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.     

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.     

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.     

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.     

Effect of ZrO2 on the performance of Co–CeO2 catalysts for hydrogen production from waste-derived synthesis gas using high-temperature water gas shift reaction

In this study, highly active and stable CeO₂, ZrO₂, and Zr_(1-x)Ce_(x)O₂-supported Co catalysts were prepared using the co-precipitation method for the high-temperature water gas shift reaction to produce hydrogen from waste-derived synthesis gas. The physicochemical properties of the catalysts were investigated by carrying out Brunauer-Emmet-Teller, X-ray diffraction, CO-chemisorption, Raman spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, and H₂-temperature-programmed reduction measurements. With an increase in the ZrO₂ content, the surface area and reducibility of the catalysts increased, while the interaction between Co and the support and the dispersion of Co deteriorated. The Co–Zr_0.4Ce_0·6O₂ and Co–Zr_0.6Ce_0·4O₂ catalysts showed higher oxygen storage capacity than that of the others because of the distortion of the CeO₂ structure due to the substitution of Ce⁴⁺ by Zr⁴⁺. The Co–Zr_0.6Ce_0·4O₂ catalyst with high reducibility and oxygen storage capacity exhibited the best catalytic performance and stability among all the catalysts investigated in this study.     

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.     

Determination of the potential of cyanobacterial strains for hydrogen production

Hydrogen (H₂) is a renewable, abundant, and nonpolluting source of energy. Photosynthetic organisms capture sunlight very efficiently and convert it into organic molecules. Cyanobacteria produce H₂ by breaking down organic compounds and water. In this study, biological H₂ was produced from various strains of cyanobacteria. Moreover, H₂ accumulation by Synechocystis sp. PCC 6803 was as high as 0.037 μmol/mg Chl/h within 120 h in the dark. The wild-type, filamentous, non-heterocystous cyanobacterium Desertifilum sp. IPPAS B-1220 was found to produce a maximum of 0.229 μmol/mg Chl/h in the gas phase within 166 h in the light, which was on par with the maximum yield reported in the literature. DCMU at 10 μM increased H₂ production by Desertifilum sp. IPPAS B-1220 by 1.5-fold to 0.348 μmol H₂/mg Chl/h. This is the first report on the capability of Desertifilum cyanobacterium to produce H₂.     

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.     

HRT control as a strategy to enhance continuous hydrogen production from sugarcane juice under mesophilic and thermophilic conditions in AFBRs

The objective of this study was to evaluate the effects of hydraulic retention time (HRT) (8–1 h) on H₂ production from sugarcane juice (5000 mg COD L⁻¹) in mesophilic (30 °C, AFBR-30) and thermophilic (55 °C, AFBR-55) anaerobic fluidized bed reactors (AFBRs). At HRTs of 8 and 1 h in AFBR-30, the H₂ production rates were 60 and 116 mL H₂ h⁻¹ L⁻¹, the hydrogen yields were 0.60 and 0.10 mol H₂ mol⁻¹ hexose, and the highest bacterial diversities were 2.47 and 2.34, respectively. In AFBR-55, the decrease in the HRT from 8 to 1 h increased the hydrogen production rate to 501 mL H₂ h⁻¹ L⁻¹ at the HRT of 1 h. The maximum hydrogen yield of 1.52 mol H₂ mol⁻¹ hexose was observed at the HRT of 2 h and was associated with the lowest bacterial diversity (0.92) and highest bacterial dominance (0.52).     

Preparation of gas standards for quality assurance of hydrogen fuel

This study has developed traceable standards for evaluating impurities in hydrogen fuel according to ISO 14687. Impurities in raw H₂, including sub μmol/mol levels of CO, CO₂, and CH₄, were analyzed using multiple detectors while avoiding contamination. The gravimetric standards prepared included mixtures of the following nominal concentrations: 1, 2, 3–5, 8–11, 17–23, and 47–65 μmol/mol for CO₂, CH₄ and CO, O₂, N₂, Ar, and He, respectively. The expanded uncertainty ranges were 0.8% for Ar, N₂, and He, 1% for CH₄ and CO, and 2% for CO₂ and O₂. These standards were stable, while that for CO varied by only 0.5% during a time span of three years. The prepared standards are useful for evaluating the compliance of H₂ fuel in service stations with ISO 14687 quality requirements.     

