while the hydrogenation reaction of nitrobenzene to aniline is carried out on the other membrane surface of the exothermic side. The differential evolution (DE) strategy is applied to optimize this reactor considering nitrobenzene and methane conversion as the main objectives. The co‐current mode is investigated in this study, and the achieved optimization results are compared with those of conventional steam reformer reactor operated under the same feed conditions. The optimum values of feed temperature of exothermic side, feed molar flow rate of nitrobenzene, the steam‐to‐nitrobenzene molar ratio and the hydrogen‐to‐nitrobenzene molar ratio are determined during the optimization process. The simulation results show that the methane conversion and consequently hydrogen recovery yield are increased by 39.3% and 1.57, respectively, which contribute to aniline production with 27.3% saving in hydrogen supply from external and a reduction in environmental problems due to 100% nitrobenzene conversion. The optimization results justify the feasibility of coupling these reactions. Experimental proof‐of‐concept is needed to establish the validity and safe operation of the novel reactor. Copyright © 2012 John Wiley & Sons, Ltd.     

DDR zeolite membrane reactor for enhanced HI decomposition in IS thermochemical process

The third section of closed loop Iodine Sulphur (IS) thermochemical cycle, dealing with HI_x processing, suffers from low equilibrium decomposition of HI to hydrogen with a conversion value of only ～22% at 700 K. Here, we report a significant enhancement in conversion of HI into hydrogen (up to ～95%) using a zeolite membrane reactor for the first time. The all silica DDR (deca dodecasil rhombohedral) zeolite membrane with dense, interlocked structure was synthesized on the seeded clay alumina substrate by sonication mediated hydrothermal process. The synthesized membranes along with seed crystals were characterized by X-ray diffraction (XRD), field emission scanning electron microscope (FESEM) and energy dispersive X-ray spectroscopy (EDX). Corrosion studies were carried out by exposing the membrane samples to simulated HI decomposition reaction environment (at 450 °C) for different durations of time upto 200 h. The FESEM, EDX and XRD analyses indicated that no significant changes occurred in the morphology, composition and structure of the membranes. Iodine adsorption on to the membrane surface was observed which got increased with the exposure duration as confirmed by secondary ion mass spectrometry studies. A packed bed membrane reactor (PBMR) assembly was fabricated with integration of in-house synthesized zeolite membrane and Pt-alumina catalyst for carrying out HI decomposition studies. The tube side was chosen as reaction zone and the shell side as the permeation zone. The HI decomposition experiments were carried out for different values of temperature and feed flow rates. DDR zeolite based PBMR was found to enhance the single-pass conversion of HI up to ～95%. The results indicate that for achieving optimal performance of PBMR, it should be operated with space velocities of 0.2–0.3 s^?1 and temperature in the range of 650 K–700 K with permeate side vacuum of 0.12 kg/cm². It is believed that the in-house developed zeolite PBMR shall be a potential technology augmentation in making the IS thermochemical cycle energy efficient.     

Numerical analysis of operation conditions and design aspects of a sulfur trioxide decomposer for solar energy conversion

A basic concept for a receiver–reactor for solar sulfuric acid decomposition as the key step of the Hybrid Sulfur Cycle for hydrogen production has been developed and realized. A prototype reactor has been built and is specialized for the second part of the reaction, the decomposition of sulfur trioxide. For a detailed understanding of the operational behavior of the developed reactor type a mathematical model was developed. The reactor model was validated using experimental data from the test operation with a prototype reactor. The present work deals with the optimization of process and design parameters and the evaluation of the achievable performance of the reactor type. Furthermore the reactor model is used for numerical simulations to predict specific operational points of the prototype reactor and the performance of a large‐scale reactor on a solar tower. Influences of operational parameters like absorber temperature, feed mass flow, residence time and initial concentration of the acid are analyzed. In many cases those analyses reveal the existence of an optimum of reactor efficiency. When varying the absorber temperature an optimum of reactor efficiency emerges due to two compensating effects: chemical conversion increases with temperature, whereas re‐radiation losses increase disproportionately at the same time. This matches the experimental findings very well. A large‐scale tower receiver–reactor consisting of several individual modules is modeled and simulated. The main differences to the prototype system are the reduced gradients of solar flux distribution on the receiver front face and the reduced thermal conduction losses due to the presence of several neighbor modules at a comparable temperature level. This leads to higher chemical conversions and better efficiencies. Reactor efficiencies up to 75% are predicted. Copyright © 2011 John Wiley & Sons, Ltd.     

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.     

