System optimization for effective hydrogen production via anaerobic digestion and biogas steam reforming

To construct a system for the effective hydrogen production from food waste, the conditions of anaerobic digestion and biogas reforming have been investigated and optimized. The type of agitator and reactor shape affect the performance of anaerobic digestion reactors. Reactors with a cubical shape and hydrofoil agitator exhibit high performance due to the enhanced axial flow and turbulence as confirmed by simulation of computational fluid dynamics. The stability of an optimized anaerobic digestion reactor has been tested for 60 days. As a result, 84 L of biogas is produced from 1 kg of food waste. Reaction conditions, such as reaction temperature and steam/methane ratio, affect the biogas steam reforming reaction. The reactant conversions, product yields, and hydrogen production are influenced by reaction conditions. The optimized reaction conditions include a reaction temperature of 700 °C and H₂O/CH₄ ratio of 1.0. Under these conditions, hydrogen can be produced via steam reforming of biogas generated from a two-stage anaerobic digestion reactor for 25 h without significant deactivation and fluctuation.     

Simulation and optimization of hydrogen production by steam reforming of natural gas for refining and petrochemical demands in Lebanon

Steam reforming of natural gas produces the majority of the world's hydrogen (H₂) and it is considered as a cost-effective method from a product yield and energy consumption point of view. In this work, we present a simulation and an optimization study of an industrial natural gas steam reforming process by using Aspen HYSYS and MATLAB software. All the parameters were optimized to successfully run a complete process including the hydrogen production zone units (reformer reactor, high temperature gas shift reactor HTS and low temperature gas shift reactor LTS) and the purification zone units (absorber and methanator). Optimum production of hydrogen (87,404 MT/year) was obtained by fixing the temperatures in the reformer and the gas shift reactors (HTS & LTS) at 900 °C, 500 °C and 200 °C respectively while maintaining a pressure of 7 atm, and a steam to carbon ratio (S/C) of 4. Moreover, ~99% of the undesired CO₂ and CO gases were removed in the purification zone and a reduction of energy consumption of 77.5% was reached in the heating and cooling units of the process.     

Design and performance of asymmetric supported membranes for oxygen and hydrogen separation

Producing syngas and hydrogen from biofuels is a promising technology in the modern energy. In this work results of authors’ research aimed at design of supported membranes for oxygen and hydrogen separation are reviewed. Nanocomposites were deposited as thin layers on Ni–Al foam substrates. Oxygen separation membranes were tested in CH₄ selective oxidation/oxi-dry reforming. The hydrogen separation membranes were tested in C₂H₅OH steam reforming. High oxygen/hydrogen fluxes were demonstrated. For oxygen separation membranes syngas yield and methane conversion increase with temperature and contact time. For reactor with hydrogen separation membrane a good performance in ethanol steam reforming was obtained. Hydrogen permeation increases with ethanol inlet concentration, then a slight decrease is observed. The results of tests demonstrated the oxygen/hydrogen permeability promising for the practical application, high catalytic performance and a good thermochemical stability.     

A review on bi/polymetallic catalysts for steam methane reforming

Blue hydrogen production by steam methane reforming (SMR) with carbon capture is by far the most commercialised production method, and with the addition of a simultaneous in-situ CO₂ adsorption process, sorption-enhanced steam methane reforming (SESMR) can further decrease the cost of H₂ production. Ni-based catalysts have been extensively used for SMR because of their excellent activity and relatively low price, but carbon deposition, sulphation, and sintering can lead to catalyst deactivation. One effective solution is to introduce additional metal element(s) to improve the overall performance. This review summarizes recent developments on bi/polymetallic catalysts for SMR, including promoted nickel-based catalysts and other transition metal-based bi/polymetallic materials. The review mainly focuses on experimental studies, but also includes results from simulations to evaluate the synergistic effects of selected metals from an atomic point of view. An outlook is provided for the future development of bi/polymetallic SMR catalysts.     

