氢能制取和储存技术研究发展综述

综述了氢能制取和储存技术研究的最新发展现状。生物质制氢、太阳能热化学循环制氢、太阳能半导体光催化制氢、核能制氢等技术具有资源丰富、使用可再生能源的优点,能克服传统电解水制氢能耗高和矿物原料有限的缺点,成为提高制氢效率、实现规模生产的研究重点。加压压缩储氢技术的研究进展主要体现在改进容器材料和研发吸氯物质方面;液化储氢技术研发重点是降低能耗和成本;金属氢化物储氢技术正努力突破储氢密度低的难题。氢能制取、储存技术正在走向实用阶段,重点技术方向是以水为原料,实现大规模、经济、高效和安全地制氢储氢,推动氢能可持续和洁净的利用,促进能源安全。     

Reactor technology options for distributed hydrogen generation via ammonia decomposition: A review

Hydrogen (H₂) fuel obtained via thermo-catalytic ammonia (NH₃) decomposition is rapidly attracting considerable interest for portable and distributed power generation systems. Consequently, a variety of reactor technologies are being developed in view of the current lack of infrastructure to generate H₂ for proton exchange membrane (PEM) fuel cells. This paper provides an extensive review of the state-of-the-art reactor technology (also referred to as reactor infrastructure) for pure NH₃ decomposition. The review strategy is to survey the open literature and present reactor technology developments in a chronological order. The primary objective of this paper is to provide a condensed viewpoint and basis for future advances in reactor technology for generating H₂ via NH₃ decomposition. Also, this review highlights the prominent issues and prevailing challenges that are yet to be overcome for possible market entry and subsequent commercialization of various reactor technologies. To our knowledge, this work presents for the first time a review of reactor infrastructure for distributed H₂ generation via NH₃ decomposition. Despite commendable research and development progress, substantial effort is still required if commercialization of NH₃ decomposition reactor infrastructure is to be realized.     

A novel hybrid iron-calcium catalyst/absorbent for enhanced hydrogen production via catalytic tar reforming with in-situ CO2 capture

An iron-calcium hybrid catalyst/absorbent (Ca–Al–Fe) is developed by a two-step sol-gel method to enhance tar conversion, cyclic CO₂ capture and mechanical strength of absorbent for hydrogen production in calcium looping gasification. The developed catalyst/absorbent consists of CaO and brownmillerite (Ca₂Fe₂O₅) with mayenite (Ca₁₂Al₁₄O₃₃) as inert support. Comparing with three candidate absorbents without Ca₂Fe₂O₅ or Ca₁₂Al₁₄O₃₃, cyclic carbonation reactivity and mechanical strength of Ca–Al–Fe are largely promoted. Meanwhile, Ca–Al–Fe approaches the maximum conversion rate of 1-methyl naphthalene (1-MN) with enhanced hydrogen yield around 0.15 mol/(h·g) under reforming conditions of present study. Ca–Al–Fe also shows the largest CO₂ absorption and lowest coke deposition. Influences of operation variables on 1-MN reforming are evaluated and recommended conditions can be iron to CaO mass ratio of 10%, reaction temperature of 800 °C and steam to carbon in 1-MN mole ratio of 2.0. Ca–Al–Fe hybrid catalyst/absorbent presents good potential to be applied in future.     

A critical review on the current technologies for the generation,storage, and transportation of hydrogen

Hydrogen production, storage, and transportation are the key issues to be addressed to realize a so-called clean and sustainable hydrogen economy. Various production methods, storage methods, and hydrogen transportations have been listed in the literature, along with their limitations. Therefore, to summarize the state of the art of these proposed technologies, a detailed discussion on hydrogen production, storage, and transportation is presented in this review. Also, to discuss the recent advancements of these methods including, hydrogen production, storage, and transportation on their kinetics, cyclic behavior, toxicity, pressure, thermal response, and cost-effectiveness. Moreover, new techniques such as ball milling, ultrasonic irradiation, ultrasonication, alloying, additives, cold rolling, alloying, and plasma metal reaction have been highlighted to address those drawbacks.Furthermore, the development of modern hydrogen infrastructure (reliability, safety, and low cost) is needed to scale up hydrogen delivery. This review summarizes promising techniques to enhance kinetic hydrogen production, storage, and transportation. Nevertheless, the search for the materials is still far from meeting the aimed target for production, storage, and transportation application. Therefore, more investigations are needed to identify promising areas for future H₂ production, storage, and transportation developments.     

