Process optimization for large-scale hydrogen liquefaction

The investment in the hydrogen infrastructure for hydrogen mobility has lately seen a significant acceleration. The demand for energy and cost efficient hydrogen liquefaction processes has also increased steadily. A significant scale-up in liquid hydrogen (LH₂) production capacity from today's typical 5–10 metric tons per day (tpd) LH₂ is predicted for the next decade. For hydrogen liquefaction, the future target for the specific energy consumption is set to 6 kWh per kg LH₂ and requires a reduction of up to 40% compared to conventional 5 tpd LH₂ liquefiers. Efficiency improvements, however, are limited by the required plant capital costs, technological risks and process complexity. The aim of this paper is the reduction of the specific costs for hydrogen liquefaction, including plant capital and operating expenses, through process optimization. The paper outlines a novel approach to process development for large-scale hydrogen liquefaction. The presented liquefier simulation and cost estimation model is coupled to a process optimizer with specific energy consumption and specific liquefaction costs as objective functions. A design optimization is undertaken for newly developed hydrogen liquefaction concepts, for plant capacities between 25 tpd and 100 tpd LH₂ with different precooling configurations and a sensitivity in the electricity costs. Compared to a 5 tpd LH₂ plant, the optimized specific liquefaction costs for a 25 tpd LH₂ liquefier are reduced by about 50%. The high-pressure hydrogen cycle with a mixed-refrigerant precooling cycle is selected as preferred liquefaction process for a cost-optimized 100 tpd LH₂ plant design. A specific energy consumption below 6 kWh per kg LH₂ can be achieved while reducing the specific liquefaction costs by 67% compared to 5 tpd LH₂ plants. The cost targets for hydrogen refuelling and mobility can be reached with a liquid hydrogen distribution and the herewith presented cost-optimized large-scale liquefaction plant concepts.     

Roadmap to economically viable hydrogen liquefaction

The distribution of hydrogen in liquid state has several advantages because of its higher volumetric density compared to compressed hydrogen gas. The demand for liquid hydrogen (LH₂), particularly driven by clean fuel cell applications, is expected to rise in the near future. Large-scale hydrogen liquefaction plants will play a major role within the hydrogen supply chain. The barriers of built hydrogen liquefiers is the low exergy efficiency and the high specific liquefaction costs. Exergy efficiency improvements, however, are limited by economic viability. The focus of this paper is to present a roadmap for the scale-up of hydrogen liquefaction technology, from state-of-the-art plants to newly developed large-scale liquefaction processes. The work is aimed at reducing the specific liquefaction costs by finding an optimal trade-off between capital costs and operating costs. To this end, two developed hydrogen liquefaction processes were optimized for specific energy consumption and specific liquefaction costs, showing the potential to reduce the specific liquefaction costs by 67% for a 100 tpd LH₂ plant compared to a conventional 5 tpd LH₂ plant while achieving a specific energy consumption between 5.9 and 6.6 kWh per kg LH₂ with technology that is or will be available within 5 years. The results make liquid hydrogen a viable distribution route for hydrogen for mobility.     

Second law analysis of hydrogen liquefiers operating on the modified Collins cycle

Hydrogen liquefaction systems have been the subject of intense investigations for many years. Some established gas liquefaction systems, such as the precooled Linde–Hampson systems, are not used for hydrogen liquefaction in part because of their relatively low efficiencies. Recently, more promising systems employing the modified Collins cycle have been introduced. This paper reports on second law analyses of a hydrogen liquefier operating on the modified Collins cycle. Two different modifications employing the cycle in question were attempted: (1) a helium‐refrigerated hydrogen liquefaction system and (2) a hydrogen‐refrigerated hydrogen liquefaction system. Analyses were carried out in order to identify potential areas of development and efficiency improvement. A computer code capable of computing system and component efficiencies; exergy losses; and optimum number and operating conditions of compressors, expanders, aftercoolers, intercoolers, and Joule–Thomson valves was developed. Evaluation of the thermodynamic and transport properties of hydrogen at different temperature levels was achieved by employing a hydrogen property code developed by researchers at the National Bureau of Standards (currently NIST). A parametric analysis was carried out and optimal decision rules pertaining to system component selection and design were reached. Economic analyses were also reported for both systems and indicated that the helium‐refrigerated hydrogen liquefier is more economically feasible than the hydrogen‐refrigerated hydrogen liquefier. Copyright © 2001 John Wiley & Sons, Ltd.     