A strategy of mid-temperature natural gas based chemical looping reforming for hydrogen production

Steam methane reforming (SMR) needs the reaction heat at a temperature above 800 °C provided by the combustion of natural gas and suffers from adverse environmental impact and the hydrogen separated from other chemicals needs extra energy penalty. In order to avoid the expensive cost and high power consumption caused by capturing CO₂ after combustion in SMR, natural gas Chemical Looping Reforming (CLR) is proposed, where the chemical looping combustion of metal oxides replaced the direct combustion of NG to convert natural gas to hydrogen and carbon dioxide. Although CO₂ can be separated with less energy penalty when combustion, CLR still require higher temperature heat for the hydrogen production and cause the poor sintering of oxygen carriers (OC). Here, we report a high-rate hydrogen production and low-energy penalty of strategy by natural gas chemical-looping process with both metallic oxide reduction and metal oxidation coupled with steam. Fe₃O₄ is employed as an oxygen carrier. Different from the common chemical looping reforming, the double side reactions of both the reduction and oxidization enable to provide the hydrogen in the range of 500–600 °C under the atmospheric pressure. Furthermore, the CO₂ is absorbed and captured with reduction reaction simultaneously.Through the thermodynamic analysis and irreversibility analysis of hydrogen production by natural gas via chemical looping reforming at atmospheric pressure, we provide a possibility of hydrogen production from methane at moderate temperature. The reported results in this paper should be viewed as optimistic due to several idealized assumptions: Considering that the chemical looping reaction is carried out at the equilibrium temperature of 500 °C, and complete CO₂ capture can be achieved. It is assumed that the unreacted methane and hydrogen are completely separated by physical adsorption. This paper may have the potential of saving the natural gas consumption required to produce 1 m³ H₂ and reducing the cost of hydrogen production.     

Effect of ammonia concentration on hythane (H2 and CH4) production in two-phase anaerobic digestion

Co-production of hydrogen and methane by two-phase anaerobic digestion (AD) may offer a sustainable solution for the centralized treatment of food waste (FW), while ammonia accumulation is potentially encountered. A mesophilic two-phase AD was investigated for hydrogen and methane production from FW at varying ammonia concentrations. The process achieved a hydrogen yield of 47.7 mL/g VS and a methane yield of 335 mL/g VS by optimizing the organic loading rate (OLR) and recirculation ratio. Total ammonia nitrogen (TAN) concentration of 4044 mg/L corresponded to a threshold in the hydrogen reactor, above which ammonia would initiate inhibition of hydrogenogenesis and acidogenesis. Methane yield was recovered in the methane reactor after acute inhibiting effects of TAN below 5800 mg/L, while TAN above 6200 mg/L caused chronic inhibition of methanogens. Adjusting hydraulic retention time (HRT) and recirculation ratio in hydrogen and methane reactors reduced TAN to 960 and 2105 mg/L respectively, resulting in successful recovery was achieved in the hydrogen reactor but not in the methane reactor. The two-phase AD for methane and hydrogen production can be a promising solution for ammonia accumulation in AD from FW.     

Renewable-powered hydrogen economy from Australia's perspective

This article broadly reviews the state-of-the-art technologies for hydrogen production routes, and methods of renewable integration. It outlines the main techno-economic enabler factors for Australia to transform and lead the regional energy market. Two main categories for competitive and commercial-scale hydrogen production routes in Australia are identified: 1) electrolysis powered by renewable, and 2) fossil fuel cracking via steam methane reforming (SMR) or coal gasification which must be coupled with carbon capture and sequestration (CCS). It is reported that Australia is able to competitively lower the levelized cost of hydrogen (LCOH) to a record $(1.88–2.30)/kg_H2 for SMR technologies, and $(2.02–2.47)/kg_H2 for black-coal gasification technologies. Comparatively, the LCOH via electrolysis technologies is in the range of $(4.78–5.84)/kg_H2 for the alkaline electrolysis (AE) and $(6.08–7.43)/kg_H2 for the proton exchange membrane (PEM) counterparts. Nevertheless, hydrogen production must be linked to the right infrastructure in transport-storage-conversion to demonstrate appealing business models.     

