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.     

Photobiologische Umwandlung der Sonnenenergie

Photosynthesis converts sunlight into chemical energy. The photosynthetic buildup of biomass is the biggest global production process although its average efficiency is only about 0.13% with respect to the radiation energy reaching the earth's surface. This is primarily due to limiting physiological factors such as CO₂, water, and fertilizer. By turning off biomass production from the photosynthetic mechanism these restraints are excluded, and the photolytic system of the photosynthetic apparatus can be used for reduction of protons. This leads to free hydrogen gas with a comparatively high theoretical efficiency.     

Raw materials for fermentative hydrogen production

The basics of hydrogen production by thermophilic fermentation and photofermentation are outlined. Various types of biomass, which can be used as raw materials for hydrogen fermentation are named and the methods of biomass pretreatment are highlighted. The approach to technical assessment of biomass suitability is reviewed and several promising raw materials are compared with respect to the attainable hydrogen yield.     

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.     

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.     

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.     

鸡粪中高温厌氧甲烷发酵产气潜能与动力学特性

采用富含氮素的鸡粪为原料,包括原料鸡粪、鸡粪固相部分和鸡粪液相部分,选取以鸡粪为原料连续稳定运行超过90d的中高温厌氧反应器新鲜出料为接种污泥,在中温（35℃）和高温（55℃）条件下开展动力学和产甲烷潜能试验.采用Gompertz模型、一级动力学模型和两阶段模型对鸡粪中高温累积产甲烷量进行拟合.结果表明,鸡粪中高温甲烷发酵均呈现明显的快速产气期和慢速产气期两阶段特征,快速产气期的动力学常数K₁分别为0.4174和0.2104d^-1,快速产气分别在4.5和6.5d结束,快速产气量占到总产气量的69%和58%.原料鸡粪和液相部分的中温发酵动力学常数（K₁）分别为0.4177和0.2330d^-1,均高于高温的0.1721,0.2214d^-1,发酵产气速率较快.鸡粪固相部分中温发酵的动力学常数为0.1960d^-1,低于液相中温发酵的0.2330d^-1和固相高温的0.2310d^-1,中温条件下,水解过程是限制鸡粪甲烷发酵速率的主要因素之一.鸡粪固体和鸡粪液体高温发酵的动力学常数K分别为0.2310,0.22214d^-1,鸡粪固体发酵产甲烷的速率快于液相部分,水解过程不是限制鸡粪高温发酵产甲烷速率的最主要因素.产甲烷潜能试验表明鸡粪在中温和高温下产甲烷潜能分别为212,177mL/gTS.因此,仅从发酵效率的角度考虑,鸡粪中温发酵比高温发酵的产甲烷潜能更高,产甲烷速率更快.     

Potential use of thermophilic dark fermentation effluents in photofermentative hydrogen production by Rhodobacter capsulatus

Biological hydrogen production by a sequential operation of dark and photofermentation is a promising route to produce hydrogen. The possibility of using renewable resources, like biomass and agro-industrial wastes, provides a dual effect of sustainability in biohydrogen production and simultaneous waste removal. In this study, photofermentative hydrogen production on effluents of thermophilic dark fermentations on glucose, potato steam peels (PSP) hydrolysate and molasses was investigated in indoor, batch operated bioreactors. An extreme thermophile Caldicellulosiruptor saccharolyticus was used in the dark fermentation step, and Rhodobacter capsulatus (DSM1710) was used in the photofermentation step. Addition of buffer, Fe and Mo to dark fermentor effluents (DFEs) improved the overall efficiency of hydrogen production. The initial acetate concentration in the DFE needed to be adjusted to 30–40 mM by dilution to increase the yield of hydrogen in batch light-supported fermentations. The thermophilic DFEs are suitable for photofermentative hydrogen production, provided that they are supplemented with buffer and nutrients. The overall hydrogen yield of the two-step fermentations was higher than the yield of single step dark fermentations.     

适宜燃气生产的逆流清洁装置设计与试验

为了减少生物质热解燃气中焦油含量,设计了一种适宜燃气生产过程净化脱焦的逆流清洁装置。该清洁装置与气化机组进行选型匹配和参数优化,确定喷嘴口径和水压后再进行性能测试试验。试验表明:该清洁装置能较好的去除生物质热解燃气中的焦油和灰尘,除焦效率大于70%;在入口焦油和灰尘平均含量为539.92 mg/m3时,采用清洁管52的平均除焦效率为80%;在其他条件相同的情况下,燃气清洁管采用管径较小的52管比62管的除焦效率高。该研究为生物质热解燃气的净化提供了一种新的手段和技术参考。     

Bioreactor systems for thermophilic fermentative hydrogen production: evaluation and comparison of appropriate systems

Numerous different bioreactor systems are applied for hydrogen production by dark fermentation. Thermophilic fermentations are gaining an increased interest due to the high hydrogen yields associated with them. In order to reach the best thermophilic fermentation system, 2 types of bioreactors, a trickling bed and a fluidized bed system, were constructed and operated under similar conditions. Both systems were designed to meet the requirements of thermophilic fermentations, such as reduction of hydrogen partial pressure, system immanence as its best as well as increasing cell densities. For comparing the 2 systems, the extreme thermophilic organism Caldicellulosiruptor owensensis OL^T and a glucose-containing medium were employed. Parameters like hydraulic retention time, glucose concentration and stripping gas amount were varied. Each bioreactor system exhibited certain advantages; the trickling bed system enabled yields close to 3 mol-H₂ (mol-glucose)^?1 and productivities of 0.2 L L^?1 h^?1, but the application of stripping gas seemed to be obligatory. The fermentations in the fluidized bed system were characterized by slightly higher productivities (0.25 L L^?1 h^?1), but generally lower yields. However, operation of this system without stripping gas was possible.     