CeO2 modified Fe2O3 for the chemical hydrogen storage and production via cyclic water splitting

The chemical hydrogen storage (hydrogen reduction) and production (water splitting) behaviour of Ce-modified Fe₂O₃ mixed oxides were investigated. Fe_1−xCe_xO_2−δ (x = 0, 0.05, 0.1, 0.2, 0.3, 0.4 and 1) oxides prepared by chemical precipitation were characterized by XRD (X-ray diffraction), H₂-TPR (hydrogen temperature-programmed reduction) and H₂O-TPO (steam temperature-programmed oxidation) tests. XRD results showed that two kinds of Fe–Ce–O solid solutions (Ce-based and Fe-based) coexisted in Fe–Ce mixed oxides. H₂-TPR experiment suggested that Ce addition could reduce hydrogen reduction temperature while H₂O-TPO experiments over reduced oxides showed that Fe–Ce mixed oxides could split water to produce hydrogen at a lower temperature and complete in a shorter time. Both redox reactions (hydrogen reduction and water splitting) were sensitive to the temperature and active at a high temperature. The successive redox cycles were carried out over the Fe_0.7Ce_0.3O_2−δ mixed oxide at 750 °C. It kept a stable production of hydrogen in the successive redox process at the condition of serious agglomeration of the materials. The highest hydrogen storage amount was up to 1.51 wt% for the Fe–Ce sample with a 30% substitution of Ce for Fe.     

A review on design strategies for metal hydrides with enhanced reaction thermodynamics for hydrogen storage applications

Hydrogen is an alternative clean energy carrier that can replace current fossil fuels for vehicular applications. Thus, it is important to develop a method that would enable a high density of hydrogen to be stored safely under the operating conditions of polymer electrolyte membrane fuel cells. Even though metal hydrides are regarded as promising candidates that can safely store a high density of hydrogen, their stable nature makes it difficult for them to release hydrogen at mild temperatures in the range of 50 to 150°C. In this review, 3 primary strategies, namely, introduction of appropriate dopants, particle size control, and design of novel reactant mixtures based on high‐throughput screening methods, are briefly described with the aim of evaluating the potential of metal hydrides for hydrogen storage applications. The review suggests that successful development of promising hydrogen storage systems will depend on collaborative introduction of these 3 primary design strategies through the combined utilization of experimental and computational techniques to overcome the major challenges associated with the reaction thermodynamics of metal hydrides.     

Boron‐ and nitrogen‐doped penta‐graphene as a promising material for hydrogen storage: A computational study

We fulfill a comprehensive study based on density functional theory (DFT) computations to cast insight into the dissociation mechanism of hydrogen molecule on pristine, B‐, and N‐doped penta‐graphene. The doping effect has been also illustrated by varying the concentration of dopant from 4.2 at% (one doping atom in 24 host atoms) to 8.3 at% (two doping atoms in 24 host atoms) and by contemplating different doping sites. Our theoretical investigation shows that the adsorption energy of H₂ molecule and H atom on the substrate can be substantially enhanced by incorporating boron or nitrogen into penta‐graphene sheet. The B‐ and N‐doped penta‐graphene can effectively decompose H₂ molecule into two H atoms. Our results demonstrate that activation energies for H₂ dissociation and H diffusion on the B‐ and N‐doped penta‐graphene are much smaller than the pristine penta‐graphene. Further investigation of increasing concentration dopants of the penta‐graphene sheet gives sufficiently low activation barrier for H₂ dissociation process. This investigation reveals that the boron and nitrogen dopants can act as effective active site for H₂ dissociation and storage.     

