Hydrogen storage and distribution systems

Hydrogen storage and transportation or distribution is closely linked together. Hydrogen can be distributed continuously in pipelines or batch wise by ships, trucks, railway or airplanes. All batch transportation requires a storage system but also pipelines can be used as pressure storage system. Hydrogen exhibits the highest heating value per weight of all chemical fuels. Furthermore, hydrogen is regenerative and environment friendly. There are two reasons why hydrogen is not the major fuel of toady’s energy consumption: First of all, hydrogen is just an energy carrier. And, although it is the most abundant element in the universe, it has to be produced, since on earth it only occurs in the form of water. This implies that we have to pay for this energy, which results in a difficult economic task, because since the industrialization we are used to consuming energy for free. The second difficulty with hydrogen as an energy carrier is the low critical temperature of 33 K, i.e. hydrogen is a gas at room temperature. For mobile and in many cases also for stationary applications the volumetric and gravimetric density of hydrogen in a storage system is crucial. Hydrogen can be stored by six different methods and phenomena: high pressure gas cylinders (up to 800 bar), liquid hydrogen in cryogenic tanks (at 21 K), adsorbed hydrogen on materials with a large specific surface area (at T < 100 K), absorbed on interstitial sites in a host metal (at ambient pressure and temperature), chemically bond in covalent and ionic compounds (at ambient pressure), oxidation of reactive metals e.g. Li, Na, Mg, Al, Zn with water. These metals easily react with water to the corresponding hydroxide and liberate the hydrogen from the water. Finally, the metal hydroxides can be thermally reduced to the metals in a solar furnace.     

Prospects of utilization of sugar beet carbohydrates for biological hydrogen production in the EU

Hydrogen can be produced through dark anaerobic fermentation using carbohydrate-rich biomass, and through photofermentation using the organic acids produced from dark fermentation. Sugar beet is an ideal energy crop for fermentative production of hydrogen in the EU due to its environmental profile and its potential availability in the area. In this work, various aspects of cultivating sugar beet in the EU for biohydrogen were highlighted, with special focus on The Netherlands and Greece. Moreover, fermentation of sugar beet juice with Caldicellulosiruptor saccharolyticus at sucrose concentration 10 g/l was performed, and was found comparable to the fermentation on pure sucrose except that the hydrogen production was 10% higher on sugar beet juice. A conservative estimate of the annual hydrogen potential in the EU was made (300 × 10⁶ kg hydrogen), considering the utilization of sugar beet pulp in hydrogen production.     

Biphasic production of hydrogen and methane from waste lactose in cyclic-batch reactors

The biphasic production of the energy gases hydrogen and methane was possible in a fed batch culture resulting in a volumetric mix of approximately 20% H₂ and 80% CH₄ and an energy conversion efficiency of 95%, based on the measured Chemical Oxygen Demand and theoretical calculations assuming that the substrate (a dairy waste permeate) was lactose. Gas production showed a rapid initial phase over 0–20 h in which the composition was up to 50% hydrogen with the balance mainly carbon dioxide. This was accompanied by the accumulation of volatile fatty acids (VFA) in which butyric was predominant. A slower second phase of gas production produced a mixture of methane and carbon dioxide with a reduction in the accumulated acids. The duration of this second phase depended on the initial load applied to the reactor, and in the experiments carried out lasted between 6 and 12 days. Where the applied initial load led to an acid accumulation such that the pH fell below 5.5, the second phase of gas production was inhibited. Where pH control was exerted to prevent the pH dropping below 6.5, ethanol accumulated alongside VFA as a first phase product, with the gas comprised entirely of carbon dioxide. Despite the excellent energy conversion and the production of biogas fuel elements matching those for hythane (a mixture of hydrogen and methane, with improved combustion characteristics), the overall process loading was considered too low for efficient volumetric conversion of the feedstock to energy. The concept could be further developed based on high rate reactor systems with granular or immobilised biomass either as a single tank biphasic system or in a split tank two phase production process.     