生物膜法光发酵制氢的研究现状与展望

21世纪被誉为氢能世纪.光发酵制氢作为绿色可持续生物制氢方式的一种,可以利用独特的光合系统固定太阳能,并利用有机物产生清洁能源氢气,因而受到广泛关注.但光发酵细菌凝集力差、底物转化效率和光能利用率低导致产氢效能下降,从而阻碍了光发酵制氢的发展.光发酵细菌可以通过形成生物膜而被有效固定,进而增加反应器内光发酵细菌的生物持有量,提高光发酵细菌对不利环境的抵抗力;同时,光发酵细菌形成生物膜后可以调控产氢细菌新陈代谢和生理活性使其更利于产氢.其中,光发酵生物膜反应器的设计尤为重要,尤其是反应器内光源的均匀分配对于光发酵制氢是一项关键因素,需要对光源设计、空间摆放和遮光性进行综合分析和设计;其次,需要考虑载体性质和载体安装以充分吸附光发酵细菌并形成生物膜;同时,结合未来可持续绿色发展的需求,光发酵生物膜反应器设计需要逐步过渡到以室外环境作为常规环境和太阳作为光源.尽管光发酵生物膜制氢前景良好,但目前对于光发酵生物膜反应器和制氢机制的研究仍然不够充分,需要更加深入地探索和优化以突破光发酵制氢的瓶颈,推动氢能行业的发展.     

Life cycle comparison of hydrothermal liquefaction and lipid extraction pathways to renewable diesel from algae

Algae biomass is an attractive biofuel feedstock when grown with high productivity on marginal land. Hydrothermal liquefaction (HTL) produces more oil from algae than lipid extraction (LE) does because protein and carbohydrates are converted, in part, to oil. Since nitrogen in the algae biomass is incorporated into the HTL oil, and since lipid extracted algae for generating heat and electricity are not co-produced by HTL, there are questions regarding implications for emissions and energy use. We studied the HTL and LE pathways for renewable diesel (RD) production by modeling all essential operations from nutrient manufacturing through fuel use. Our objective was to identify the key relationships affecting HTL energy consumption and emissions. LE, with identical upstream growth model and consistent hydroprocessing model, served as reference. HTL used 1.8 fold less algae than did LE but required 5.2 times more ammonia when nitrogen incorporated in the HTL oil was treated as lost. HTL RD had life cycle emissions of 31,000 gCO₂ equivalent (gCO₂e) compared to 21,500 gCO₂e for LE based RD per million BTU of RD produced. Greenhouse gas (GHG) emissions increased when yields exceeded 0.4 g HTL oil/g algae because insufficient carbon was left for biogas generation. Key variables in the analysis were the HTL oil yield, the hydrogen demand during upgrading, and the nitrogen content of the HTL oil. Future work requires better data for upgrading renewable oils to RD and requires consideration of nitrogen recycling during upgrading.     

A Greenhouse Gas Balance of two Existing International Biomass Import Chains

Various utility companies are considering or already initiated the import of biomass from abroad for electricity generation, especially via co-firing in coal-fired power plants. This results in international logistic biomass supply chains, which raise questions on the environmental performance of such chains. In this study, a life cycle inventory has been performed on two existing biomass import chains to evaluate the greenhouse gas balance of biomass import for co-firing. We considered production, transport and co-firing of wood pellets from Canada and palm kernel shells from Malaysia in a 600 MW _e coal-fired power plant in the Netherlands. Those chains are compared with various reference systems for energy production and the alternative use of biomass. Primary energy savings of these import and co-firing chains are between 70% and 100% of the biomass energy content. Net avoided greenhouse gas emissions are in the range of 340–2100 g/kWh. In the most optimistic scenario, pellet co-firing avoids methane emissions that would have occurred if the pellets were decomposed at landfills when not applied for energy production. In the most pessimistic scenario, palm kernel shell co-firing competes with the application as resource for animal feed production, which requires production and transport of an alternative resource. As the energy reference systems of the importing and exporting country and the alternative application of biomass have a significant impact on the net avoided greenhouse gas emissions, these factors should be considered explicitly when studying biomass trade for energy purposes.     