Experimental investigation of the effect of physical pre-treatment on air-blown fluidized bed biomass gasification

The effect of comminution, drying, and densification on bubbling fluidized bed gasification was investigated by fractionating a forestry residue into a feedstock consisting of different particle sizes, moisture levels, and by densifying to pellets. The gasification performance was evaluated at nominal average bed temperatures of 725°, 800° and 875 °C at a constant fluidizing velocity (0.91 m s⁻¹) with feed input rates between 9 and 24 kg h⁻¹.The gas composition was observed to be influenced by both the particle size and form. Smaller particles led to a gas richer in carbon monoxide and depleted in hydrogen. The gasification of pellets led to a gas with the greatest hydrogen to carbon monoxide ratio. The smallest particles tested resulted in the worst gasification performance, as defined by cold gas efficiency, carbon conversion, and tar production. Despite differences in the gas composition among the larger particles and the pellets, similar carbon conversion and cold gas efficiency was observed.Relative to comparable test conditions with dry feed fractions (having a moisture mass fraction of 7–12%), an average 11% increase in carbon conversion was observed for the wetter feed fractions containing a moisture mass fraction of 24–31%. This increase in carbon conversion offset much of the expected decrease in cold gas efficiency by using a wetter feed material. A slight increase in hydrogen production and negligible change in tar production was observed for the wetter feed fractions relative to the dry feed fraction.     

A study of methanol steam reforming on distributed catalyst bed

Heterogeneous catalytic fixed bed usually suffers from severe limitations of mass and heat transfer. These disadvantages limit reformers to a low efficiency of catalyst utilization. Three catalyst activity distributions have been applied to force the reactor temperature profile to be near isothermal operation for maximization of methanol conversion. A plate-type reactor has been developed to investigate the influence of catalyst activity distribution on methanol steam reforming. Cold spot temperature gradients are observed in the temperature profile along the reactor axis. It has been experimentally verified that reducing cold spot temperature gradients contributes to the improvement of the catalytic hydrogen production. The lowest cold spot temperature gradient of 3 K is obtained on gradient catalyst distribution type A. This is attributed to good characteristics of local thermal effect. Low activity at the reactor inlet with gradual rise along with the reactor flow channel forms the optimal activity distribution. Hydrogen production rate of 161.3 L/h is obtained at the methanol conversion of 93.1% for the gradient distribution type A when the inlet temperature is 543 K.     

Simulation analysis of methanol flash distillation circulation process in biodiesel production with supercritical method

High methanol-to-oil ratio is required to obtain a high conversion of oil for the production of biodiesel with supercritical methanol. Recovering the methanol of a stream issuing from a transesterification supercritical reactor by flash distillation instead of evaporation was analyzed. The one-stage and two-stage flash distillation processes were presented and compared. The difference of the recovery percentage of methanol of the above two flash processes is less than 0.5% and the methanol concentration in the vapor for the one-stage process decreases rapidly when feed temperature increases. The process in which the product of transesterification of soybean oil with supercritical methanol is cooled to an appropriate temperature (about 240°C) first and then flashed was put forward. The effect of cooling temperature, feed pressure and flash pressure on methanol concentration and recovery percentage was investigated. According to this study, when the feed pressure range is 15–30 MPa, the flash pressure equals 0.4 MPa, and cooling temperature range is 240°C–250°C, the recovery percentage of methanol is not less than 85%, and the concentration of the vapor in mass fraction of methanol is approximately 99%. Thus, the vapor leaving the flash tank can be directly circulated to the transesterification reactor.     

A comparison of hydrogen and methanol production in a thermally coupled membrane reactor for co‐current and counter‐current flows

This work considers three concentric tube reactors to prepare pure hydrogen, especially applicable in fuel cell technologies, with zero CO₂ emission. Hydrogen and methanol production rates are compared in a thermally coupled exothermic and endothermic reactor for co‐current and counter‐current modes. Synthesis of methanol is coupled with dehydrogenation of cyclohexane as a high content hydrogen carrier (7.1 wt%). The efficient coupling of exothermic and endothermic reactions increases the profitability of operation of the reactor, reduces the size of reactor and decreases the operational and capital costs. By inserting a hydrogen‐perm selective membrane into the reactor configuration, hydrogen can permeate selectively into the membrane, and hence, the third tube receives hydrogen. The simulation results are compared with the corresponded results for an industrial methanol fixed‐bed reactor, which operates under the same feed conditions. The influence of some operating variables is investigated on methanol and hydrogen yields during the performance of reactor. The results show higher methanol conversion, as the same as conventional reactor, and hydrogen for co‐current flow. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydrogen production from the methanolysis of ammonia borane by Pd-Co/Al2O3 coated monolithic catalyst

The aim of this study is to enable high hydrogen production yield from catalytic methanolysis of ammonia borane (AB) in the presence of a cordierite type ceramic monolithic. The monolithic channel surfaces were coated with Al₂O₃ by wash-coating method and then this layer was impregnated with 1 wt%Pd-2 wt%Co bimetallic catalyst. SEM-EDX and multi-point BET analysis were used in order to characterize the catalyst. The experimental studies were conducted in a continuous flow type reactor, which was used for the first time in this study. The reactions were carried on low temperature (40 °C), and with various AB feed concentrations and flow rates. It was found that the highest hydrogen production yield (88.5%) was obtained from AB flow rate of 3.3 mL/min, and AB feed concentration of 0.1 wt%. It was concluded that Pd-Co/Al₂O₃ coated monolithic, which is a stable, active and low-cost catalyst, was a very promising catalyst for on-board hydrogen production from the methanolysis of ammonia borane.     

