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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Enhancing resistance of carbon deposition and reaction stability over nickel loaded fibrous silica-alumina (Ni/FSA) for dry reforming of methane

Syngas production from the dry reforming of methane is now the most extensively utilized method for removing massive amounts of greenhouse emissions. Effective solutions towards the utilization of greenhouse gases such as CO₂ and CH₄ are scarce, except for power generation in the energy sector, which is a major source of CO₂. Herein, dry reforming of methane was experimented for the first time using an effective catalytic system composed of 5% Ni fibrous silica-alumina (FSA) that was successfully fabricated using a hydrothermal method. The characterization results from XRD, FESEM mapping, TEM, BET,XRF, FTIR, H₂-TPR, TGA/DTA, and Raman spectra demonstrated that Ni/FSA is composed of orderly Ni dispersion, small particles of Ni, robust basic sites, and high oxygen vacancies which enhanced the catalytic efficiency. The synthesized Ni/FSA also reduced coke formation and had long-term stability with no evidence of inactivation during and after the catalytic cycles. The superior activity of Ni/FSA was manifested in the high conversion rates of CH₄ and CO₂ at 97% and 92% respectively, with a H₂:CO ratio of ≈ 1. The stability of Ni/FSA was also sustained over 30 h of operation at 800 °C. The findings of the Raman, TEM, and TGA/DTA tests revealed that the spent Ni/FSA catalysts did not exhibit graphitic carbon or metal sintering in significant amounts when compared to commercial Ni–Si/Al catalysts.     

Effect of organic fraction of municipal solid waste addition to high rate activated sludge system for hydrogen production from carbon rich waste sludge

Municipal solid waste has been used for bio-methane production for many years. However, both methane and carbon dioxide that is produced during bio-methanization increases the greenhouse gas emissions; therefore, hydrogen production can be one of the alternatives for energy production from waste. Hydrogen production from the organic substance was studied in this study with the waste activated sludge from the municipal wastewater treatment. High rated activated sludge (HRAS) process was applied for the treatment to reduce energy consumption and enhance the organic composition of WAS. The highest COD removal (76%) occurred with the 12 g/L organic fraction of municipal solid waste (OFMSW) addition at a retention time of 120 min. The maximum hydrogen and methane yields for the WAS was 18.9 mL/g VS and 410 mL/g VS respectively. Total carbon emission per g VS of the substrate (OFMSW + waste activated sludge) was found as 0.087 mmol CO₂ and 28.16 mmol CO₂ for dark fermentation and bio-methanization respectively. These kinds of treatment technologies required for the wastewater treatment plantcompensate it some of the energy needs in a renewable source. In this way, the HRAS process decreases the energy requirement of wastewater treatment plant, and carbon-rich waste sludge enables green energy production via lower carbon emissions.     

The economic feasibility study of a 100-MW Power-to-Gas plant

Power-to-Gas (PtG) is a grid-scale energy storage technology by which electricity is converted into gas fuel as an energy carrier. PtG utilizes surplus renewable electricity to generate hydrogen from Solid-Oxide-Cell, and the hydrogen is then combined with CO₂ in the Sabatier process to produce the methane. The transportation of methane is mature and energy-efficient within the existing natural gas pipeline or town gas network. Additionally, it is ideal to make use of the reverse function of SOC, the Solid-Oxide-Fuel-Cell, to generate electricity when the grid is weak in power. This study estimated the cost of building a hypothetical 100-MW PtG power plant with energy storage and power generation capabilities. The emphasis is on the effects of SOC cost, fuel cost and capacity factor to the Levelized Cost of Energy of the PtG plant. The net present value of the plant is analyzed to estimate the lowest affordable contract price to secure a positive present value. Besides, the plant payback period and CO₂ emission are estimated.     

Dark fermentative biohydrogen production using pretreated Scenedesmus obliquus biomass under an integrated paradigm of biorefinery

In recent times, biohydrogen production from microalgal feedstock has garnered considerable research interests to sustainably replace the fossil fuels. The present work adapted an integrated approach of utilizing deoiled Scenedesmus obliquus biomass as feedstock for biohydrogen production and valorization of dark fermentation (DF) effluent via biomethanation. The microalgae was cultivated under different CO₂ concentration. CO₂-air sparging of 5% v/v supported maximum microalgal growth and carbohydrate production with CO₂ fixation ability of 727.7 mg L^?1 d^?1. Thereafter, lipid present in microalgae was extracted for biodiesel production and the deoiled microalgal biomass (DMB) was subjected to different pretreatment techniques to maximize the carbohydrate recovery and biohydrogen yield. Steam heating (121 °C) in coherence with H₂SO₄ (0.5 N) documented highest carbohydrate recovery of 87.5%. DF of acid-thermal pretreated DMB resulted in maximum H₂ yield of 97.6 mL g^?1 VS which was almost 10 times higher as compared to untreated DMB (9.8 mL g^?1 VS). Subsequent utilization of DF effluent in biomethanation process resulted in cumulative methane production of 1060 mL L^?1. The total substrate energy recovered from integrated biofuel production system was 30%. The present study envisages a microalgal biorefinery to produce biohydrogen via DF coupled with concomitant CO₂ sequestration.     

