Hydrogen production from waste activated sludge by using separation membrane acid fermentation reactor and photosynthetic reactor

The possibility and characteristics of hydrogen production from waste activated sludge were investigated using separation membrane acid fermentation reactor (AR) and photosynthetic reactor (PR). The AR used submerged and external separation membranes and it was followed by the PR. The COD removal efficiencies in the AR with submerged and external separation membrane were about 65% and 40%, respectively. More VFA was produced in the AR with external separation membrane than AR with submerged separation membrane. Hydrogen was produced in the PR but not in the AR and hydrogen productions in the PR connected with submerged membrane AR and external membrane AR were about 50.1 and 160.5 ml _H2/g${\mathrm{H}}_2/\mathrm{g}$ T-VFA, respectively.     

Hydrogen production and carbon dioxide enrichment using a catalytic membrane reactor with Ni metal catalyst and Pd-based membrane

We prepared a catalytic membrane reactor (CMR) by adopting a high-performance metal catalyst and Pd–Au membrane to investigate the possibility of hydrogen production concurrently with carbon dioxide enrichment (up to >80%) in a single-stage reactor from a simulated syngas of a coal gasification, via simultaneous WGS reaction and hydrogen separation process. The CO conversion was above 99% and the H₂ recovery was above 94% at del-P = 30 bar in a CMR. The best result for the concentration of the enriched CO₂ in the retentate side was 85.3% under the conditions of 350 °C, del-P = 30 bar and steam to carbon ratio of 2.0. These results show promise for a feasible simplified process able to achieve CO removal from a high-concentration CO mixture gas coming out of coal gasification via a water-gas shift reaction (WGS), to separate hydrogen and also to enrich CO₂ for pre-combustion capture and storage of CO₂ (CCS) in substitution for the conventional WGS and CO₂ separation stages in integrated gasification and combined cycle process integrated with CCS.     

Production of synthesis gas by co-gasifying coke and natural gas in a fixed bed reactor

The production of synthesis gas has gained increasing importance because of its use as raw material for various industrial syntheses. In this paper synthesis gas generation during the reaction of a coal/methane with steam and oxygen, which is called the co-gasification of coal and natural gas, was investigated using a laboratory scale fixed bed reactor. It is found that about 95% methane conversion and 80% steam decomposition have been achieved when the space velocity of input gas (oxygen and methane) is less than 200 h⁻¹ and reaction temperature about 1000 °C. The product gas contains about 95% carbon monoxide and hydrogen. The reaction system is near the equilibrium when leaving the reactor.     

Hydrogen production with integrated CO2 capture in a membrane assisted gas switching reforming reactor: Proof-of-Concept

This paper presents a new membrane reactor concept for ultra-pure hydrogen production with integrated CO₂ capture: the membrane-assisted gas switching reforming (MA-GSR). This concept integrates alternating exothermic and endothermic redox reaction stages in a single fluidized bed consisting of catalytically active oxygen-carrier particles, by switching the feed between air and methane/steam, where the produced hydrogen is selectively removed via Pd-based membranes. This concept results in overall autothermal conditions and allows easier operation at high pressure compared to alternative novel technologies. In this work, the MA-GSR concept is demonstrated at lab scale using four metallic supported membranes (Pd–Ag based) immersed into a fluidized bed consisting of a Ni-based oxygen carrier. The performance of the reactor has been tested under different experimental operating conditions and high methane conversions (>50%) have been obtained, well above the thermodynamic equilibrium conversion of a conventional fluidized bed as a result of the selective H₂ extraction, with (ultra-pure) H₂ recoveries above 20% at relatively low temperatures (<550 °C). These results could be further improved by working at elevated pressures or by integrating more membranes. Even though the concept has been successfully demonstrated, further research is required to develop suitable membranes since post-mortem membrane characterization has revealed defects in the membrane selective layer as a consequence of the frequent exposure to thermal cycles with alternating oxidative and reducing atmospheres.     