Hydrogen generation via the catalytic hydrolysis of morpholine-borane: A new,efficient and cost-effective hydrogen storage medium

Herein, for the first time, we introduce the morpholine-borane complex (MB) as a new, efficient, cost-effective and commercially available chemical hydrogen storage material for mobile applications. In this regard, hydrogen production from the hydrolysis of MB catalyzed by in situ generated water-soluble polymer stabilized Ag(0) and Pd(0) nanoparticles (NPs) is reported for the first time. In situ generated PSMA-stabilized Ag(0) and Pd(0) NPs showed remarkable activity in hydrogen production from the hydrolysis of MB at room temperature, providing initial TOFs of 16.1 min⁻¹ and 37.3 min⁻¹, respectively. A set of kinetic studies on the catalytic hydrolysis of MB were conducted by changing the catalyst/substrate amount and temperature, and the rate law expression and activation parameters were produced by collecting the kinetic data. The apparent activation energies for the in situ generated Ag(0) and Pd(0) NPs catalyzed MB hydrolysis were calculated to be 71.4 and 32.5 kJ mol⁻¹, respectively.     

Performance analysis of various hybrid renewable energy systems using battery,hydrogen, and pumped hydro‐based storage units

The aim of this research is to analyze the techno‐economic performance of hybrid renewable energy system (HRES) using batteries, pumped hydro‐based, and hydrogen‐based storage units at Sharurah, Saudi Arabia. The simulations and optimization process are carried out for nine HRES scenarios to determine the optimum sizes of components for each scenario. The optimal sizing of components for each HRES scenario is determined based on the net present cost (NPC) optimization criterion. All of the nine optimized HRES scenarios are then evaluated based on NPC, levelized cost of energy, payback period, CO₂ emissions, excess electricity, and renewable energy fraction. The simulation results show that the photovoltaic (PV)‐diesel‐battery scenario is economically the most viable system with the NPC of US$2.70 million and levelized cost of energy of US$0.178/kWh. Conversely, PV‐diesel‐fuel cell system is proved to be economically the least feasible system. Moreover, the wind‐diesel‐fuel cell is the most economical scenario in the hydrogen‐based storage category. PV‐wind‐diesel‐pumped hydro scenario has the highest renewable energy fraction of 89.8%. PV‐wind‐diesel‐pumped hydro scenario is the most environment‐friendly system, with an 89% reduction in CO₂ emissions compared with the base‐case diesel only scenario. Overall, the systems with battery and pumped hydro storage options have shown better techno‐economic performance compared with the systems with hydrogen‐based storage.     

A review on hydrogen production and utilization: Challenges and opportunities

Environment-friendly, safe and reliable energy supplies are indispensable to society for sustainable development and high life quality where even though social, environmental, political and economic challenges may play a vital role in their provision. Our continuously growing energy demand is driven by extensive growth in economic development and population and places an ever-increasing burden on fossil fuel utilization that represent a substantial percentage of this increasing energy demand but also creates challenges associated with increased greenhouse gas (GHG) emissions and resource depletion. Such challenges make the global transition obligatory from conventional to renewable energy sources. Hydrogen is emerging as a new energy vector outside its typical role and receiving more recognition globally as a potential fuel pathway, as it offers advantages in use cases and unlike synthetic carbon-based fuels can be truly carbon neutral or even negative on a life cycle basis. This review paper provides critical analysis of the state-of-the-art in blue and green hydrogen production methods using conventional and renewable energy sources, utilization of hydrogen, storage, transportation, distribution and key challenges and opportunities in the commercial deployment of such systems. Some of the key promising renewable energy sources to produce hydrogen, such as solar and wind, are intermittent; hydrogen appears to be the best candidate to be employed for multiple purposes blending the roles of fuel energy carrier and energy storage modality. Furthermore, this study offers a comparative assessment of different non-renewable and renewable hydrogen production systems based on system design, cost, global warming potential (GWP), infrastructure and efficiency. Finally the key challenges and opportunities associated with hydrogen production, storage, transportation and distribution and commercial-scale deployment are addressed.     

A critical review on improving hydrogen storage properties of metal hydride via nanostructuring and integrating carbonaceous materials