Supercritical water gasification mechanism of polymer-containing oily sludge

In the offshore petroleum industry, polymer-containing oily sludge (PCOS) hinders oil extraction and causes tremendous hazards to the marine ecological environment. In this paper, an effective pretreatment method is proposed to break the adhesive structure of PCOS, and the experiments of supercritical water gasification are carried out under the influencing factors including residence time (5–30 min) and temperature (400–750 °C) in batch reactors. The increase of time and temperature all show great promoting effects on gas production. Polycyclic aromatic hydrocarbons, including naphthalene and phenanthrene, are considered as the main obstacles for a complete gasification. Carbon gasification efficiency (CE) reaches maximum of 95.82% at 750 °C, 23 MPa for 30 min, while naphthalene makes up 70% of the organic compounds in residual liquid products. The highest hydrogen yield of 19.79 (mol H₂/kg of PCOS) is observed in 750 °C for 25 min. A simplified reaction pathway is presented to describe the gaseous products (H₂, CO, CO₂, CH₄). Two intermediates are defined for describing the reaction process bases on the exhaustive study on organic matters in residual liquid products. The results show that the calculated data and the experimental data have a high degree of fit and tar formation reaction is finished within 10 min.     

Utilization of laterite ore as an oxygen carrier in chemical looping reforming of methane for syngas production

Growing energy demands in various sectors have resulted in overusing fossil fuel sources and rise in greenhouse gases in the atmosphere. This necessitates the need for reducing greenhouse gases and shifting to cleaner, renewable energy sources like H₂. Chemical looping is one such renewable method to produce clean H₂. The efficiency of this process depends on the oxygen carrier. Generally, oxygen carriers (OC) are transition metal oxides (Fe₂O₃ or NiO) or some complex metal oxides like spinel or perovskites, but usage of these OCs are restricted due to their availability and redox performance. One solution for selecting OCs can be using industrial waste like slag or low-grade ores because of their composition, which consists of metal oxides. One such low-grade ore is Ni-laterite ore or chromite overburden, a mining waste found in the chromite mines of Sukinda (India). In this work, we have focused on utilizing this laterite ore as an OC for the chemical looping reforming of methane to produce syngas. The reactivity analysis of laterite ore with CH₄ was performed in DSC-TG and the reaction products were analyzed in gas chromatography along with microscopy and spectroscopic techniques. Results showed the formation of H₂ and CO gases along with reduced metallic phases. The total H₂ yield at 750 °C is determined to 53.67 (±1.09) ml/g of OC which is comparable or even higher than existing CeO₂ based OCs. Further, thermodynamic calculations are presented to calculate the theoretical yield for our process and compared with the experimental H₂ yield. This study effectively demonstrates the performance of laterite ore as an OC for generating clean and renewable energy through chemical looping technique.     

Characteristics and performance of the Co–CeO2 catalyst as a function of the promoter (La,Pr, and Zr) used in high temperature water gas shift reaction

The catalysts used to facilitate the water gas shift reaction (WGSR) are generally harmful to the environment. Therefore, catalysts that have high activity and stability in WGSR and do not pollute the environment need to be fabricated. Herein, three promoters (La, Pr, and Zr) are added into Co–CeO₂ (CoCe) catalyst to improve catalytic performance in a high temperature WGSR to produce high-purity hydrogen from waste-derived synthesis gas. Various techniques are employed to confirm the changes in the properties that affect the catalytic performance. The catalytic reaction is performed at a high gas hourly space velocity to screen the performance of the promoted CoCe catalysts. The CoCeZr catalyst shows the highest CO conversion (X_CO = 88% at 450 °C) due to its high Co dispersion and oxygen vacancy resulting from the addition of Zr to the CoCe catalyst; thus, it is most suitable for use in high temperature WGSR.     