Hydrogen production for PEM fuel cell by gas phase reforming of glycerol as byproduct of bio-diesel. The use of a Pd-Ag membrane reactor at middle reaction temperature

Glycerol as a byproduct of biodiesel production represents a renewable energy source. In particular, glycerol can be used in the field of hydrogen production via gas phase reforming for proton exchange membrane fuel cell (PEMFC) applications. In this work, glycerol steam reforming (GSR) reaction was investigated using a dense palladium-silver membrane reactor (MR) in order to produce pure (or at least CO-free) hydrogen, using 0.5 wt% Ru/Al₂O₃ as reforming catalyst. The experiments are performed at 400 °C, water to glycerol molar feed ratio 6:1, reaction pressure ranging from 1 to 5 bar and weight hourly space velocity (WHSV) from 0.1 to 1.0 h⁻¹. Moreover, a comparative study is given between the Pd-Ag MR and a traditional reactor (TR) working at the same MR operating conditions. The effect of the WHSV and reaction pressure on the performances of both the reactors in terms of glycerol conversion and hydrogen yield is also analyzed. The MR exhibits higher conversion than the TR (∼60% as best value for the MR against ∼40% for the TR, at WHSV = 0.1 h⁻¹ and 5 bar), and high CO-free hydrogen recovery (around 60% at WHSV = 0.1 h⁻¹ and 5 bar). During reaction, carbon coke is formed limiting the performances of the reactors and inhibiting, in particular, the hydrogen permeation through the membrane with a consequent reduction of hydrogen recovery in the permeate side.     

Hydrogen enrichment effects on the second law analysis of a lean burn natural gas engine

This paper presents a computational work aimed at investigating the effects of hydrogen addition on the exergy (or availability) balance in a lean burn natural gas spark ignition (SI) engine. A thermodynamic engine cycle simulation was extended to perform the exergy analysis. A zero dimensional, two-zone computational model of the engine operation was used for the closed part of the cycle. The results of the model were compared with experimental data to demonstrate the validation of the model. Exergetic terms, such as exergy transfer with heat, exergy transfer with work, irreversibilities, fuel chemical exergy, and total exergy, were computed based on principles of the second law. The exergetic (the second law) efficiency was also calculated. The results of exergy analysis show that increasing hydrogen content and lean burn have considerably affected the exergy transfers, irreversibilities and second law efficiency. With increasing hydrogen content, the irreversibility produced during combustion decreases, and the second-law efficiency sharply increases at near the lean limit.     

Hydrogen networks synthesis considering separation performance of purifiers

In hydrogen networks, purifiers are quite often used to reduce operating costs. They should be properly integrated with the whole network in order to maximize the benefit. In this paper, a graphical method is proposed for targeting the minimum fresh resource consumption of hydrogen networks considering separation performance of purifiers. The material balance of the whole hydrogen network shows that the extent of fresh hydrogen reduction is subject to the maximum hydrogen surplus. Based on such observation, the mass transfer triangle is developed to describe the hydrogen transformation from maximum hydrogen surplus to fresh hydrogen. With both the purity and the flow rate of purification streams optimized, the minimum fresh hydrogen consumption can be determined through the proposed graphical method. Two cases are studied to illustrate the proposed methodology.     

Hydrogen production by silica membrane reactor during dehydrogenation of methylcyclohexane: CFD analysis

A comprehensive computational fluid dynamic model has been developed using COMSOL Multiphysics 5.4 software to predict the behavior of a membrane reactor in dehydrogenation of methylcyclohexane for hydrogen production. A reliable reaction kinetic of dehydrogenation reaction and a permeation mechanism of hydrogen through silica membrane have been used in computational fluid dynamic modeling. For performance comparison, an equivalent traditional fixed bed reactor without hydrogen removal has been also modeled. After model validation, it has been used to evaluate the operating parameters effect on the performance of both the silica membrane reactor and the equivalent traditional reactor as well. The operating temperature ranged between 473 and 553 K, pressure between 1 and 2.5 bar, sweep factor from ?6.22 to 25 and feed flow rate from 1 to 5 × 10^?6 mol/s. The membrane reactor performed better than the equivalent traditional reactor, achieving as best result complete methylcyclohexane conversion and 96% hydrogen recovery.     

Enhancement of pure hydrogen production through the use of a membrane reactor

Pure hydrogen production is of great interest as it is an energy carrier which can be used in PEM fuel cells for power production. Methane Steam Reforming (MSR) is commonly used for hydrogen production although the produced hydrogen is not free of other components. Membrane Reactors (MR) enable a pure hydrogen product stream and allows the reaction to take place at significantly lower temperatures (lower than 550 °C) than in conventional reactors (greater than 800 °C) with comparable methane conversion. This is achieved by hydrogen removal through a permselective Pd–Ag based membrane that cause a favorable shift in chemical equilibrium towards hydrogen production. In the present study, a two-dimensional, nonlinear, and pseudo-homogeneous mathematical model of a catalytic fixed-bed membrane reactor for methane steam reforming over a nickel-based foam supported catalyst is presented. Simulated results referring to the distribution of species, methane conversion, temperature and hydrogen flowrate along the reactor for different radial positions are obtained and analyzed. The performance of structured catalyst and catalyst supported on foam configurations under the same operating conditions is also studied. Experimental results for the membrane facilitate the identification of suitable operating conditions.     