Hydrogen-based economy has a great potential for addressing the world's environmental concerns by using hydrogen as its future energy carrier. Hydrogen can be stored in gaseous, liquid and solid-state form, but among all solid-state hydrogen storage materials (metal hydrides) have the highest energy density. However, hydrogen accessibility is a challenging step in metal hydride-based materials. To improve the hydrogen storage kinetics, effects of functionalized catalysts/dopants on metal atoms have been extensively studied. The nanostructuring of metal hydrides is a new focus and has enhanced hydrogen storage properties by allowing higher surface area and thus reversibility, hydrogen storage density, faster and tunable kinetics, lower absorption and desorption temperatures, and durability. The effect of incorporating nanoparticles of carbon-based materials (graphene, C60, carbon nanotubes (CNTs), carbon black, and carbon aerogel) showed improved hydrogen storage characteristics of metal hydrides. In this critical review, the effects of various carbon-based materials, catalysts, and dopants are summarized in terms of hydrogen-storage capacity and kinetics. This review also highlights the effects of carbon nanomaterials on metal hydrides along with advanced synthesis routes, and analysis techniques to explore the effects of encapsulated metal hydrides and carbon particles. In addition, effects of carbon composites in polymeric composites for improved hydrogen storage properties in solid-state forms, and new characterization techniques are also discussed. As is known, the nanomaterials have extremely higher surface area (100–1000 time more surface area in m²/g) when compared to the bulk scale materials; thus, hydrogen absorption and desorption can be tuned in nanoscale structures for various industrial applications. The nanoscale tailoring of metal hydrides with carbon materials is a promising strategy for the next generation of solid-state hydrogen storage systems for different industries.     

A combined thermodynamic and experimental study on chemical‐looping ethanol reforming with carbon dioxide capture for hydrogen generation

Chemical‐looping ethanol reforming with carbon dioxide capture is proposed. It combines chemical‐looping reforming and carbon dioxide capture for pure hydrogen generation from ethanol with inherent separation of carbon dioxide. A thermal analysis of the process using NiO oxygen carrier is performed by simulating reactions using the Gibbs energy minimization method. The promising systems are investigated further with respect to temperature, NiO/C₂H₅OH molar ratio, CaO/C₂H₅OH molar ratio and pressure changes as well as possible carbon formation in the reformer. Favorable operation conditions in the presence of CaO are: pressures around 3 atm, reactor temperatures around 850 K, NiO/C₂H₅OH molar ratio = 3 and CaO/C₂H₅OH = 3. The H₂ yield and thermal efficiency with CaO addition are higher than that without CaO addition, showing that the addition of a CO₂ sorbent in the process increases the H₂ production. Copyright © 2012 John Wiley & Sons, Ltd.     

Frontiers in combustion techniques and burner designs for emissions control and CO2 capture: A review

The use of fossil fuel is expected to increase significantly by midcentury because of the large rise in the world energy demand despite the effective integration of renewable energies in the energy production sector. This increase, alongside with the development of stricter emission regulations, forced the manufacturers of combustion systems, especially gas turbines, to develop novel combustion techniques for the control of NO_x and CO₂ emissions, the latter being a greenhouse gas responsible for more than 60% to the global warming problem. The present review addresses different burner designs and combustion techniques for clean power production in gas turbines. Combustion and emission characteristics, flame instabilities, and solution techniques are presented, such as lean premixed air‐fuel (LPM) and premixed oxy‐fuel combustion techniques, and the combustor performance is compared for both cases. The fuel flexibility approach is also reviewed, as one of the combustion techniques for controlling emissions and reducing flame instabilities, focusing on the hydrogen‐enrichment and the integrated fuel‐flexible premixed oxy‐combustion approaches. State‐of‐the‐art burner designs for gas turbine combustion applications are reviewed in this study, including stagnation point reverse flow (SPRF) burner, dry low NO_x (DLN) and dry low‐emission (DLE) burners, EnVironmental burners (including EV, AEV, and SEV burners), perforated plate (PP) burner, and micromixer (MM) burner. Special emphasis is made on the MM combustor technology, as one of the most recent advances in gas turbines for stable premixed flame operation with wide turndown and effective control of NO_x emissions. Since the generation of pure oxygen is prerequisite to oxy‐combustion, oxygen‐separation membranes became of immense importance either for air separation for clean oxy‐combustion applications or for conversion/splitting of the effluent CO₂ into useful chemical and energy products. The different carbon‐capture technologies, along with the most recent carbon‐utilization approaches towards CO₂ emissions control, are also reviewed.     