Review on the design and optimization of hydrogen liquefaction processes

The key technologies of liquefied hydrogen have been developing rapidly due to its prospective energy exchange effectiveness, zero emissions, and long distance and economic transportation. However, hydrogen liquefaction is one of the most energy-intensive industrial processes. A small reduction in energy consumption and an improvement in efficiency may decrease the operating cost of the entire process. In this paper, the detailed progress of design and optimization for hydrogen liquefaction in recent years are summarized. Then, based on the refrigeration cycles, the hydrogen liquefaction processes are divided into two parts, namely precooled liquefaction process and cascade liquefaction process. Among the existing technologies, the SEC of most hydrogen liquefaction processes is limited in the range of 5–8 kWh/ {\mathrm{k}\mathrm{g}}_{{\mathrm{L}\mathrm{H}}_2} : liquid hydrogen). The exergy efficiencies of processes are around 40% to 60%. Finally, several future improvements for hydrogen liquefaction process design and optimization are proposed. The mixed refrigerants (MRs) as the working fluids of the process and the combination of the traditional hydrogen liquefaction process with the renewable energy technology will be the great prospects for development in near future.     

Simulation on a proposed large-scale liquid hydrogen plant using a multi-component refrigerant refrigeration system

A proposed liquid hydrogen plant using a multi-component refrigerant (MR) refrigeration system is explained in this paper. A cycle that is capable of producing 100 tons of liquid hydrogen per day is simulated. The MR system can be used to cool feed normal hydrogen gas from 25 °C to the equilibrium temperature of −193 °C with a high efficiency. In addition, for the transition from the equilibrium temperature of the hydrogen gas from −193 °C to −253 °C, the new proposed four H₂ Joule–Brayton cascade refrigeration system is recommended. The overall power consumption of the proposed plant is 5.35 kWh/kg_LH2, with an ideal minimum of 2.89 kWh/kg_LH2. The current plant in Ingolstadt is used as a reference, which has an energy consumption of 13.58 kWh/kg_LH2 and an efficiency of 21.28%: the efficiency of the proposed system is 54.02% or more, where this depends on the assumed efficiency values for the compressors and expanders. Moreover, the proposed system has some smaller-size heat exchangers, much smaller compressor motors, and smaller crankcase compressors. Thus, it could represent a plant with the lowest construction cost with respect to the amount of liquid hydrogen produced in comparison to today’s plants, e.g., in Ingolstadt and Leuna. Therefore, the proposed system has many improvements that serve as an example for future hydrogen liquefaction plants.     

Techno-economic modeling of zero-emission marine transport with hydrogen fuel and superconducting propulsion system: Case study of a passenger ferry

This paper proposes a techno-economic model for a high-speed hydrogen ferry. The model can describe the system properties i.e. energy demand, weight, and daily operating expenses of the ferry. A novel aspect is the consideration of superconductivity as a measure for cost saving in the setting where liquid hydrogen (LH₂) can be both coolant and fuel. We survey different scenarios for a high-speed ferry that could carry 300 passengers. The results show that, despite higher energy demand, compressed hydrogen gas is more economical compared with LH₂ for now; however, constructing large-scale hydrogen liquefaction plants make it competitive in the future. Moreover, compressed hydrogen gas is restricted to a shorter distance while LH₂ makes longer distances possible, and whenever LH₂ is accessible, using a superconducting propulsion system has a beneficial impact on both energy and cost savings. These effects strengthen if the operational time or the weight of the ferry increases.     