氢燃料电池汽车动力系统生命周期评价及关键参数对比

发展氢燃料电池汽车被认为是解决能源安全和环境污染问题的理想解决方案之一,为量化探究氢燃料电池汽车动力系统的化石能源消耗和排放情况,运用GaBi软件建模,以新能源汽车相关技术路线为参考,构建我国氢燃料电池汽车动力系统的数据清单并对其全生命周期化石能源消耗和全球变暖潜值情况进行定量评价计算和预测分析,对不同类型的双极板、不同能量控制策略和不同制氢方式对环境的影响分别进行了对比研究,并对关键数据进行了不确定分析.结果表明,预计到2030年我国每台氢燃料电池汽车动力系统生命周期的化石能源消耗量（ADP_f）、全球变暖潜值（GWP,以CO₂ eq计）和酸化潜值（AP,以SO₂ eq计）分别为1.35×10⁵ MJ、9108 kg和15.79 kg.动力系统生产制造阶段的化石能源消耗和全球变暖潜值均高于使用阶段,主要原因是燃料电池堆栈和储氢罐的制造过程.金属双极板、石墨复合双极板和石墨双极板的制造工艺中石墨复合双极板的综合环境效益最好.能量控制策略的优化会使得氢能消耗降低,当氢能消耗降低22.8%时,动力系统的生命周期化石能源消耗和全球变暖潜值分别降低10.4%和8.3%.相比于甲烷蒸气重整制氢,基于混合电网电解水制氢的动力系统生命周期全球变暖潜值高出53.7%[KG-*6],而基于水电电解水制氢降低39.6%.降低动力系统生命周期化石能源消耗和全球变暖潜值的措施包括优化能量控制策略降低氢能消耗、规模化发展可再生能源发电电解水制氢产业和聚焦突破燃料电池堆栈关键技术实现性能提升.     

Biological removal of air loaded with a hydrogen sulfide and ammonia mixture

The nuisance impact of air pollutant emissions from wastewater pumping stations is a major issue of concern to China. Hydrogen sulfide and ammonia are commonly the primary odor and are important targets for removal. An alternative control technology, biofiltration, was studied. The aim of this study is to investigate the potential of unit systems packed with compost in terms of ammonia and hydrogen sulfide emissions treatment, and to establish optimal operating conditions for a full-scale conceptual design. The laboratory scale biofilter packed with compost was continuously supplied with hydrogen sulfide and ammonia gas mixtures. A volumetric load of less than 150 gH2S/(m^3.d) and 230 gNH3/(m^3.d) was applied for about fifteen weeks. Hydrogen sulfide and ammonia elimination occurred in the biofilter simultaneously. The removal efficiency, removal capacity and removal kinetics in the biofilter were studied. The hydrogen sulfide removal efficiency reached was very high above 99%, and ammonia removal efficiency was about 80%. Hydrogen sulfide was oxidized into sulphate. The ammonia oxidation products were nitrite and nitrate. Ammonia in the biofilter was mainly removed by adsorption onto the carrier material and by absorption into the water fraction of the carrier material. High percentages of hydrogen sulfide or ammonia were oxidized in the first section of the column. Through kinetics analysis, the presence of ammonia did not hinder the hydrogen sulfide removal. According to the relationship between pressure drop and gas velocity for the biofilter and Reynolds number, non-Darcy flow can be assumed to represent the flow in the medium.     

中国氢燃料电池车燃料生命周期的化石能源消耗和CO2排放

氢燃料电池车(FCV)具有运行阶段高能效和零排放的优点,近年来得到快速的商业化发展.氢能生产具有多种技术路径,不同路径的能源和环境效益存在显著差异.本研究采用生命周期评价方法,运用GREET模型对不同氢燃料路径下的FCV燃料周期(WTW)的化石能源消耗和CO_2排放进行了全面评价.选取了多种制氢路径作为评价对象,建立了中国本地化的FCV燃料生命周期数据库,在此基础上分析了FCV相对传统汽油车的WTW节能减排效益,并和混合动力车和纯电动车进行比较.结果表明,使用可再生电力和生物质等绿色能源制氢供应FCV能取得显著的WTW节能减排效益,可削减约90%的化石能耗和CO_2排放.在发展相对成熟的传统能源制氢路径中,以焦炉煤气制得氢气为原料的FCV,能产生显著的节能减排效益,其化石能耗低于混合动力车,CO_2排放低于混合动力车和纯电动车.结合对资源储备和技术成熟度的考虑,我国在发展氢能及FCV过程中,近期可考虑利用焦炉煤气等工业副产物制氢,并且规划中远期的绿色制氢技术发展.     

Cleaner pathways of hydrogen,carbon nano-materials and metals production via solar thermal processing

This paper describes various solar thermochemical processes for the production of hydrogen, carbon nano particles, industrial grade carbon black, and metals with substantially reduced CO₂ emission footprint. The paper introduces an innovative approach of a three-dimensional volumetric production of carbon nano particles via thermal cracking of methane gained by carbon seeding as an alternative to the existing two dimensional modes. The paper also describes an alternative pathway for hydrogen production via three consecutive solar thermochemical processes, namely, solar cracking of methane, solar carbo-reduction of ZnO and CO reduction of CdO, providing long term storage of solar energy. Finally, the paper provides an example solar windowed reactor for clean production of hydrogen, and it presents numerical analysis of the solar reactor based on computational fluid dynamics results, simulating one of the major problems with natural gas cracking in solar reactors, namely, carbon contamination of the transparent window and clogging of the reactor.     