Parametric study of chemical looping combustion for tri‐generation of hydrogen,heat, and electrical power with CO2 capture

In this article, a novel cycle configuration has been studied, termed the extended chemical looping combustion integrated in a steam‐injected gas turbine cycle. The products of this system are hydrogen, heat, and electrical power. Furthermore, the system inherently separates the CO₂ and hydrogen that is produced during the combustion. The core process is an extended chemical looping combustion (exCLC) process which is based on classical chemical looping combustion (CLC). In classical CLC, a solid oxygen carrier circulates between two fluidized bed reactors and transports oxygen from the combustion air to the fuel; thus, the fuel is not mixed with air and an inherent CO₂ separation occurs. In exCLC the oxygen carrier circulates along with a carbon carrier between three fluidized bed reactors, one to oxidize the oxygen carrier, one to produces and separate the hydrogen, and one to regenerate the carbon carrier. The impacts of process parameters, such as flowrates and temperatures have been studied on the efficiencies of producing electrical power, hydrogen, and district heating and on the degree of capturing CO₂. The result shows that this process has the potential to achieve a thermal efficiency of 54% while 96% of the CO₂ is captured and compressed to 110 bar. Copyright © 2005 John Wiley & Sons, Ltd.     

Recent insights in synthesis and energy storage applications of porous carbon derived from biomass waste: A review

In the last few decades, global warming, environmental pollution, and an energy shortage of fossil fuel may cause a severe economic crisis and health threats. Storage, conversion, and application of regenerable and dispersive energy would be a promising solution to release this crisis. The development of porous carbon materials from regenerated biomass are competent methods to store energy with high performance and limited environmental damages. In this regard, bio-carbon with abundant surface functional groups and an easily tunable three-dimensional porous structure may be a potential candidate as a sustainable and green carbon material. Up to now, although some literature has screened the biomass source, reaction temperature, and activator dosage during thermochemical synthesis, a comprehensive evaluation and a detailed discussion of the relationship between raw materials, preparation methods, and the structural and chemical properties of carbon materials are still lacking. Hence, in this review, we first assess the recent advancements in carbonization and activation process of biomass with different compositions and the activity performance in various energy storage applications including supercapacitors, lithium-ion batteries, and hydrogen storage, highlighting the mechanisms and open questions in current energy society. After that, the connections between preparation methods and porous carbon properties including specific surface area, pore volume, and surface chemistry are reviewed in detail. Importantly, we discuss the relationship between the pore structure of prepared porous carbon with surface functional groups, and the energy storage performance in various energy storage fields for different biomass sources and thermal conversion methods. Finally, the conclusion and prospective are concluded to give an outlook for the development of biomass carbon materials, and energy storage applications technologies. This review demonstrates significant potentials for energy applications of biomass materials, and it is expected to inspire new discoveries to promote practical applications of biomass materials in more energy storage and conversion fields.     

Tuning the hydrogen storage properties of MOF-650: A combined DFT and GCMC simulations study

Combined density functional theory and grand canonical monte Carlo (GCMC) calculations were performed to study the electronic structures and hydrogen adsorption properties of the Zn-based metal-organic framework MOF-650. The benzene azulenedicarboxylate linkers of MOF-650 were substituted by B atoms, N atoms, and boronic acid B(OH)₂ linkers, and the Zn atoms were substituted by Mg and Ca atoms. The calculated electronic densities of states (DOSs) of MOF-650 showed that introduction of B atoms reduces the band gap but damages the structure of MOF-650. Introduction of single N bonds cannot provide active electrons to attract H₂ molecules. Thus, substitutions of B and N into MOF-650 are not suggested. B(OH)₂ substitute in MOF-650 decreased its band gap, slightly improved its hydrogen storage ability and made H₂ molecules more intensively distributed besides organic linkers. GCMC calculations were carried out by estimating the H₂ storage amount of the pure and modified MOFs at 77 and 298 K and from 1 bar to 20 bar. B(OH)₂ linker and Mg/Ca co-doped MOF-650 showed increased H₂ adsorption by approximately 20 wt%. The adsorption of H₂ around different bonds showed the order N–C < C = C < B–C < C–O < B–O.     