Economics of hydrogen production and liquefaction by geothermal energy

Seven models are considered for the production and liquefaction of hydrogen by geothermal energy. In these models, we use electrolysis and high-temperature steam electrolysis processes for hydrogen production, a binary power plant for geothermal power production, and a pre-cooled Linde–Hampson cycle for hydrogen liquefaction. Also, an absorption cooling system is used for the pre-cooling of hydrogen before the liquefaction process. A methodology is developed for the economic analysis of the models. It is estimated that the cost of hydrogen production and liquefaction ranges between 0.979 $/kg H₂ and 2.615 $/kg H₂ depending on the model. The effect of geothermal water temperature on the cost of hydrogen production and liquefaction is investigated. The results show that the cost of hydrogen production and liquefaction decreases as the geothermal water temperature increases. Also, capital costs for the models involving hydrogen liquefaction are greater than those for the models involving hydrogen production only.     

A novel hydrogen liquefaction process configuration with combined mixed refrigerant systems

A novel large-scale plant for hydrogen liquefying is proposed and analyzed. The liquid hydrogen production rate of the proposed plant is 100 tons per day to provide the required LH₂ for a large urban area with 100,000–200,000 hydrogen vehicles supply. In the pre-cooling section of the process, a new mixed refrigerant (MR) refrigeration cycle, combined with a Joule–Brayton refrigeration cycle, precool gaseous hydrogen feed from 25 °C to the temperature ?198.2 °C. A new refrigeration system with six simple Linde–Hampson cascade cycles cools low-temperature gaseous hydrogen from ?198.2 °C to temperature ?252.2 °C. The process specific energy consumption (SEC) is $7.69{\text{kWh/kg}}_{L{H}_2}$ which minimum value is $2.89{\text{kWh/kg}}_{L{H}_2}$ in ideal conditions. The exergy efficiency of the system is 39.5%, which is considerably higher than the existing hydrogen liquefier plants around the world. However, assuming more efficiency values for the equipment can improve it. The energy analysis specifies that coefficient of performance (COP) of the process is 0.1710 which is a high quantity of its kind between other similar processes. Effect of various refrigerant components concentration, discharge pressure of the high pressure compressors of the pre-cooling section, and hydrogen feed pressure on the process COP, exergy efficiency, and SEC are investigated. After that, a new MR will be offered for the cryogenic section of the plant. The system improvements are considerable comparing to current hydrogen liquefying plants, therefore, the proposed conceptual system can be used for future hydrogen liquefaction plants design.     

Canada’s program on nuclear hydrogen production and the thermochemical Cu–Cl cycle

This paper presents an overview of the status of Canada’s program on nuclear hydrogen production and the thermochemical copper–chlorine (Cu–Cl) cycle. Enabling technologies for the Cu–Cl cycle are being developed by a Canadian consortium, as part of the Generation IV International Forum (GIF) for hydrogen production with the next generation of nuclear reactors. Particular emphasis in this paper is given to hydrogen production with Canada’s Super-Critical Water Reactor, SCWR. Recent advances towards an integrated lab-scale Cu–Cl cycle are discussed, including experimentation, modeling, simulation, advanced materials, thermochemistry, safety, reliability and economics. In addition, electrolysis during off-peak hours, and the processes of integrating hydrogen plants with Canada’s nuclear plants are presented.     

Dynamic flowgraph modeling of process and control systems of a nuclear-based hydrogen production plant

Modeling and analysis of system reliability facilitate the identification of areas of potential improvement. The Dynamic Flowgraph Methodology (DFM) is an emerging discrete modeling framework that allows for capturing time dependent behaviour, switching logic and multi-state representation of system components. The objective of this research is to demonstrate the process of dynamic flowgraph modeling of a nuclear-based hydrogen production plant with the copper–chlorine (Cu–Cl) cycle. Modeling of the thermochemical process of the Cu–Cl cycle in conjunction with a networked control system proposed for monitoring and control of the process is provided. This forms the basis for future component selection.     