Indicative assessment of the feasibility of Ni and Au phytomining in Australia

Phytomining involves the extraction of metals from solid and liquid substrates using specially selected hyperaccumulating plants. Phytomining is commercially motivated, the objective being to produce a viable metal yield, at production costs low enough to compete with traditional mining techniques, e.g. heap leaching. In this work we assess the technical feasibility of nickel and gold phytomining in Australia by identifying possible sites, plant species most suited to these regions and methods of recovering the metals from the plants once sequestered. We then investigate the economic viability using published technical and financial models. In the near term, phytomining appears most viable where there are comparatively high metal concentrations around existing mines and mineral processing plants, e.g. near tailings dams or smelters, and in recovering metals from low grade ores considered unprofitable using conventional techniques. Phytomining has the added advantage of improving the quality of the land following completion of the operation. The indicative profitability for a Ni phytomine in Australia is predicted to be ～11,500 AU$/ha/harvest, using the hyperaccumulator Berkheya coddii on nickel rich serpentine soils and with energy generation from the harvested biomass. For Au, a profit of ～26,000 AU$/ha/harvest is predicted using induced accumulation (with thiocyanate) with a crop of Brassica juncea coupled with energy generation from the harvested biomass. In both cases, profitability is most sensitive to the metal price and the extractable metal content.     

CaO对城市生活垃圾原位水蒸气气化制备富氢燃气的影响

为高效资源化利用城市生活垃圾,提出了一种城市生活垃圾原位水蒸气气化制备富氢燃气方法. 在城市生活垃圾原位水蒸气气化过程中添加CaO,对CO₂进行高温吸收,促进H₂产生. 考察了n(Ca)/n(C)(CaO与垃圾原料中碳元素的摩尔比)、反应温度及垃圾含水率等因素对H₂产率以及气化特性的影响. 结果表明:随着n(Ca)/n(C)由0增至1.5,φ(H₂)和H₂产率(以w计)分别由25.89%、10.86g/kg增至45.90%、31.56g/kg;水蒸气的引入提高了CaO的碳酸化反应活性,促进了H₂的产生,但当含水率高于39.45%时,则会降低产气品质;反应温度高于750℃时,虽能强化城市生活垃圾、焦油的热分解等反应产生更多的H₂,但不利于CaO的碳酸化反应,最佳的操作温度为700～750℃;对固体残留物进行XRD和SEM分析可知,反应温度高于750℃会降低CaO的活性,不利于CaO对CO₂的吸收. 以CaO为添加剂的城市生活垃圾原位水蒸气气化制备富氢燃气是一种有效的城市生活垃圾资源化利用方式.      

钯/泡沫镍对水体中4-氯酚的氢解脱氯研究

采用置换沉积法制备泡沫镍负载钯(Pd/Ni)催化剂,研究了其在H2作为供氢体时对水相中4-氯酚(4-CP)的催化氢解脱氯作用.考察了Pd负载量、H2流量和反应液pH值对4-CP转化率的影响.结果表明,在相对较低的Pd负载量和H2流量下即可实现4-CP的快速高效去除,且反应液pH值在3.04~10.97的范围对反应影响不显著.当Pd负载量为0.1%、H2流量为10mL/min、pH值为6.80时,反应1h,4-CP转化率达92.6%.Pd/Ni具有较高的稳定性,重复实验表明,该催化剂使用3次后,催化活性仅下降了2.0%.     

氢含量分析在军民品质量控制中的应用

冶炼、表面处理、电镀等过程都有可能使氢气进入金属内部,氢含量偏高时会使产品氢脆,影响产品质量和使用安全.近年来军品、民品产生裂纹或断裂的质量事故时有发生.介绍了氢含量分析在军民品质量控制中的应用实例.     

利用有机质发酵产氢的影响因素与应用前景

煤、石油等化石能源的紧缺,使得氢气等可再生能源的开发与利用备受关注.生物制氢技术由于在获得清洁能源氢气的同时,还使得大量有机废弃物得到处理或净化,从而使得该技术成为当前研究的热点.总结了发酵产氢的微生物种类及产氢基质,阐述了不同有机物种类的发酵产氢机理,综述了温度、pH值、金属离子、气相条件及氧化还原电位等生态因子对发酵产氢的影响,并论述了生物制氢技术的发展方向和应用前景.     