Pt‐Rh/TiO2/activated carbon as highly active and stable HI decomposition catalyst for hydrogen production in sulfur‐iodine (SI) process

Pt‐TiO₂ loaded on activated carbon was studied as an active and stable catalyst to HI decomposition for H₂ formation in the sulfur‐iodine process. Although the activity of TiO₂‐loaded catalyst was slightly lower HI conversion than that of CeO₂ loaded one, the higher stability against HI decomposition reaction was achieved and almost equilibrium conversion was sustained over ~65 h examined. Moreover, effects of Rh or Ir addition on HI conversion were studied and it was found that Pt‐Rh bimetallic system was highly active and stable to HI decomposition. Scanning transmission electron micrograph observation suggested that the increased HI decomposition activity was assigned to the increased dispersion of Pt particles. High dispersion state of Pt was sustained after HI decomposition at 773 K by addition of Rh. Since the formation of PtI₄ was suggested by X‐ray photoelectron spectroscopy measurement during HI decomposition, increased stability by addition of Rh seems to be assigned to the high chemical stability of Rh against iodine. Almost the equilibrium HI conversion on Pt‐Rh‐TiO₂/M563 was sustained over 300 hours at 673 K.     

A comprehensive study of hydrogen production from ammonia borane via PdCoAg/AC nanoparticles and anodic current in alkaline medium: experimental design with response surface methodology

In this paper, the optimization of hydrogen (H₂) production by ammonia borane (NH₃BH₃) over PdCoAg/AC was investigated using the response surface methodology. Besides, the electro-oxidation of NH₃BH₃ was determined and optimized using the same method to measure its potential use in the direct ammonium boran fuel cells. Moreover, the ternary alloyed catalyst was synthesized using the chemical reduction method. The synergistic effect between Pd, Co and Ag plays an important role in enhancement of NH₃BH₃ hydrolysis. In addition, the support effect could also efficiently improve the catalytic performance. Furthermore, the effects of NH₃BH₃ concentration (0.1–50 mmol/5 mL), catalyst amount (1–30 mg) and temperature (20°C–50°C) on the rate of H₂ production and the effects of temperature (20°C–50°C), NH₃BH₃ concentration (0.05–1 mol/L) and catalyst amount (0.5–5 µL) on the electro-oxidation reaction of NH₃BH₃ were investigated using the central composite design experimental design. The implementation of the response surface methodology resulted in the formulation of four models out of which the quadratic model was adjudged to efficiently appropriate the experimental data. A further statistical analysis of the quadratic model demonstrated the significance of the model with a p-value far less than 0.05 for each model and coefficient of determination (R²) of 0.85 and 0.95 for H₂ production rate and NH₃BH₃ electrroxidation peak current, respectively.     

CO2 valorization through direct methanation of flue gas and renewable hydrogen: A technical and economic assessment

Under the scenario of an increasing sharing of renewable energy, Power to Gas technology may offer an effective and valuable solution for surplus energy management, accounting for a large and long-term chemical storage. In the present study an innovative Power to Synthetic Natural Gas (SNG) process has been described and investigated from a techno-economic and environmental point of view. The configuration is based on a methanation process, directly applied on flue gas stream thus acting both as a CO₂ capture and sequestration technology and as renewable energy storage mechanism. Reacting hydrogen is produced via water electrolysis powered by surplus of renewable energy, normally low-priced otherwise wasted. With a reference capacity factor around 4000 h/y, the resulting SNG cost is 0.34 €/Nm³ based on a carbon tax equal to 30 €/t CO₂. The obtained results are attractive and consistent with the fact that future investment cost for water electrolysis is decreasing accordingly.     

Future applications of hydrogen production and CO2 utilization for energy storage: Hybrid Power to Gas-Oxycombustion power plants

Power to Gas (PtG) has appeared in the last years as a potential long-term energy storage solution, which converts hydrogen produced by renewable electricity surplus into synthetic methane. However, significant economic barriers slow down its massive deployment (e.g. operating hours, expensive investments). Within this framework, the PtG-Oxycombustion hybridization can palliate these issues by improving the use of resources and increasing the overall efficiency. In this study we assess the requirements for electrolysis, depending on the size of the oxycombustion plant, the fuel physical and chemical properties and the final application of the hybrid system. Most suitable heat demanding options to implement this PtG-Oxycombustion hybridization are district heating, industrial processes and small combined cycled power plants. The latter case is modelled and simulated in detail and thermally integrated. The global efficiency of this hybrid system increases from 56% to 68%, thanks to avoiding the requirement of an air separation unit and integrating up to 88% of the available heat from methanation in a LP steam cycle.