Hydrogen production from aqueous-phase reforming of sorghum biomass: An application of the response surface methodology

Aqueous-phase reforming (APR) of sorghum hydrolyzate was performed in a fixed bed reactor applying response surface methodology (RSM) based on the Box–Behnken design (BBD) to produce hydrogen gas. The results showed that RSM based on the BBD was a well-matched method for optimizing of APR of sorghum hydrolyzate. The independent variables such as interactive effects of temperature, feed flow rate, and carbon content of sorghum hydrolyzate on the APR were investigated. The mathematical model and experimental results showed that the operation temperature was the main positive linear effect whereas the interaction between temperature and feed flow rate was the main negative linear effect on the hydrogen yield. The highest hydrogen production was found to be a temperature of 270 °C, a hydrolyzate flow rate of 0.30 mL/min, and a carbon content of biomass concentration of 2500 mg/L. The highest H₂/CO₂ mole ratio (7.9) obtained at 270 °C when carbon content of sorghum hydrolyzate was 1000 mg/L.     

Hydrogen production by aqueous phase catalytic reforming of glycerine

Hydrogen is believed to be the one of the main energy carriers in the near future. In this research glycerine, which is produced in large quantities as a by-product of biodiesel process, was converted to hydrogen aiming to contribute to clean energy initiative. Conversion of glycerol to hydrogen was achieved via aqueous-phase reforming (APR) with Pt/Al₂O₃ catalyst. The experiments were carried out in an autoclave reactor and a continuous fixed-bed reactor. The effects of reaction temperature (160-280 °C), feed flow rate (0.05-0.5 mL/dak) and feed concentration (5-85 wt-% glycerine) on product distribution were investigated. Optimum temperature for hydrogen production with APR was determined as 230 °C. Maximum gas production rate was found at the feed flow rates around 0.1 mL/min. It was also found that hydrogen concentration in the gas product increased with decreasing glycerol concentration in the feed.     

Biomass-derived CO2 rich syngas conversion to higher hydrocarbon via Fischer-Tropsch process over Fe–Co bimetallic catalyst

Biomass-derived syngas (CO₂ + CO + H₂) has emerged as a potential non-fossil fuel source to yield transportation fuel via Fischer Tropsch Synthesis (FTS) reaction. Thus, the present study demonstrates the conversion of CO₂ containing syngas into fuel range hydrocarbon via Fischer Tropsch Synthesis over Fe–Co bimetallic catalyst. The experimental tests were carried out in a fixed bed continuous reactor to investigate the effect of CO₂ on CO/CO₂ conversion. Accordingly, obtained data were validated by FTS kinetic model for a plug flow reactor. It was found that the unique combination of Fe and Co bimetallic catalyst facilitates both FTS and water gas shift (WGS) reaction simultaneously that helps to convert CO₂ along with CO. It was also observed that the presence of iron in the catalyst helps in conversion of CO₂ into hydrocarbons, only when a particular concentration of CO₂ in syngas is reached, i.e., critical ratio R_C (CO₂/CO + CO₂) due to the occurrence of reverse water gas reaction (RWGS) which varies with the temperature and the feed gas composition (H₂/CO/CO₂ molar ratio). At 240 °C and hydrogen deficient condition, the critical ratio was measured to be 0.74 whereas for hydrogen balanced condition, it was measured 0.6. The kinetic model developed in the present study predicted trends for % CO conversion, % carbon conversion, and % CO₂ conversion which is applicable for a wide range of critical ratio R_C (CO₂/(CO + CO₂) = 0 to 1). The model also predicted that a positive conversion of CO₂ could be achieved at lower CO₂ concentration by increasing the reaction temperature. At 260 °C and 280 °C, the value of Rc were 0.31 and 0.18 were measured.     

The use of inert porous media based reactors for hydrogen production

The present review paper examines the production of hydrogen in inert porous media based reformer by thermal partial oxidation. Here we consider, specifically, the rich combustion of hydrocarbon fuels and the conversion of H₂S to hydrogen. The different technologies to produce hydrogen beside the experimental and numerical work done in this field are presented. The effect of different operating conditions, such as the equivalence ratio, the mass flow rate and the reactant feed temperature are explained. Additionally, design parameters, including the reactor geometry and porous material specifications, are discussed.