Performance analysis of a novel solar PTC integrated system for multi-generation with hydrogen production

The performance analysis of a novel multi-generation (MG) system that is developed for electricity, cooling, hot water and hydrogen production is presented in this study. MG systems in literature are predominantly built on a gas cycle, integrated with other thermodynamic cycles. The aim of this study is to achieve better thermodynamic (energy and exergy) performance using a MG system (without a gas cycle) that produces hydrogen. A proton exchange membrane (PEM) utilizes some of the electricity generated by the MG system to produce hydrogen. Two Rankine cycles with regeneration and reheat principles are used in the MG configuration. Double effect and single effect absorption cycles are also used to produce cooling. The electricity, hot water, cooling effect, and hydrogen production from the multi-generation are 1027 kW, 188.5 kW, 11.23 kg/s and 0.9785 kg/h respectively. An overall energy and exergy efficiency of 71.6% and 24.5% respectively is achieved considering the solar parabolic trough collector (PTC) input and this can increase to 93.3% and 31.9% if the input source is 100% efficient. The greenhouse gas emission reduction of this MG system is also analyzed.     

Recent advances in artificial neural network research for modeling hydrogen production processes

Artificial Neural Networks (ANN) have been widely used by scientists in a variety of energy modes (biomass, wind, solar, geothermal, and hydroelectric). This review highlights the assistance of ANN for researchers in the quest for discovering more advanced materials/processes for efficient hydrogen production (HP). The review is divided into two parts in this context. The first section briefly mentions, in terms of technologies, economy, energy consumption, and costs symmetrically outlined the advantages and disadvantages of various HP routes such as fossil fuel/biomass conversion, water electrolysis, microbial fermentation, and photocatalysis. Subsequently, ANN and ANN hybrid studies implemented in HP research were evaluated. Finally, statistics of hybrid studies with ANN are given, and future research proposals and hot research topics are briefly discussed. This research, which touches upon the types of ANNs applied to HP methods and their comparison with other modeling techniques, has an essential place in its field.     

Pd-decorated CNT as sensitive material for applications in hydrogen isotopes sensing - Application as gas sensor

Applicability of multiwall carbon nanotubes (MWCNTs) decorated with palladium nanoparticles as sensitive layer in a resistive microsensor for identification of hydrogen isotopes, Deuterium (²H) and Protium (¹H), has been demonstrated. Palladium nanoparticles were anchored on the MWCNTs surface via a chemical process involving micellization, from a precursor chloride solution, in high ultrasonic density field. Pd-MWCNTs are quasi-aligned between the interdigitated gold electrodes of a SiO₂ substrate by drop casting and di-electrophoretic alignment in Tetrahydrofuran (THF) and Nafion solution. The morphostructural characterization of the sensitive material has been carried out through SEM, TEM and Raman spectroscopy and its gas sensing properties were evaluated using electrical measurements performed on a series of isotope concentrations (ranging from 0.1% up to 1%, and from 1% to 4%, value to which hydrogen becomes explosive) diluted in argon, to observe the evolution of the sensor sensibility. The two hydrogen isotopes have different behaviors related to the adsorption on the Pd-MWCNT, which is well observed in the resistance change. Therefore, the sensor based on Pd-MWCNTs could be a viable solution to be integrated in systems for hydrogen leakage detection.     

The production and application of hydrogen in steel industry

Due to the increasingly serious environmental issues and continuous depletion of fossil resources, the steel industry is facing unprecedented pressure to reduce CO₂ emissions and achieve the sustainable energy development. Hydrogen is considered as the most promising clean energy in the 21st century due to the diverse sources, high calorific value, good thermal conductivity and high reaction rate, making hydrogen have great potential to apply in the steel industry. In this review, different hydrogen production technologies which have potential to provide hydrogen or hydrogen-rich gas for the great demand of steel plants are described. The applications of hydrogen in the blast furnace (BF) production process, direct reduction iron (DRI) process and smelting reduction iron process are summarized. Furthermore, the functions of hydrogen or hydrogen-rich gas as fuels are also discussed. In addition, some suggestions and outlooks are provided for future development of steel industry in China.     

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.     

