Renewable hydrogen production: a technical evaluation based on process simulation

An evaluation of different hydrogen production technologies based on renewable raw materials and/or renewable energy is presented. The evaluation comprises alkaline electrolysis, steam reforming of both biogas and gasification gas, the coupled dark and photo fermentation as well as the coupled dark and biogas fermentation. Each technology is investigated with different plant layouts and/or different raw materials. All examined technologies are designed to produce hydrogen in a quality suitable for the use in mobile fuel cells. The presented evaluation is based on the hydrogen production efficiency and the energy efficiency of the processes.     

耦合发酵产氢尾液处理的微生物电化学系统研究

区别于传统的稀释或加缓冲剂调节pH值的方法,本文提出采用微生物电解池（MEC）电调控暗发酵尾液pH值,并进一步采用微生物电合成系统（MES）降解废液产甲烷.结果表明,在MEC处理产氢暗发酵尾液过程中,伴随着阴极侧氢气的产生,暗发酵尾液中大量H⁺被消耗,溶液pH值从4.5升高到8.7;随后在MES中,产氢发酵尾液中有机物被进一步降解产生甲烷,其平均产甲烷速率达到4.5mmol/（L·d）,且在21d内化学需氧量（COD）去除率达到89%,远优于没有经过pH调控的产氢发酵尾液MES中的产甲烷性能.     

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.     

生物质能利用技术-厌氧消化技术的研究新进展

厌氧消化技术是最重要的生物质能利用技术之一。厌氧消化技术是实现废物污染防治和能源回收利用的有效方法。本文综述了厌氧消化技术利用生物质废物回收利用生物质能的最新研究进展,分别介绍了生物质废物厌氧发酵产乳酸,氢气和甲烷的机理,研究现状和存在的问题,并对其进一步发展和未来的应用前景进行了分析和展望,为寻找适合中国的垃圾处理技术提供一些参考。     

利用养殖场废水厌氧发酵生物制氢技术研究

在批式厌氧反应器中,以厌氧消化污泥作为天然产氢菌源,通过养殖场废水的厌氧发酵生产氢气,考察了厌氧污泥和碳氮营养物质对养殖场废水产氢的影响,并对液相产物的分布、产氢动力学进行了分析.试验分为4个处理.结果表明,加入营养物质接种污泥的养殖场废水氢气含量、累积产氢量和单位COD氢气产量最高可达到50.65%、334.80mL和287.10mL/g.而未接种污泥的原始养殖场废水累积产氢量和单位COD氢气产量仅为59.24mL和67.05mL/g.污泥和碳氮营养物质对产氢能力均有显著地促进作用,加入碳氮源后微生物群促进了原养殖废水有机物的氢的形成.液相末端产物中,乙酸、丁酸占总挥发酸的61%～86%,产氢过程属于典型的乙酸-丁酸型发酵.总挥发性酸含量的提高,其产氢能力也增大. Gompertz模型能够很好地拟合其产氢过程.     

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.     

固体废物厌氧暗发酵生物产氢技术进展

文章总结了固体废物厌氧发酵生物产氢技术进展,包括产氢废物种类、暗发酵生物制氢方向、微生物培养、生物工艺条件以及一些新近研究成果。暗发酵产氢速率快。联合式暗发酵—光发酵是生物产氢工艺中较有前途的方法。富含碳水化合物的有机废物,诸如纤维素与淀粉含量高的农业与食品垃圾以及食品废水,例如奶酪乳与橄榄加工厂以及面包发酵废水等,都可以采用合适的生物工艺技术产氢。     

Integration studies on a two-stage fermentation process for the production of biohydrogen

Fermentation of biomass residues and second generation biomasses is potentially a way to enable a sustainable production of hydrogen. Simulation models which calculate mass and energy balances, developed with Aspen Plus^®, are used to integrate the process steps necessary to produce pure hydrogen from biomass in a 2-stage fermentation process. Process and heat integration are introduced to reduce the high water and heat demand of the process, connected to the low substrate concentrations in the involved process streams. The results show that the recirculation of process effluents, together with the use of properly designed heat exchangers, can reduce the water and heat demand up to 90% from a non-integrated process, but is also subject to restrictions due to an increase in osmolality in the system.     

Estimation of energy demand of fermentation-based hydrogen production

The paper is concerned with estimation of heat and power consumption in a conceptual plant to produce hydrogen from sucrose-containing or starchy biomass by fermentation. A hydrogen plant connected with a sugar factory is regarded as the basic option; the sugar factory serves as a source of sucrose-containing thick juice for the hydrogen plant, where this feedstock is processed to hydrogen. As another option, a stand-alone hydrogen plant in which starch must initially be converted to fermentable glucose solution is considered. The values of key process parameters are assumed on the basis of preliminary experimental data. For both options of the hydrogen plant, heat consumption is estimated taking heat recovery in a heat exchanger network into account. Power consumption is estimated by calculating power needed for pumping of liquid and gaseous process media.     