Hydrogen for a sustainable global economy

The topic of this special issue of the Journal of Cleaner Production is “Sustainable Hydrogen from Biomass.” It is of interest to practitioners in the energy sector, governmental policy makers, researchers, educators, as well as to the general public. The purpose of this special issue is to increase public awareness and to stimulate exchange of information among actors expected to play important roles in making hydrogen available for the sustainable energy system of the future.Hydrogen as a biofuel, that is, hydrogen produced from biomass in a sustainable way is recognised as an important component of the fuel market for the future low or non-carbon based energy systems. In this special issue, the main focus is on hydrogen produced from vegetable biomass by fermentation. The development of a two-stage bioprocess for the cost-effective and environmentally friendly production of pure hydrogen from multiple biomass feedstocks is elucidated by a collection of papers presenting preliminary results of Integrated Research Project HYVOLUTION supported by the 6th Framework Programme of the European Union. The attention is turned to:- the over-all concept and characteristics of the two-stage hydrogen fermentation process,- key technological issues of fermentative hydrogen production,- the availability of vegetable feedstocks including agricultural byproducts that suitable for fermentative processing,- prospects of societal integration and sustainability of the fermentative hydrogen production technology.Other papers included in this special issue are devoted to:- simultaneous production of hydrogen and methane by fermentation of lactose-containing feedstocks derived from byproducts of milk processing,- hydrogen gas generation from organic material by electrohydrogenesis, that is, a bioelectrochemical process performed in reactors known as a microbial electrolysis cells,- the ideas for Europe-wide effort on education of hydrogen users and training of skilled staff needed for facilitating the transition to the future hydrogen economy.     

Ex-ante environmental assessments of novel technologies - Improved caprolactam catalysis and hydrogen storage

Utrecht University has conducted a pilot sustainability assessment for the executive board of the chemistry program ACTS (Advanced Chemical Technologies for Sustainability) of the Netherlands’ Organization for Scientific Research (NWO). These assessments represent prospective, i.e. ’ex-ante’ studies on the production of caprolactam by an improved catalyst and on different hydrogen storage options (i.e. compressed and liquefied hydrogen, storage in metal hydrides and storage in a metal organic framework). The pilot sustainability assessments followed the principles of environmental life cycle assessment (LCA), thereby focusing on non-renewable energy use (NREU) and climate change (GWP100). It was found that caprolactam with the novel catalyst has lower impacts than petrochemical caprolactam production from benzene but higher impacts than bio-based caprolactam produced via fermentation. Regarding hydrogen storage, it was found that compressed and liquid hydrogen have the highest impacts. The impacts of the metal hydrides and the metal organic frameworks show by far the lowest environmental impacts. The main reason is that these materials can be reused up to 1500 times (refilling of tank), while for compressing and liquefaction of hydrogen energy is needed each time a tank needs to be refilled. The study demonstrates the successful application of ex-ante technology assessment.     

Assessing the environmental impact of metal production processes

Evaluating both new and existing processes for primary metal production to assess their environmental impacts is often difficult due to the many inputs and outputs involved. Life Cycle Assessment (LCA) is a methodology that can be used for such purposes to identify those parts of the metal production life cycle that have significant environmental impacts. LCA has been used by CSIRO Minerals to assess the “cradle-to-gate” environmental impacts of a number of metal production processes practised either currently or potentially in Australia. The metals considered included copper, nickel, aluminium, lead, zinc, steel, stainless steel and titanium, by both pyrometallurgical and hydrometallurgical routes in some instances. The environmental profile included greenhouse and acid rain gas emissions, solid waste emissions and gross energy consumption. The results for various metals are compared in this paper. New process technologies for primary metal production can be expected to reduce the environmental impacts of metal production, and estimates of likely reductions for technologies involving stainless steel, titanium and aluminium are also presented in this paper.     