Economic viability assessment of sustainable hydrogen production,storage, and utilisation technologies integrated into on- and off-grid micro-grids: A performance comparison of different meta-heuristics

In recent years, there has been considerable interest in the development of zero-emissions, sustainable energy systems utilising the potential of hydrogen energy technologies. However, the improper long-term economic assessment of costs and consequences of such hydrogen-based renewable energy systems has hindered the transition to the so-called hydrogen economy in many cases. One of the main reasons for this is the inefficiency of the optimization techniques employed to estimate the whole-life costs of such systems. Owing to the highly nonlinear and non-convex nature of the life-cycle cost optimization problems of sustainable energy systems using hydrogen as an energy carrier, meta-heuristic optimization techniques must be utilised to solve them. To this end, using a specifically developed artificial intelligence-based micro-grid capacity planning method, this paper examines the performances of twenty meta-heuristics in solving the optimal design problems of three conceptualised hydrogen-based micro-grids, as test-case systems. Accordingly, the obtained numeric simulation results using MATLAB indicate that some of the newly introduced meta-heuristics can play a key role in facilitating the successful, cost-effective development and implementation of hydrogen supply chain models. Notably, the moth-flame optimization algorithm is found capable of reducing the life-cycle costs of micro-grids by up to 6.5% as compared to the dragonfly algorithm.     

Comparative techno-economic study of typically combustion-less hydrogen production alternatives

A techno-economic study is performed for a large scale combustion-less hydrogen production process based on Steam Methane Reforming (SMR). Two process versions relying on different renewable heat sources are compared: (1) direct solar heating from a concentrated solar power system, and (2) radiation from resistive electrical heaters (electric SMR). Both processes are developed around an integrated micro-reactor technology, incorporating in a monolithic block most sub-processes needed to perform SMR. A baseline techno-economic scenario with low-cost feedstock and electricity, priced at $4/MMBtu and $0.04/kWh respectively, results in an LCOH of $2.31/kg_H2 for solar SMR and $1.59/kg_H2 for electric SMR. Results further show that solar SMR is currently more attractive economically than electric SMR coupled with distributed wind power systems, but electric SMR is more favourable in the long term due to the expected future improvements in the LCOE and capacity factor of wind power systems.     

Transition metal/carbon nanoparticle composite catalysts as platinum substitutes for bioelectrochemical hydrogen production using microbial electrolysis cells

Various metal nanoparticle catalysts supported on Vulcan XC-72 and carbon-nanomaterial-based catalysts were fabricated and compared and assessed as substitutes of platinum in microbial electrolysis cells (MECs). The metal-nanoparticle-loaded cathodes exhibited relatively better hydrogen production and electrochemical properties than cathodes coated with carbon nanoparticles (CNPs) and carbon nanotubes (CNTs) did. Catalysts containing Pt (alone or mixed with other metals) most effectively produced hydrogen in terms of overall conversion efficiency, followed by Ni alone or combined with other metals in the order: Pt/C (80.6%) > PtNi/C (76.8%) > PtCu/C (72.6%) > Ni/C (73.0%) > Cu/C (65.8%) > CNPs (47.0%) > CNTs (38.9%) > plain carbon felt (38.7%). Further, in terms of long-term catalytic stability, Ni-based catalysts degraded to a lesser extent over time than did the Cu/C catalyst (which showed the maximum degradation). Overall, the hydrogen generation efficiency, catalyst stability, and current density of the Ni-based catalysts were almost comparable to those of Pt catalysts. Thus, Ni is an effective and inexpensive alternative to Pt catalysts for hydrogen production by MECs.     

Wind-powered 250 kW electrolyzer for dynamic hydrogen production: A pilot study

Alkaline water electrolysis is the most promising approach for the industrial production of green hydrogen. This study investigates the dynamic operational characteristics of an industrial-scale alkaline electrolyzer with a rated hydrogen production of 50 m³/h. Strategies for system control and equipment improvement in dynamic-mode alkaline electrolytic hydrogen production are discussed. The electrolyzer can operate over a 30%–100% rated power load, thereby facilitating high-purity (>99.5%) H₂ production, competitive DC energy efficiency (4.01–4.51 kW h/Nm³ H₂, i.e., 73.1%–65.0% LHV), and good gas–liquid fluid balance. A safe H₂ content of 2% in O₂ (50% LFL) can be guaranteed by adjusting the system pressure. In transient operation, the electrolyzer can realize minute-level power and pressure modulation with high accuracy. The results confirm that the proposed alkaline electrolyzer can absorb highly fluctuating energy output from renewables because of its capability to operate in a dynamic mode.