Current situation and development prospects of metallurgical by-product gas utilization in China's steel industry

China's annual metallurgical by-product gas production exceeds 1400 billion Nm³, the calorific equivalent of ∼266 million tonnes of coal. The widely-studied blast furnace gas used in hydrogen-enriched carbonic oxide recycling oxygenate furnaces ensures carbon-reduction. Converter gas contains abundant heat resources, equivalent to ∼6.5 million tonnes of coal. Using high-temperature by-product gas online reforming methods to convert thermal energy into chemical energy and combining it with power generation and other industries imparts physical heat recovery exceeding 60%. China's annual coke oven gas (COG) production could support more than 100 million tonnes of direct reduced iron production, thus reducing CO₂ emissions by more than 150 million tonnes (nearly 10% of China's steel industry CO₂ emissions). We summarise the characteristics, availability, and steel-chemical co-production utilisation of three by-product gases, and discuss the application of COG in direct reduced iron production and development of metallurgical by-product gas utilisation for carbon reduction in China.     

Potential of renewable surplus electricity for power-to-gas and geo-methanation in Switzerland

Energy systems are increasingly exposed to variable surplus electricity from renewable sources, particularly photovoltaics. This study estimates the potential to use surplus electricity for power-to-gas with geo-methanation for Switzerland by integrated energy system and power-to-gas modelling. Various CO₂ point sources are assessed concerning exploitable emissions for power-to-gas, which were found to be abundantly available such that 60 TWh surplus electricity could be converted to methane, which is the equivalent of the current annual Swiss natural gas demand. However, the maximum available surplus electricity is only 19 TWh even in a scenario with high photovoltaic expansion. Moreover, making this surplus electricity available for power-to-gas requires an ideal load shifting capacity of up to 10 times the currently installed pumped-hydro capacity. Considering also geological and economic boundary conditions for geo-methanation at run-of-river and municipal waste incinerator sites with nearby CO₂ sources reduces the exploitable surplus electricity from 19 to 2 TWh.     

Effect of manifold injection of hydrogen gas in producer gas and neem biodiesel fueled CRDI dual fuel engine

The high flammability of hydrogen gas gives it a steady flow without throttling in engines while operating. Such engines also include different induction/injection methods. Hydrogen fuels are encouraging fuel for applications of diesel engines in dual fuel mode operation. Engines operating with dual fuel can replace pilot injection of liquid fuel with gaseous fuels, significantly being eco-friendly. Lower particulate matter (PM) and nitrogen oxides (NO_x) emissions are the significant advantages of operating with dual fuel.Consequently, fuels used in the present work are renewable and can generate power for different applications. Hydrogen being gaseous fuel acts as an alternative and shows fascinating use along with diesel to operate the engines with lower emissions. Such engines can also be operated either by injection or induction on compression of gaseous fuels for combustion by initiating with the pilot amount of biodiesel. Present work highlights the experimental investigation conducted on dual fuel mode operation of diesel engine using Neem Oil Methyl Ester (NeOME) and producer gas with enriched hydrogen gas combination. Experiments were performed at four different manifold hydrogen gas injection timings of TDC, 5°aTDC, 10°aTDC and 15°aTDC and three injection durations of 30°CA, 60°CA, and 90°CA. Compared to baseline operation, improvement in engine performance was evaluated in combustion and its emission characteristics. Current experimental investigations revealed that the 10°aTDC hydrogen manifold injection with 60°CA injection duration showed better performance. The BTE of diesel + PG and NeOME + PG operation was found to be 28% and 23%, respectively, and the emissions level were reduced to 25.4%, 14.6%, 54.6%, and 26.8% for CO, HC, smoke, and NO_x, respectively.     

Screening and optimisation of hydrogen production by newly isolated nitrogen-fixing cyanobacterial strains

Recently, there has been a propensity to postpone dealing with the world's climate concerns until later, resulting in a 1.5 °C rise in temperature over the last century. Therefore, interest in biologically derived, inexhaustible energy sources based on solar energy is growing. Cyanobacteria have the potential to produce clean, renewable fuels in the form of hydrogen (H₂) gas, derived from solar energy and water. The current study reports the screening 11 cyanobacterial strains isolated from rice paddies and hotsprings for efficient H₂ producers. According to our findings, H₂ concentrations in the species ranged from 3.6 to 48.9 μmol mg⁻¹ Chl a h⁻¹. H₂ production by isolated species was shown to have a 2% positive influence on oxygen (O₂) and carbon dioxide (CO₂) concentrations and a 2% negative effect on all nitrogen gas (N₂) concentrations. It was discovered that at high CO₂ concentrations, photosynthesis is enhanced but H₂ production is suppressed. Anabaena variabilis BTA-1047 was found to be the most active H₂-producing species, with an H₂ production activity of 21.3 μmol mg⁻¹ Chl a h⁻¹. Moreover, a 1% O₂: 2% CO₂ gas mixture doubled the strain activity of H₂ production. The findings of the study called into the question the notion that only an anaerobic environment is required for H₂ production by N₂-fixing cyanobacterial species and explored whether H₂ productivity can be increased by stimulating the micro-anaerobic environment with a carbon source.     

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.