Technoeconomic analysis of a methanol plant based on gasification of biomass and electrolysis of water

Methanol production process configurations based on renewable energy sources have been designed. The processes were analyzed in the thermodynamic process simulation tool DNA. The syngas used for the catalytic methanol production was produced by gasification of biomass, electrolysis of water, CO₂ from post-combustion capture and autothermal reforming of natural gas or biogas. Underground gas storage of hydrogen and oxygen was used in connection with the electrolysis to enable the electrolyser to follow the variations in the power produced by renewables. Six plant configurations, each with a different syngas production method, were compared. The plants achieve methanol exergy efficiencies of 59–72%, the best from a configuration incorporating autothermal reforming of biogas and electrolysis of water for syngas production. The different processes in the plants are highly heat integrated, and the low-temperature waste heat is used for district heat production. This results in high total energy efficiencies (∼90%) for the plants. The specific methanol costs for the six plants are in the range 11.8–25.3 €/GJ_exergy. The lowest cost is obtained by a plant using electrolysis of water, gasification of biomass and autothermal reforming of natural gas for syngas production.     

Technical challenges for developing thermal methane cracking in small or medium scales to produce pure hydrogen - A review

Hydrogen is an important chemical commodity and plays a key role in the clean, secure and affordable energy scenarios of the future. There is a significant interest in the development of small plants for hydrogen generation besides other plants where hydrogen has been consumed as raw material and it is because of the very high cost of compression and transportation of hydrogen.Thermal methane cracking (TMC) is an alternative process for high purity hydrogen manufacturing along with the traditional commercial processes such as steam reforming, coal gasification, partial oxidation, and water electrolysis. Employing the TMC process for very high purity hydrogen production on a small or medium-scale plant with the minimum requirement of separation units is the main incentive of this review.Given the results of the review, using catalysts for TMC can decrease the working temperature to below 800 °C but it could create some significant issues, especially catalyst deactivation (a low catalyst life due to carbon deposition), so it is not yet a viable method to employ on the production plants. On the other hand, supplying the heat of reaction and reactor blockages are two basic challenges for a non-catalytic reaction way.     

Solar thermochemical plant analysis for hydrogen production with the copper–chlorine cycle

In this article, a solar-based method of generating hydrogen from the copper–chlorine water-splitting cycle is developed and evaluated. An analysis is performed for solar plants with different hydrogen production capacities at three locations across Canada. Operating parameters of the solar field and the storage units are presented. The thermal efficiency and cost parameters of the hydrogen plant are also examined. A binary mixture of 60% NaNO₃ and 40% KNO₃ is used as the molten salt for solar energy storage. Different hydrogen production rates are analyzed. Since the solar irradiation in Calgary is much less than Toronto and Sarnia in the winter, it is found that a larger storage unit is required. The size of the storage unit increases for larger hydrogen production rates. The results support the feasibility of solar thermochemical Cu–Cl cycle as a promising and efficient pathway for large-scale production of hydrogen.     