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.     

Hydrogen production from ethanol steam reforming in a micro-channel reactor

Ethanol steam reforming was studied over a supported Ir/CeO₂ catalyst in a micro-channel structured reactor. The catalyst coating was deposited on the channel walls and showed a remarkably high homogeneity and an excellent adherence to the stainless steel substrate, leading to stable performance during long-term runs. Hydrogen yields exceeding 40 L_H2 g_cat⁻¹ h⁻¹ were achieved during testing with partial ethanol conversion of 65% and a residence time in the order of a few milliseconds. This hydrogen productivity was found significantly higher than in a comparable conventional fixed-bed reactor hence being extremely promising for hydrogen production in micro fuel cell applications.     

Hydrogen amplification from coke oven gas using a CO2 adsorption enhanced hydrogen amplification reactor

To improve coke oven gas (COG) energy conversion, alternative configurations for amplifying hydrogen from COG are proposed in this paper. In these new configurations, a CO₂ adsorption enhanced hydrogen amplification reactor is combined with a pressure swing adsorption separation unit (PSA) to produce pure hydrogen. Hydrogen production was integrated with desorption gas utilization, in situ CO₂ capture and waste heat recovery to improve COG energy conversion efficiency and decrease CO₂ emissions. To analyze the advantages of the flowsheet modifications, technical and economic performance indicators were used to evaluate and compare the performances of the various system configurations. Simulation results show that the alternative configurations proposed in this paper have higher energy conversion efficiencies, higher hydrogen yields and shorter dynamic payback periods. The variation of technical performance with reaction temperature, pressure, sorbent to carbon ratio and steam to carbon ratio were also analyzed using a sensitivity study. Optimal operating conditions for the CO₂ adsorption enhanced hydrogen amplification reactor were obtained based on the simulation results.     

Hydrogen production from nuclear fission product waste heat and use in gas turbines

An analysis has been made on the feasibility of producing hydrogen using fission product waste heat and its subsequent combustion in gas turbines. The work has been performed in three distinct phases.In the first phase, a system using heat generated from radioactive wastes has been designed which produces saturated steam. This steam is sent through a turbogenerator to produce electricity. The electrical power output of this system has been calculated as a function of fission product decay time, solidified form of fission products, as well as numerous other parameters.In the second phase, the electrical energy produced is used to electrolyze water, which in turn produces hydrogen. The amount of hydrogen produced (lb/h) has been calculated for varying electrical inputs, electrolyzer efficiencies, and feedwater temperatures. This hydrogen is then assumed to be liquified and stored. Finally, the third phase considers the burning of this hydrogen in a standard marine gas turbine.     

Hydrogen production from hydrogen sulfide in a packed-bed DBD reactor

The effect of different reactor packing materials on the nonthermal plasma (NTP) assisted decomposition of hydrogen sulfide (H₂S) in a coaxial dielectric barrier discharge (DBD) reactor has been described in the present investigation. The packing materials studied include ceramic beads, glass material with different geometries like spherical (glass beads), hollow cylinder (glass tubes) and honeycomb (glass wool), and for comparison the reaction was carried out in the absence of any packing material. The packing material studied in the present work do not exhibit any catalytic activity in the traditional sense; however, they do have different dielectric constants and morphologies that may influence the plasma discharge behavior and may also affect the residence time of the gas molecules in the discharge zone. From the experimental results, it has been found that the ceramic pellets and hollow cylindrical glass material packed reactor showed better performance for H₂S decomposition into H₂ and S.     

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 from glycerol by supercritical water gasification in a continuous flow tubular reactor

In this work, glycerol was used for hydrogen production by supercritical water gasification. Experiments were conducted in a continuous flow tubular reactor at 445∼600 °C, 25 MPa, with a short residence time of 3.9∼9.0 s. The effects of reaction temperature, residence time, glycerol concentration and alkali catalysts on gasification were systematically studied. The results showed that the gasification efficiency increased sharply with increasing temperature above 487 °C. A short residence time of 7.0 s was enough for 10 wt% glycerol gasification at 567 °C. With the increase of glycerol concentration from 10 to 50 wt%, the gasification efficiency decreased from 88% to 71% at 567 °C. The alkali catalysts greatly enhanced water-gas shift reaction and the hydrogen yield in relation to catalysts was in the following order: NaOH > Na₂CO₃>KOH > K₂CO₃. The hydrogen yield of 4.93 mol/mol was achieved at 526 °C with 0.1 wt% NaOH. No char or tar was observed in all experiments. The apparent activation energy and apparent pre-exponential factor for glycerol carbon gasification were obtained by assuming pseudo first-order kinetics.     

