Hydrofluoroolefin-based mixed refrigerant for enhanced performance of hydrogen liquefaction process

Hydrogen has the highest gravimetric energy density of all fuels; however, it has a low volumetric energy density, unfavorable for storage and transportation. Hydrogen is usually liquefied to meet the bulk transportation needs. The exothermic interconversion of its spin isomers is an additional activity to an already energy-intensive process. The most significant temperature drop occurs in the precooling cycle (between ?150 °C and up to ?180 °C) and consumes more than 50% of the required energy. To reduce the energy consumption and improve the exergy efficiency of the hydrogen liquefaction process, a new high-boiling component, Hydrofluoroolefin (HFO-1234yf), is added to the precooled mixed refrigerant. As a result, the specific energy consumption of precooling cycle reduces by 41.8%, from 10.15 kWh/kg_LH2 to 5.90 kWh/kg_LH2, for the overall process. The exergy efficiency of the proposed case increases by 43.7%; however, the total equipment cost is also the highest. The inflated cost is primarily due to the added ortho-to-para hydrogen conversion reactor, boosting the para-hydrogen concentration. From the perspective of bulk storage and transportation of liquid hydrogen, the simplicity of design and low energy consumption build a convincing case for considering the commercialization of the process.     

Evaluating influences of impurities on hydrogen production in the reaction of Si with water using Si sludge

Hydrogen has attracted much attention as a next-generation energy resource. Among various technologies, one of the promising approaches for hydrogen production is the use of the reaction between Si and water, which does not require any heat, electricity, and light energy as an input. Notwithstanding the usefulness of Si as a prospective raw material of hydrogen production, the manufacturing process of Si requires a significant amount of energy. Therefore, as an alternative to pure Si, this study used a wasted Si sludge, generated though the manufacturing process of Si wafer, for the direct reuse. Thus, the Si-water reaction for the hydrogen generation was investigated in comparison with pure Si and Si sludge by employing X-ray absorption near edge structure (XANES) to evaluate the feasibility of hydrogen production with the use of Si sludge and to identify the influence of impurities contained in Si sludge. As a result, hydrogen was not produced with the use of Si sludge because of containing Al compound as the impurity. Through the XANES analysis, the formation of SiO(OH)₂ was found as core-shell structure, which potentially would hinder the hydrogen generation.     

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.     

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.     

Reinforcement learning based energy management systems and hydrogen refuelling stations for fuel cell electric vehicles: An overview

This paper examines the current state of the art of hydrogen refuelling stations-based production and storage systems for fuel cell hybrid electric vehicles (FCHEV). Nowadays, the emissions are increasing rapidly due to the usage of fossil fuels and the demand for hydrogen refuelling stations (HRS) is emerging to replace the conventional vehicles with FCHEVs. Hence, the availability of HRS and its economic aspects are discussed. In addition, a comprehensive study is presented on the energy storage systems such as batteries, supercapacitors and fuel cells which play a major role in the FCHEVs. An energy management system (EMS) is essential to meet the load requirement with effective utilisation of power sources with various optimizing techniques. A detailed comparative analysis is presented on the merits of Reinforcement learning (RL) for the FCHEVs. The significant challenges are discussed in depth with potential solutions for future work.     

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.     

Review of hydrogen economy in Malaysia and its way forward

Heavy fossil fuels consumption has raised concerns over the energy security and climate change while hydrogen is regarded as the fuel of future to decarbonize global energy use. Hydrogen is commonly used as feedstocks in chemical industries and has a wide range of energy applications such as vehicle fuel, boiler fuel, and energy storage. However, the development of hydrogen energy in Malaysia is sluggish despite the predefined targets in hydrogen roadmap. This paper aims to study the future directions of hydrogen economy in Malaysia considering a variety of hydrogen applications. The potential approaches for hydrogen production, storage, distribution and application in Malaysia have been reviewed and the challenges of hydrogen economy are discussed. A conceptual framework for the accomplishment of hydrogen economy has been proposed where renewable hydrogen could penetrate Malaysia market in three phases. In the first phase, the market should aim to utilize the hydrogen as feedstock for chemical industries. Once the hydrogen production side is matured in the second phase, hydrogen should be used as fuel in internal combustion engines or burners. In the final phase hydrogen should be used as fuel for automobiles (using fuel cell), fuel-cell combined heat and power (CHP) and as energy storage.     