Evaluation of a thermally-driven metal-hydride-based hydrogen compressor

Currently, the hydrogen storage method used aboard fuel cell electric vehicles utilizes pressures up to 70 MPa. Attaining such high pressures requires mechanical gas compression or hydrogen liquefaction followed by heating to form a high-pressure gas, and these processes add to the cost and reduce the energy efficiency of a hydrogen fueling system. In previous work we have evaluated the use of high-pressure electrolysis, in which hydrogen is generated from water and the electrolyzer boosts the hydrogen pressure to values from 13 to 45 MPa. While electrolytic compression is a novel and energy efficient method to produce high-pressure hydrogen, it has several limitations at present and will require more development work. Another concept is to use hydrogen absorbing alloys that form metal hydrides, in combination with a heat engine (hot and cold reservoirs), to drive a cyclic process in which hydrogen gas is absorbed and desorbed to compress hydrogen. Furthermore, by using a thermally-driven compressor, the hot and cold reservoirs can be obtained using renewable energy such as sunlight for heating together with ambient air or water for cooling. In this work we evaluated the thermodynamics and kinetics of a prototype metal hydride hydrogen compressor (MHHC) built for us by a research group in China. The compressor utilized a hydrogen input pressure of approximately 14 MPa, and, operating between an initial temperature of approximately 300 K and a final temperature of 400 K, a pressure of approximately 41 MPa was attained. In a series of experiments with those conditions the average compression ratio for a single-stage compression was approximately three. In the initial compression cycles, up to 300 g of hydrogen was compressed for each 100 K temperature cycle. The enthalpy of the metallic-alloy-hydriding reaction was found to be approximately 20.5 kJ per mole of H₂, determined by measuring the pressure composition isotherm at three temperatures and using a Van't Hoff plot. The thermodynamic efficiency of the compressor, as measured by the value of the compression work performed divided by the heat energy added and removed in one complete cycle, was determined via first and second law analyses. The Carnot efficiency was approximately 25%, the first law efficiency was approximately 3–5%, and the second law efficiency was approximately 12–20%, depending on the idealized compression cycle used to assign a value to the compression work, as well as other assumptions. These efficiencies compare favorably with values reported for other thermally-driven compressors.     

Advances in hydrogen production by thermochemical water decomposition: A review

Hydrogen demand as an energy currency is anticipated to rise significantly in the future, with the emergence of a hydrogen economy. Hydrogen production is a key component of a hydrogen economy. Several production processes are commercially available, while others are under development including thermochemical water decomposition, which has numerous advantages over other hydrogen production processes. Recent advances in hydrogen production by thermochemical water decomposition are reviewed here. Hydrogen production from non-fossil energy sources such as nuclear and solar is emphasized, as are efforts to lower the temperatures required in thermochemical cycles so as to expand the range of potential heat supplies. Limiting efficiencies are explained and the need to apply exergy analysis is illustrated. The copper–chlorine thermochemical cycle is considered as a case study. It is concluded that developments of improved processes for hydrogen production via thermochemical water decomposition are likely to continue, thermochemical hydrogen production using such non-fossil energy will likely become commercial, and improved efficiencies are expected to be obtained with advanced methodologies like exergy analysis. Although numerous advances have been made on sulphur–iodine cycles, the copper–chlorine cycle has significant potential due to its requirement for process heat at lower temperatures than most other thermochemical processes.     

Research on non-grid-connected wind power/water-electrolytic hydrogen production system

Hydrogen has been recognized as the most promising future energy carrier. At present, industrial hydrogen production processes are not independent of traditional energy resources, which could easily cause secondary pollution. China has abundant wind energy resources. The total installed capacity of wind power doubled every year in the last five years, and reached 26 000 MW by the end of 2009, but over 9880 MW wind turbines were not integrated into grid because of the peak shaving restraint. In this paper, wind power is directly used in water-electrolytic process by some technical improvements, to design non-grid-connected wind power/water-electrolytic hydrogen production system. The system all works properly, based on not only the wind/grid complementary power supply but also the independent supply of simulation wind power. The large-scale fluctuation of current density has little impact on current efficiency and gas quality, and only affects gas output. The new system can break through the bottlenecks of wind power utilization, and explore a diversified development way of large-scale wind power, which will contribute to the development of green economy and low carbon economy in China.     

Raman spectroscopy for ortho-para hydrogen catalyst studies

For the design of efficient hydrogen liquefaction plants and for the production of accurate ortho-para hydrogen samples, precise knowledge about the kinetics of ortho-para catalysts and accurate ortho-para monitoring is mandatory. Raman spectroscopy as a direct measurement of the ortho-para ratio is independent of other gas parameters, such as temperature, pressure, and flow rate and also undisturbed by impurities, such as nitrogen and oxygen in the gas. Therefore, Raman spectroscopy is a superior technique for ortho-para monitoring, com-pared to methods based on thermodynamic properties like heat conductivity. Within this work, an experimental proof of concept of a Raman based system to study ortho-para catalyst kinetics is shown.     