循环流化床脱除氯化氢研究

在直径200mm、高2560mm自制循环流化床上进行了脱除氯化氢的研究。实验结果表明本实验采用的循环流化床尾气净化装置，在士湿两种状况下的净化效率都比周类型装置有较大提高。当喷水活化增湿以后，净化效率可达90％以上，并考察了停留时间、Ca/Cl 当量比、粒径和入口氯 化氢浓度等因素对氯化氢脱除效率的影响。证实延长停留时间、增大Ca/Cl当量比、减 小粒径和增加入口氯化浓度有利于提高氯化氢脱除效率。     

Advancing Towards a Hydrogen Energy Economy: Status,Opportunities and Barriers

Performance reliability advances and cost reductions have been achieved with hydrogen and fuel cell technologies in both the transportation and distributed energy sectors. This paper reviews the status of hydrogen and fuel cell technologies, identifies key business and policy drivers for the hydrogen economy, critically examines key barriers to implementing the hydrogen economy, identifies and discusses key national initiatives to advance the hydrogen economy, and identifies and discusses key intergovernmental initiatives and activities to advance the hydrogen economy. Hydrogen and fuel cell technology advances, coupled with a reduction in costs and improvements in performance reliability, present new opportunities for developed and developing countries to achieve energy, economic and environmental security. Substantial national research and development investments in hydrogen production, storage, transport, end-use technologies (e.g., fuel cells), safety and public education underscore future opportunities. Intergovernmental bodies such as Asia Pacific Economic Cooperation (APEC), International Energy Agency (IEA) and the International Partnership for the Hydrogen Economy (IPHE) provide a multilateral framework for development of a global hydrogen economy. While the pathway forward for the hydrogen economy is precarious alternative energy options offer substantially fewer public benefits.     

化学淋滤法去除污泥中Cr、Cu的研究

文章利用柠檬酸、硝酸以及硝酸和过氧化氢混合液对污泥进行淋滤处理,研究了污泥中重金属Cr、Cu的去除率,实验结果表明,混合淋滤优于单独淋滤,随着溶液浓度和淋滤量的增大,重金属去除率也呈增大趋势。在柠檬酸浓度为0．5mol／L,硝酸和过氧化氢混合液浓度为1．0mol／L。淋滤量为1000ml／kg的混合淋滤条件下,污泥中Cr、Cu去除率可以分别达到70．97％、90．33％,经处理后的污泥符合国家污泥农用标准。     

Bioreduction of vanadium (V) in groundwater by autohydrogentrophic bacteria: Mechanisms and microorganisms

As one of the transition metals, vanadium (V) (V(V)) in trace amounts represents an essential element for normal cell growth, but becomes toxic when its concentration is above 1 mg/L. V(V) can alter cellular differentiation, gene expression, and other biochemical and metabolic phenomena. A feasible method to detoxify V(V) is to reduce it to V(IV), which precipitates and can be readily removed from the water. The bioreduction of V(V) in a contaminated groundwater was investigated using autohydrogentrophic bacteria and hydrogen gas as the electron donor. Compared with the previous organic donors, H₂ shows the advantages as an ideal electron donor, including nontoxicity and less production of excess biomass. V(V) was 95.5% removed by biochemical reduction when autohydrogentrophic bacteria and hydrogen were both present, and the reduced V(IV) precipitated, leading to total-V removal. Reduction kinetics could be described by a first-order model and were sensitive to pH and temperature, with the optimum ranges of pH 7.5–8.0 and 35–40°C, respectively. Phylogenetic analysis by clone library showed that the dominant species in the experiments with V(V) bioreduction belonged to the β-Proteobacteria. Previously known V(V)-reducing species were absent, suggesting that V(V) reduction was carried out by novel species. Their selective enrichment during V(V) bioreduction suggests that Rhodocyclus, a denitrifying bacterium, and Clostridium, a fermenter known to carry out metal reduction, were responsible for V(V) bioreduction.     

可见光驱动微生物光电化学池处理剩余污泥同步产氢

氢气是一种理想的清洁能源.太阳能驱动的微生物光电化学池(Microbial photoelectrochemical cell, MPEC)因可同时实现废物处理与自发产氢而受到人们的关注.本文以剩余污泥为底物,构建了一种由无定型硫化钼改性硅纳米线(MoS_3/SiNWs)光阴极和生物阳极组成的MPEC系统,研究了3组MPEC在不同的酸性阴极液pH和外加电压条件下的产氢及污泥减量效果.研究结果表明,MPEC在阴极液pH为1和3的条件下均能在无外加电压下自发产氢;pH=1的MPEC-1实验中平均产氢速率为(0.66±0.02) mL·h~(-1),约是pH=3的MPEC-2实验平均产氢速率的1.5倍,但阴极过酸的条件限制了其实际应用; pH为3、外加0.2 V电压的MPEC-3与MPEC-2相比,产氢周期由15 h增加到40 h,平均产氢速率由(0.44±0.05) mL·h~(-1)提高到(0.52±0.04) mL·h~(-1),污泥TCOD、SCOD、TSS、VSS的降解率分别可达53.96%、70.18%、38.21%和61.76%.可见本文构建的MPEC系统是一种有前景的利用太阳能进行废物处理和资源化的新技术.