Preparation of hydrogen from metals and water without CO2 emissions

Considering the high calorific value and low-carbon characteristics of hydrogen energy, it will play an important role in replacing fossil energy sources. The production of hydrogen from renewable energy sources for electricity generation and electrolysis of water is an important process to obtain green hydrogen compared with classic low-carbon hydrogen production methods. However, the challenges in this process include the high cost of liquefied hydrogen and the difficulty of storing hydrogen on a large scale. In this paper, we propose a new route for hydrogen storage in metals, namely, electricity generation from renewable energy sources, electrolysis to obtain metals, and subsequent hydrogen production from metals and water. Metal monomers facilitate large-scale and long-term storage and transportation, and metals can be used as large-scale hydrogen storage carriers in the future. In this technical route, the reaction between metal and water for hydrogen production is an important link. In this paper, we systematically summarize the research progress, development trend, and challenges in the field of metal to hydrogen production. This study aim to aid in the development of this field.     

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.     

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.     

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.     

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.     

Economic valuation of green hydrogen charging compared to gray hydrogen charging: The case of South Korea

The South Korean government promotes hydrogen-powered vehicles to reduce greenhouse gas (GHG) emissions but these vehicles use gray hydrogen while charging, which causes GHG emissions. Therefore, converting this fuel into green hydrogen is necessary to help reduce GHG emissions, which will incur investment costs of approximately USD 20 billion over a decade. In this study, a contingent valuation method is applied in an analysis to examine the extent to which consumers are willing to pay for green hydrogen charging compared to gray hydrogen charging. The results indicate that the monthly mean of willingness to pay per driver is 51,674 KRW (USD 45.85), equivalent to 4302 KRW per kg (USD 3.82). Additionally, consumers accept a 28.5% increase in the monthly average fuel expenses when converting to green hydrogen. These findings can be used in the development of pricing and energy use plans to finance the expansion of green hydrogen infrastructure.     

A techno-economic study for a hydrogen storage system in a microgrid located in baja California,Mexico. Levelized cost of energy for power to gas to power scenarios

In this work a techno economic feasibility study is carried out to implement a Hydrogen based Power to Gas to Power (P2G2P) in a Microgrid, located in a rural area in Baja California, Mexico. The study aims to define the feasibility to store energy throughout seasons with this novel alternative using an electrolyzer to produce green hydrogen from excess renewable energy in winter, to store it during months and re inject it to the grid as electricity by a fuel cell in the high energy demanding season. The Microgrid was modeled in Homer software and simulations of the P2G2P lead to Levelized Cost of Energy data to compare between the P2G2P scenarios and the current diesel-battery based solution to complete the high demand by the community. This study shows that using hydrogen and fuel cells to substitute diesel generators it is possible to reduce CO₂ emissions up to a 27% and that in order for the P2G2P to be cost competitive, the fuel cell should reduce its cost in 50%; confirming that, in the medium to long term, the hydrogen storage system is a coherent alternative towards decarbonization of the distributed energy generation.     

Molecular simulation of copper based metal-organic framework (Cu-MOF) for hydrogen adsorption

Metal organic framework (MOF) are widely used in adsorption and separation due to their porous nature, high surface area, structural diversity and lower crystal density. Due to their exceptional thermal and chemical stability, Cu-based MOF are considered excellent hydrogen storage materials in the world of MOFs. Efforts to assess the effectiveness of hydrogen storage in MOFs with molecular simulation and theoretical modeling are crucial in identifying the most promising materials before extensive experiments are undertaken. In the current work, hydrogen adsorption in four copper MOFs namely, MOF-199, MOF 399, PCN-6′, and PCN-20 has been analyzed. These MOFs have a similar secondary building unit (SBU) structure, i.e., twisted boracite (tbo) topology. The Grand Canonical Monte Carlo (GCMC) simulation was carried at room temperature (298 K) as well as at cryogenic temperature (77 K) and pressures ranging from 0 to 1 bar and 0–50 bar. These temperatures and pressure were selected to comply with the conditions set by department of energy (DOE) and to perform a comparative study on hydrogen adsorption at two different temperatures. The adsorption isotherm, isosteric heat, and the adsorption sites were analyzed in all the MOFs. The findings revealed that isosteric heat influenced hydrogen uptake at low pressures, while at high pressures, porosity and surface area affected hydrogen storage capacity. PCN-6′ is considered viable material at 298 K and 77 K due to its high hydrogen uptake.     