Techno-economic assessment of renewable hydrogen production and the influence of grid participation

Large-scale hydrogen production facilities will be required to supply the chemical energy demand of certain industries in the future. The case for such production plants based on individual adapted PV and wind farms has been addressed in several studies. However, most studies focus on an island solution of the evaluated plant and therefore, do not allow grid assistance which significantly reduce the installed capacity of the corresponding units. To address this issue, we developed a tool with a linear programming approach to evaluate any location around the world for its renewable hydrogen production costs and the influence on the plant layout depending on its interaction with the grid. A detailed techno-economic evaluation has been performed for five locations where hydrogen production costs in the range of 4–6 €₂₀₂₀/kg have been retrieved. Furthermore, it is shown that with perspective cost data the costs can further be reduced to 2.50 €₂₀₂₀/kg.     

Comparison of thermochemical,electrolytic, photoelectrolytic and photochemical solar-to-hydrogen production technologies

Hydrogen produced from solar energy is one of the most promising solar energy technologies that can significantly contribute to a sustainable energy supply in the future. This paper discusses the unique advantages of using solar energy over other forms of energy to produce hydrogen. Then it examines the latest research and development progress of various solar-to-hydrogen production technologies based on thermal, electrical, and photon energy. Comparisons are made to include water splitting methods, solar energy forms, energy efficiency, basic components needed by the processes, and engineering systems, among others. The definitions of overall solar-to-hydrogen production efficiencies and the categorization criteria for various methods are examined and discussed. The examined methods include thermochemical water splitting, water electrolysis, photoelectrochemical, and photochemical methods, among others. It is concluded that large production scales are more suitable for thermochemical cycles in order to minimize the energy losses caused by high temperature requirements or multiple chemical reactions and auxiliary processes. Water electrolysis powered by solar generated electricity is currently more mature than other technologies. The solar-to-electricity conversion efficiency is the main limitation in the improvement of the overall hydrogen production efficiency. By comparison, solar powered electrolysis, photoelectrochemical and photochemical technologies can be more advantageous for hydrogen fueling stations because fewer processes are needed, external power sources can be avoided, and extra hydrogen distribution systems can be avoided as well. The narrow wavelength ranges of photosensitive materials limit the efficiencies of solar photovoltaic panels, photoelectrodes, and photocatalysts, hence limit the solar-to-hydrogen efficiencies of solar based water electrolysis, photoelectrochemical and photochemical technologies. Extension of the working wavelength of the materials is an important future research direction to improve the solar-to-hydrogen efficiency.     

Estimating the cost savings and avoided CO2 emissions in Brazil by implementing energy efficient policies

Investing more in renewable energy sources and using this in a rational and efficient way is vital for the sustainable growth of world. Energy efficiency (EE) will play an increasingly important role in future generations. The aim of this work is to estimate how much the PNEf (National Plan for Energy Efficiency) launched by the Brazilian government in 2011 will save over the next 5 years by avoiding the construction of additional power plants, as well as the amount of the CO₂ emission.The marginal operating cost is computed for medium term planning of the dispatching of power plants in the hydro-thermal system using Stochastic Dynamic Dual Programming, after incorporating stochastic energy efficiencies into the demand for electricity. We demonstrate that even for a modest improvement in energy efficiency (<1% per year), the savings over the next 5 years range from R$ 237 million in the conservative scenario to R$ 268 million¹ in the optimistic scenario. By comparison the new Belo Monte hydro-electric plant will cost R$ 26 billion to be repaid over a 30 year period (i.e. R$ 867 million in 5 years). So in Brazil EE policies are preferable to building a new power plant.