Production of hydrogen enriched syngas from municipal solid waste gasification with waste marble powder as a catalyst

Marble processing leads to the production of high amount of waste marble powder (WMP) as a byproduct, which can be a potential health risk and has hazardous impacts on the surrounding environment. However, marble is composed of calcite making it suitable for the calcium-based catalyst. Moreover, no study has been carried out to utilize this WMP in municipal solid waste (MSW) gasification process. Therefore, there is a need to address its utilization as a potential catalyst/sorbent in the gasification of municipal solid waste (MSW). A laboratory scale batch-type fixed bed reactor was used to study the effect of WMP addition on the CO₂ adsorption, steam reforming capability and char gasification in the presence of steam. Produced gas composition, gas yield, carbon conversion efficiency and tar yield were examined at different WMP to MSW ratios. Effect of temperature and steam rate varying from 700 to 900 °C and 2.5–10 ml/min respectively were also considered in this study. WMP showed a good capacity towards hydrogen enriched syngas production as well as CO₂ adsorption and tar reforming. The H₂ concentration increased significantly with an increase in the WMP to MSW mass ratio, while CO₂ decreased. A significant effect of temperature and steam rate was also observed on the produced gas composition, gas yield, and tar content. This study helps us to understand the effect of WMP addition in MSW gasification process and thus assists in the industrial application.     

Catalyst modification strategies to enhance the catalyst activity and stability during steam reforming of acetic acid for hydrogen production

A high energy content (∼122 MJ/kg H₂) and presence of hydrogen-bearing compounds abundance in nature make hydrogen forth runner candidate to fulfill future energy requirements. Biomass being abundant and carbon neutral is one of the promising source of hydrogen production. In addition, it also addresses agricultural waste disposal problems and will bring down our dependency on fossil fuel for energy requirements. Biomass-derived bio-oil can be an efficient way for hydrogen production. Acetic acid is the major component of bio-oil and has been extensively studied by the researchers round the globe as a test component of bio-oil for hydrogen generation. Hydrogen can be generated from acetic acid via catalytic steam reforming process which is thermodynamically feasible. A number of nickel-based catalysts have been reported. However, the coke deposition during reforming remains a major challenge. In this review, we have investigated all possible reactions during acetic acid steam reforming (AASR), which can cause coke deposition over the catalyst surface. Different operating parameters such as temperature and steam to carbon feed ratio affect not only the product distribution but also the carbon formation during the reaction. Present review elaborates effects of preparation methods, active metal catalyst including bimetallic catalysts, type of support and microstructure of catalysts on coke resistance behavior and catalyst stability during reforming reactions. The present study also focuses on the effects of a combination of a variety of alkali and alkaline earth metals (AAEM) promoters on coke deposition. Effect of specially designed reactors and the addition of oxygen on carbon deposition during AASR have also been analyzed. This review based on the available literature focuses mainly on the catalyst deactivation because of coke deposition, and possible strategies to minimize catalyst deactivation during AASR.     

Performance evaluation of a solarized gas turbine system integrated to a high temperature electrolyzer for hydrogen production

In this paper, the performance of a solar gas turbine (SGT) system integrated to a high temperature electrolyzer (HTE) to generate hybrid electrical power and hydrogen fuel is analyzed. The idea behind this design is to mitigate the losses in the electrical power transmission and use the enthalpy of exhaust gases released from the gas turbine (GT) to make steam for the HTE. In this context, a GT system is coupled with a solar tower including heliostat solar field and central receiver to generate electrical power. To make steam for the HTE, a flameless boiler is integrated to the SGT system applying the SGT extremely high temperature exhaust gases as the oxidizer. The results indicate that by increasing the solar receiver outlet temperature from 800 K to 1300 K, the solar share increases from 22.1% to 42.38% and the overall fuel consumption of the plant reduces from 7 kg/s to 2.7 kg/s. Furthermore, flameless mode is achievable in the boiler while the turbine inlet temperature (TIT) is maintained at the temperatures higher than 1314 K. Using constant amounts of the SGT electrical power, the HTE voltage decreases by enhancing the HTE steam temperature which result in the augmentation of the overall hydrogen production. To increase the HTE steam temperature from 950 K to 1350 K, the rate of fuel consumption in the flameless boiler increases from 0.1 m/s to 0.8 m/s; however, since the HTE hydrogen production increases from 4.24 mol/s to 16 mol/s it can be interpreted that the higher steam temperatures would be affordable. The presented hybrid system in this paper can be employed to perform more thermochemical analyses to achieve insightful understanding of the hybrid electrical power-hydrogen production systems.     