Enhancement of membrane hydrogen separation on glycerol steam reforming in a fluidized bed reactor

Membrane hydrogen separation can effectively promote fuel conversion and hydrogen yield by means of altering chemical equilibrium of reforming reactions. In this work, the enhancing process of glycerol steam reforming via a fluidized bed membrane reactor is numerically investigated. Under the framework of the Euler-Euler method, chemical kinetic model is implemented and the reforming performance with and without membrane separation is compared. The effect of densified zones caused by membrane separation is examined. Meanwhile, the impacts of operating parameters including hydrogen partial pressure on the permeate side and fuel gas velocity on densified zones and hydrogen yield are evaluated. The results demonstrate that the excessive reduction of hydrogen partial pressure on the permeate side and the increase of feed gas velocity are detrimental to fuel conversion and hydrogen yield.     

Hydrogen from ethanol by steam iron process in fixed bed reactor

This research is devoted to the use of ethanol (i.e. bio-ethanol) in the combined production and purification of hydrogen by redox processes. The process has been studied in a single lab scale fixed bed reactor. Iron oxides, apart from their remarked redox behavior, exert an important catalytic role allowing the complete decomposition of ethanol at temperatures in the range from 625 to 750 °C. The resulting gas stream (mainly H₂ and CO) reduces the solid to metallic iron. During a subsequent oxidation with steam, the solid can be regenerated to magnetite producing high purity hydrogen (suitable to be used in PEM fuel cells). Even though small amounts of coke are deposited during the reduction step, this is barely gasified by steam during the oxidation step (detection of CO_x in concentrations lower than 1 ppm). Influence of parameters like temperature, ethanol partial pressure and alternate cycles' effect has been studied in order to maximize the production of pure hydrogen.     

A novel configuration for hydrogen production from coupling of methanol and benzene synthesis in a hydrogen-permselective membrane reactor

Coupling energy intensive endothermic reaction systems with suitable exothermic reactions improve the thermal efficiency of processes and reduce the size of the reactors. One type of reactor suitable for such a type of coupling is the heat-exchanger reactor. In this work, a distributed mathematical model for thermally coupled membrane reactor that is composed of three sides is developed for methanol and benzene synthesis. Methanol synthesis takes place in the exothermic side and supplies the necessary heat for the endothermic dehydrogenation of cyclohexane reaction. Selective permeation of hydrogen through the Pd/Ag membrane is achieved by co-current flow of sweep gas through the permeation side. A steady-state heterogeneous model of the two fixed beds predicts the performance of this novel configuration. The co-current mode is investigated and the simulation results are compared with corresponding predictions for an industrial methanol fixed-bed reactor operated at the same feed conditions. The results show that although methanol productivity is the same as conventional methanol reactor, but benzene is also produced as an additional valuable product in a favorable manner, and auto-thermal conditions are achieved within the both reactors and also pure hydrogen is produced in permeation side. This novel configuration can increase the rate of methanol synthesis reaction and shift the thermodynamics equilibrium. The performance of the reactor is numerically investigated for various key operating variables such as inlet temperatures, molar flow rates of exothermic and endothermic streams, membrane thickness and sweep gas flow rate. The reactor performance is analyzed based on methanol yield, cyclohexane conversion and hydrogen recovery yield. The results suggest that coupling of these reactions in the presence of membrane could be feasible and beneficial. Experimental proof-of-concept is needed to establish the validity and safe operation of the novel reactor.     

Hydrogen gas production from distillery wastewater by dark fermentation

The influence of concentration of distillery wastewaters, concentration of inoculum and pH value on hydrogen generation in batch dark fermentation process was studied. Anaerobic digested sludge from municipal purification unit was applied as the source of bacteria mixture. The best specific yield was obtained in system containing 10% v/v of inoculum and 20% v/v of the waste (S₀/X₀ = 2.8), whereas the maximum amount of hydrogen and the highest rate of reaction was achieved in system containing 25% v/v inoculum and 40% v/v of waste (S₀/X₀ = 2.2). The content of generated hydrogen in biogas was always higher than 62%. Maximum amount of generated hydrogen was 1 l H₂/l medium and the rate was 0.12 l/l/h. Liquid metabolites of hydrogen generation process were mainly acetic and butyric acids. Ethanol and propionic acid were in traces. The ratio of HBu/HAc in medium influenced the yield of generated hydrogen.