颗粒活性炭促进高温厌氧消化的研究

近年来的研究表明,颗粒活性炭（GAC）可以通过种间电子传递（DIET）过程,来提高中温厌氧消化（MAD）产甲烷.然而,GAC是否能够提高高温厌氧消化（TAD）产甲烷,以及其促进产甲烷原理尚不明确.通过乙酸钠为基质的批试验研究了投加GAC对高温消化产甲烷的影响.批试验结果表明GAC的加入促进了高温消化效果.定量PCR结果表明GAC的加入对生物量的贡献微小,说明促进效果可能不是通过生物量实现的.高通量测序结果发现高温下添加GAC富集了Thermodesulfolbiaceae,Anaerobaculaceae,以及古菌Methanosacinacea.该研究推测GAC的促进作用可能与直接种间电子传递有关.     

温度对FBAR反应器的运行特性及古菌微生物群落影响

为探讨固定床厌氧反应器（FBAR）在不同温度下的运行特性及微生物群落变化,比较了高温（50℃）、中温（35℃）、低温（4℃）3个温度阶段反应器产甲烷特性及古菌群落变化.结果表明;绝对产气量由大至小依次为高（50℃）、中（35℃）、低温（4℃）,单位负荷产气量依次为中温（2.84L/OLR）,低温（2.5L/OLR）,高温（1.8L/OLR）;甲烷含量依次为低温（74.5%）、中温（63.5%）,高温（57.3%）,不同温度阶段对挥发性有机酸含量变化有一定的影响.克隆文库分析表明：不同温度条件下固定床厌氧反应器内部微生物群落的丰富性存在很大的差异.定量PCR分析表明：甲烷鬃毛菌是中温和高温反应器内的优势菌,低温4℃炭纤维载体和污泥中的优势菌都是甲烷微菌.从能耗、经济效益角度分析低温条件更适合沼气发酵,而主要是以嗜氢产甲烷菌代谢途径为主.     

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.     

木质生物燃料与其半焦的混燃实验研究

生物质半焦作为生物质气化的副产物,其固定碳含量和热值均高于原生物质.若将生物质半焦充分利用将大幅提高生物质利用的能量效率,具有很大的经济和环境效益.在综合热分析基础上,考察了生物质半焦添加比例(掺烧比)对生物质微米燃料旋风炉燃烧炉膛温度、烟气及灰分的影响.试验研究发现掺烧比为20%(空气当量比为1.2,粉体粒径在0.177 mm以下,生物质含水率控制在8.1%以下),燃烧效果最好,燃烧效率高达98%,燃烧烟气中有害气体NOx和SO2的含量较少.     

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.     

酸性冲击对微生物电解产氢阳极菌群影响及功能基因变化解析

微生物电解产氢工艺是借助能够直接与电极传递电子的功能菌在阳极降解有机质并将产生的电子在阴极与质子结合回收氢气能源的新技术.采用市政废水在固定外加电压相同条件下直接启动15个反应器,以葡萄糖为碳源驯化获得电极功能菌群,稳定运行1个月获得反应器稳定产氢和伴随产甲烷效能.初始稳定时采用pH为7的磷酸盐缓冲液可以获得稳定的产气量,平行反应器表现出不同的氢气和甲烷产量.最高产氢反应器的氢气转化率为32.2%,氢气产率为(3.9±0.6)mol·mol-1(以每mol葡萄糖产生的H2量(mol)计,下同);相同条件下最低产氢效率反应器的甲烷转化率则可达到48.4%.通过48 h阳极生物膜的酸性冲击试验对阳极菌群功能恢复效果进行分析,发现消除冲击10~15 d反应器的电子传递效率得到恢复,但功能菌群多样性增加,氢气与甲烷比例发生变化.最高产氢反应器氢气产率降低1.8 mol·mol-1,而甲烷增量为0.4 mol·mol-1(以每mol葡萄糖产生的CH4量(mol)计,下同).通过关键功能基因分析发现,初始产氢效能高的反应器功能菌群中电子传递功能菌优势较大;阳极功能菌群受到短暂酸性冲击后,基于细胞色素C基因的相关菌群能够较快恢复,其电子传递能力恢复更快;与碳源降解和产甲烷相关基因群落受酸性冲击后变化较为显著,甲烷增量与氢气减少量基本符合反应计量关系.     

中温和高温厌氧生物产氢反应器连续运行的研究

采用2个厌氧生物产氢反应器分别在中温(37℃)和高温(55℃)下连续运行.以河底沉积物接种,葡萄糖为基质,在CSTR中成功实现了连续中温厌氧产氢,最高产氢量达8.6L/(L·d),基质产氢摩尔比(H₂/葡萄糖)为1.98.以厌氧产甲烷颗粒污泥接种,蔗糖为基质,在UASB反应器中成功实现了连续高温厌氧产氢过程,最高产氢量达6.8L/(L·d),基质产氢摩尔比(H₂/蔗糖)为3.6.在高温UASB反应器中培养获得了灰白色的产氢颗粒污泥,平均粒径为0.8～1.2mm,沉速为30～40m/h,电镜观察发现其表层生长大量杆状细菌.对2种产氢污泥的总DNA进行提取和纯化,通过PCR扩增和DGGE分析,发现高温和中温厌氧产氢污泥中的大部分真细菌种类相同,但各自的优势菌种明显不同.