Biomass gasification coupled with producer gas cleaning,bottling and HTS catalyst treatment for H2-rich gas production

The aim of the present study is to demonstrate the production of hydrogen-rich fuel gas from J. curcas residue cake. A comprehensive experimental study for the production of hydrogen rich fuel gas from J. curcas residue cake via downdraft gasification followed by high temperature water gas shift catalytic treatment has been carried out. The gasification experiments are performed at different equivalence ratios and performance of the process is reported in terms of producer gas composition & its calorific value, gas production rate and cold gas efficiency. The producer gas is cleaned of tar and particulate matters by passing it through venturi scrubber followed by sand bed filter. The clean producer gas is then compressed at 0.6 MPa and bottled into a gas cylinder. The bottled producer gas and a simulated mixture of producer gas are then subjected to high temperature shift (HTS) catalytic treatment for hydrogen enriched gas production. The effect of three different operating parameters GHSV, steam to CO ratio and reactor temperature on the product gas composition and CO conversion is reported. From the experimental study it is found that, the presence of oxygen in the bottled producer gas has affected the catalyst activity. Moreover, higher concentration of oxygen concentration in the bottled producer gas leads to the instantaneous deactivation of the HTS catalyst.     

Hydrogen sulphide to hydrogen via H2S methane reformation: Thermodynamics and process scheme assessment

Hydrogen Sulphide Methane Reformation (HSMR) represents a valid alternative for the simultaneous H₂S valorisation and hydrogen production at the industrial scale, without direct CO₂ emissions. The major concerns about the process commercialization are the possible coke formation in the reaction zone and the lack of active and selective catalysts. The study of the thermodynamics is the essential preliminary step for the reaction phenomena understanding. In this work, a deep thermodynamic analysis is performed to explore the system behaviour as a function of temperature, pressure, and inlet feed composition, using the Aspen Plus RGibbs module. In this way, the optimal process operating conditions to avoid carbon lay down can be identified.Assessed the system's thermodynamics, a preliminary process scheme is developed and simulated in Aspen Plus V11.0®, considering hydrogen production and its distribution in pipeline with methane. The process performances are discussed in terms of products' purity and process energy consumptions.     

Hydrogen production by methane pyrolysis in molten binary copper alloys

The utilization of hydrogen as an energy carrier and reduction agent in important industrial sectors is considered a key parameter on the way to a sustainable future. Steam reforming of methane is currently the most industrially used process to produce hydrogen. One major drawback of this method is the simultaneous generation of carbon dioxide. Methane pyrolysis represents a viable alternative as the basic reaction produces no CO₂ but solid carbon besides hydrogen. The aim of this study is the investigation of different molten copper alloys regarding their efficiency as catalytic media for the pyrolysis of methane in an inductively heated bubble column reactor. The conducted experiments demonstrate a strong influence of the catalyst in use on the one hand on the conversion rate of methane and on the other hand on the properties of the produced carbon. Optimization of these parameters is of crucial importance to achieve the economic competitiveness of the process.     

Steam reforming of 1-methylnaphthalene over pure CeO2 under model coke oven gas conditions containing high H2S concentrations

Tar and H₂S are obstacles to the efficient production of H₂ from unused industrial gases and biomass gasification gases. Robust catalysts against tar and H₂S are required to produce H₂ from such resources. Herein, a stable steam reforming reaction is demonstrated over pure CeO₂ under reaction conditions consisting of ~2 vol% 1-methylnaphthalene and ~1000 ppm H₂S. The presence of H₂S significantly suppressed Ni/MgO/Al₂O₃ activity and increased carbon deposition, regardless of the steam to carbon (S/C) ratio. In contrast, the promotion or suppression of CeO₂ activity in the presence of H₂S was dependent on the S/C ratio. At S/C = 1.2, H₂S deactivated the CeO₂ catalyst and increased carbon deposition. Conversely, H₂S promoted the reforming reaction and decreased carbon deposition on CeO₂ at S/C ≥ 2.0. The results of this study clarify that pure CeO₂ exhibits outstanding and stable activity for the steam reforming reaction of 1-methylnaphthalene in the presence of H₂S by controlling the S/C of the inlet gas.     