Cooling effect analysis on para-ortho hydrogen conversion coupled in vapor-cooled shield

The conversion process from parahydrogen to orthohydrogen accompanies an endothermic effect. Embedment of a para-ortho hydrogen converter into the thermal insulation could enhance the thermal protection of a liquid hydrogen storage tank. A physical model was proposed to simulate the heat transfer behavior of the insulation structure that integrates a polyurethane foam, a blanket of multilayer insulation, a vapor-cooled shield, and a para-ortho hydrogen converter. The effect of the para-ortho conversion process was considered. The model was validated by experimental data and then used to investigate how the para-ortho hydrogen conversion influences the temperature distribution inside the composite insulation. It was found that a single converter improves the cooling performance most effectively if it is placed at the middle length of the venting pipe mounted on the vapor-cooled shield. Either incorporating more converters or extending the length of the vapor-cooled shield pipes brings limited further improvement. The optimum position of the vapor-cooled shield inside the multilayer insulation moves towards the cold boundary in the presence of para-ortho conversion, compared to conventional vapor-cooled shield and multilayer insulation structures. A net heat flux reduction of over 10% could be achieved when the para-ortho conversion is located at the optimal position inside the vapor-cooled shield.     

Environmental sustainability assessment of large-scale hydrogen production using prospective life cycle analysis

The need for a rapid transformation to low-carbon economies has rekindled hydrogen as a promising energy carrier. Yet, the full range of environmental consequences of large-scale hydrogen production remains unclear. Here, prospective life cycle analysis is used to compare different options to produce 500 Mt/yr of hydrogen, including scenarios that consider likely changes to future supply chains. The resulting environmental and human health impacts of such production levels are further put into context with the Planetary Boundaries framework, known human health burdens, the impacts of the world economy, and the externality-priced production costs that embody the environmental impact. The results indicate that climate change impacts of projected production levels are 3.3–5.4 times higher than the allocated planetary boundary, with only green hydrogen from wind energy staying below the boundary. Human health impacts and other environmental impacts are less severe in comparison but metal depletion and ecotoxicity impacts of green hydrogen deserve further attention. Priced-in environmental damages increase the cost most strongly for blue hydrogen (from ～2 to ～5 USD/kg hydrogen), while such true costs drop most strongly for green hydrogen from solar photovoltaic (from ～7 to ～3 USD/kg hydrogen) when applying prospective life cycle analysis. This perspective helps to evaluate potentially unintended consequences and contributes to the debate about blue and green hydrogen.     

Optimization on volume ratio of three-stage cascade storage system in hydrogen refueling stations

Three-stage cascade storage systems are widely adopted in hydrogen refueling stations. Their volume ratio has a remarkable impact on the performance of refueling systems. In this study, a thermodynamic model that considers the complete refueling–recovery process is developed. The effects of volume ratio on the utilization ratio and the specific energy consumption of the model is investigated, and the optimization of the volume ratio is explored and discussed. The utilization ratio decreases with the increase in the proportion of low-pressure stage volume (pLP), and a proper volume of medium-pressure stage improves the utilization ratio. The specific energy consumption decreases as pLP increases when the stationary storage capacity is relatively small. However, when the stationary storage capacity is relatively large, the specific energy consumption does not decrease monotonically, and a low specific energy consumption and a high utilization ratio can be simultaneously obtained at low pLP.     

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.     

Techno-economic feasibility of power to gas–oxy-fuel boiler hybrid system under uncertainty

One of the main challenges associated with utilisation of the renewable energy is the need for energy storage to handle its intermittent nature. Power-to-Gas (PtG) represents a promising option to foster the conversion of renewable electricity into energy carriers that may attend electrical, thermal, or mechanical needs on-demand. This work aimed to incorporate a stochastic approach (Artificial Neural Network combined with Monte Carlo simulations) into the thermodynamic and economic analysis of the PtG process hybridized with an oxy-fuel boiler (modelled in Aspen Plus^®). Such approach generated probability density curves for the key techno-economic performance indicators of the PtG process. Results showed that the mean utilisation of electricity from RES, accounting for the chemical energy in SNG and heat from methanators, reached 62.6%. Besides, the probability that the discounted cash flow is positive was estimated to be only 13.4%, under the set of conditions considered in the work. This work also showed that in order to make the mean net present value positive, subsidies of 68 €/MW_elh are required (with respect to the electricity consumed by PtG process from RES). This figure is similar to the financial aids received by other technologies in the current economic environment.