Variations of methane conversion process with the geometrical effect in rotating gliding arc reactor

Controllability of the kinetic path of methane conversion in plasma driven oxidation reaction is investigated. Different geometries in a rotating gliding arc reactor are adopted to control reaction paths in methane oxidation reaction. Diverging and converging type reactor product different reaction environments in view point of both the reaction time and the degree of thermal activation. In the diverging reactor, the partial oxidation process is dominant with high methane conversion because the diverging section facilitates to elongate the arc length and decrease the flow velocity. Thus, the convective and radiative heat transfer from the arc column to the reactants could be enhanced. The role of plasma in the diverging reactor is mainly igniting and sustaining the partial oxidation, which is rather different from that in the converging reactor where the plasma plays as a heat source for thermal pyrolysis of methane with the help of focusing thermal energy of the arc.     

Effects of hydrogen enrichment of methane on diffusion flame structure and emissions in a back-pressure combustion chamber

In the present study, the effects of hydrogen enrichment of methane are investigated numerically from the diffusion flame structure and emissions aspect. Fluent code is utilised as the simulation tool. In the first part of the study, four experiments were conducted using natural gas as fuel. A non-premixed burner and a back-pressure boiler were utilised as the experimental setup. The natural gas fuel consumption rate was changed between 22 Nm³/h and 51 Nm³/h. After the experimental studies, the numerical simulations were performed. The non-premixed combustion model with the steady laminar flamelet model (SFM) approach was used for the calculations. The methane-air extinction mechanism was utilised for the calculation of the chemical species. The numerical results were verified with the experimental results in terms of the flue gas emissions and flue gas temperature values. In the second part of the study, four different hydrogen-enriched methane combustion cases were simulated using the same methane-air extinction mechanism, which included the hydrogen oxidation mechanism as a sub mechanism. The same energy input (432 kW) was supplied into the boiler for all the studied cases. The obtained results show that the hydrogen addition to methane significantly change the diffusion flame structure in the combustion chamber. The hydrogen-enriched flames become broader and shorter with respect to the pure methane flame. This provides better mixing of the reactants and combustion products in the flame regions due to the use of a back-pressure boiler. In this way, the maximum flame temperature values and thermal NO emissions are reduced in the combustion chamber, when the hydrogen addition ratio is less than 15% by mass. The maximum temperature value is calculated as 2030 K for the case with 15% hydrogen addition ratio by mass, while it is 2050 K for the case without hydrogen enrichment. Therefore, it is determined that the hydrogen-enriched methane combustion in a back-pressure combustion chamber has the potential of reducing both the carbon and thermal NO emissions.     

Hydrogen production using chemical looping technology: A review with emphasis on H2 yield of various oxygen carriers

Natural H₂ in useful quantities is negligible, which makes hydrogen unsuitable as an energy resource compared to other fuels. H₂ production by solar, biological, or electrical sources needs more energy than obtained by combusting it. Lower generation of pollutants and better energy efficiency makes hydrogen a potential energy carrier. Hydrogen finds potential applications in automobile and energy production. However, the cost of producing hydrogen is extremely high. Chemical-looping technology for H₂ generation has caught widespread attention in recent years. This work, presents some recent findings and provides a comprehensive overview of different chemical looping techniques such as chemical looping reforming, syngas chemical looping, coal direct chemical looping, and chemical looping hydrogen generation method for H₂ generation. The above processes are discussed in terms of the relevant chemical reactions and the associated heat of reactions to ascertain the overall endothermicity or exothermicity of the H₂ production. We have compared the H₂ yield data of different Fe/Ni, spinel and perovskites-based oxygen carriers (OC) reported in previous literature. This review is the first comprehensive study to compare the H₂ yield data of all the previously reported oxygen carriers as a function of temperature and redox cycles. In addition, the article summarizes the characteristics and reaction mechanisms of various oxygen carrier materials used for H₂ generation. Lastly, we have reviewed the application of Density Function Theory (DFT) to study the effect of various dopant addition on the efficiency of H₂ production of the oxygen carriers and discussed ASPEN simulations of different chemical looping techniques.     

Hydrogen-rich syngas production by gasification of Urea-formaldehyde plastics in supercritical water

Supercritical water is a promising medium to convert plastics into hydrogen and other recyclable products efficiently. In previous research, supercritical water gasification characteristics investigations focus on thermoplastics instead of thermoset plastics due to its chemical, thermal and mechanical stability. Urea-formaldehyde (UF) plastics were selected as a typical kind of thermoset plastics for investigation in this paper and quartz tubes were used as the reactor in order to avoid the potential catalytic effect of metal reactor wall. Conversion characteristic were studied and the influence of different operating parameters such as temperature, reaction time, feedstock mass fraction and pressure were investigated respectively. The molar fraction of hydrogen could reach about 70% in 700 °C. Products in gas phase and solid phase were analyzed, and properties, chemical structures and inhibition mechanism of thermoset plastics was analyzed after comparing with polystyrene (PS) plastics. The result showed that increase of high temperature and long reaction time could promote gasification process, meanwhile the increase in the feedstock mass fraction would result in suppression of the gasification process. Finally, kinetic study of UF was carried out and the activation energy and pre-exponential factor of the Arrhenius equation were calculated as 30.09 ± 1.62 kJ/mol and 0.1199 ± 0.0049 min⁻¹, respectively.     

Life Cycle Assessment (LCA) for use on renewable sourced hydrogen fuel cell buses vs diesel engines buses in the city of Rosario,Argentina

The purpose of this paper is to build the first Energy and Life Cycle Analysis (LCA) comparison between buses with internal combustion engine currently used in the city of Rosario, Province of Santa Fe, Argentina, and some technological alternatives and their variants focusing on buses with an electrical engine powered by compressed hydrogen that feet fuel cells of polymer electrolyte membrane (PEM). This LCA comprehend raw material extraction up to its consumption as fuel. Specifically, hydrogen production considering different production processes from renewable sources called “green hydrogen” (Velazquez Abad and Dodds, 2020) [1] and non-renewable sources called “grey hydrogen” (Velazquez Abad and Dodds, 2020) [1]. Renewable sources for hydrogen production are rapid cut densified poplar energy plantation, post-industrial wood residues such as chips pallets, and maize silage. For non-renewable hydrogen production sources are the local electrical power grid from water electrolysis and natural gas from the steam methane reforming process.Buses whose fuel would be renewable hydrogen, produced near the City of Rosario, Province of Santa Fe, Argentina, meet one of the main criteria of sustainability biofuels of the European Union (EU) taken into account Renewable Energy Directive (RED) 2009/28 [2] and EU RED Directive 2018/2001 [3] that need significant reduction on net greenhouse gases (GHG) from biomass origin row material respect fossil fuels. At least 70% of GHG would be avoided from its main fossil counterpart of the intern combustion engine (ICE), in the worst and current scenario of the emission factor of the electrical grid of Argentina in the point of use that is about 0.40 kg CO_2eq/kWh with energy and environmental load of 100% in the allocation factor in the hydrogen production stage of the LCA analysis.     

Transient performances of the gas turbine recuperating waste heat through hydrogen rich fuels

Operational rules and control strategies of the chemically recuperated gas turbine (CRGT) in the marine propulsion are investigated in this paper. The Minimization of Gibbs free energy method is used to calculate the diesel-steam reforming reaction which products synthetic hydrogen rich fuels, and a universal model of the chemical regenerator which is easily applied to different application environments is created. The hydrogen production and hydrogen molar fraction are investigated to verify that the CRGT improve the combustion performances under low working conditions. Off-design calculations are performed to derive proper operational rules, and transient calculations are performed to investigate the best control strategies for the systems. The modelling approach of the chemical regenerator can be generally used in the chemically recuperated gas turbine. The elaborate operational rules can greatly improve the thermal efficiencies under every working condition. The system using synchronous control strategies have better regulation speed and operation stability than that using asynchronous control strategies.