金属盐催化生物质热解动力学特性研究

在论述国内外生物质热解技术研究进展的基础上,就金属盐对生物质的催化热解展开动力学研究。以秸秆、稻壳和稻草为原料,利用热重分析仪等实验设备进行热解实验,即在对典型的生物质及生物质和金属盐的混合物进行热解特性实验研究的基础上,分析反应速率与各项物理因素（如金属盐种类、浓度、升温速率等）之间的关系。实验结果表明,金属盐对生物质热解反应具有促进作用,在一定范围内其浓度增加,热解转化率增加,反应速度提高。     

污泥厌氧发酵产氢的影响因素

污水生物处理过程中产生大量剩余污泥, 通常采用厌氧发酵处理并获取甲烷气体. 产氢产酸是污泥厌氧消化过程中的一个中间阶段. 本研究考察了原污泥和经碱处理的污泥在不同初始pH(3.0～12.5)条件下的产氢效果, 以及污泥性质和污泥浓度等对产氢效果的影响. 结果表明, 当初始pH为11.0时污泥发酵的产氢率达到最大值.采用原污泥发酵产氢时, 在初始pH为11.0的条件下发酵产氢获得的最大产氢率为8.1 mL/g, 而经碱处理的污泥在同样初始pH的条件下发酵产氢可将其产氢率提高一倍左右, 达到16.9 mL/g. 污泥经碱处理后厌氧发酵4d无甲烷产生, 且可有效地降低氢气消耗的速率. 另外, 污泥的VSS/SS值过低时会大大降低污泥的产氢率, 而污泥浓度对产氢率无明显影响.     

一株稻田土壤梭状芽孢杆菌的分离及其固氮产氢能力研究

为研究水稻土壤中协同固氮产氢菌的固氮产氢特性,拓展协同固氮产氢菌菌种资源,利用厌氧微生物富集培养、亨盖特厌氧滚管等技术,从华南稻田土壤中筛选到一株同时具有产氢和固氮能力的菌株BZ-1. 经形态学观察及16S rRNA基因序列系统发育分析,鉴定菌株BZ-1属于梭状芽孢杆菌属(Clostridium sp.). 通过测定产氢量、生物量、发酵产物及固氮酶酶活等,对菌株BZ-1的产氢能力及协同固氮产氢特性进行分析. 结果表明:菌株BZ-1发酵34.55 mmol/L葡萄糖可产生42.19 mmol/L H₂,主要副产物为丁酸(15.96 mmol/L)、乙酸(7.14 mmol/L)和乳酸(5.09 mmol/L);菌株BZ-1具有固氮酶活性,能够以N₂为唯一氮源进行生长;菌株BZ-1固氮产氢时,相比于添加7 mmol/L氯化铵的试验组,产氢量提高了14.71%,最大生物量降低了33.33%,乙酸产量提升了61.49%. 研究显示,菌株BZ-1在协同固氮产氢条件下固氮能力的提升、生物量的降低以及核心碳代谢途径的改变可能是其产氢量提升的原因. 固氮产氢菌株BZ-1的获得将为提高土壤肥力以及缓解铅、镉等重金属对农作物的胁迫作用提供新的思路.      

磷酸盐水泥对^90Sr固化性能的研究

以含95%MgO的重烧镁砂、磷酸盐和硼砂为原料,制备了磷酸盐水泥,研究其对90Sr的固化性能.同时,通过XRD、SEM等手段对固化体物相组成及显微结构进行分析,参照国家标准＂放射性废物固化体长期浸出试验＂（GB7023—86）对固化体进行抗浸出性能试验.结果表明,90Sr的加入会降低磷酸盐水泥固化体的抗压强度,随着90...     

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.     

糖蜜、淀粉与乳品废水厌氧发酵法生物制氢

采用连续流厌氧发酵法研究了糖蜜废水、淀粉废水与牛奶废水生物制氢,讨论了有机物中3大类物质的厌氧发酵产氢的可行性,并对几种底物的产氢稳定性进行了探讨.结果表明,糖蜜废水与淀粉废水都是较好的厌氧发酵法生物产氢底物,在3大类有机物中碳水化合物是目前技术条件下最具有可能性的原材料.在碳水化合物中,溶解性好的糖比溶解性差的淀粉在目前的技术条件下具有生物产氢可行性,而淀粉比溶解性糖更具有产氢前景.不同底物厌氧生物制氢的生态位范围有所不同,对于溶解性好的糖,稳定运行的工程控制参数为pH 4.5±0.3,而溶解性较差的淀粉废水为pH 4.0±0.2;厌氧发酵产氢的ORP值也随底物的不同而不同,但总体必须低于-220mV,在-300mV左右时较好.牛奶废水不适用于作为CSTR反应器中发酵法生物制氢底物.     

乙醇型发酵过程优化及代谢调控分子机制

乙醇型发酵是3种主要厌氧产酸发酵类型之一.乙醇型发酵细菌具有高产氢效率、耐酸性、自凝集生长和发酵产物可直接被产甲烷利用等优势,因此被广泛关注和研究.近年来,在乙醇型发酵产氢过程优化和代谢途径研究方面取得了大量进展.本文对乙醇型发酵产氢反应器优化和运行控制、高效产氢细菌分离和代谢调控分子机制,以及耦合系统强化能源回收等研究进展进行了综述.此外,本文提出了乙醇型发酵的可持续高效产氢及代谢产物的定向回收梯级利用的思路,探讨了乙醇型发酵制氢技术的发展趋势和未来应用中存在的问题.     

C/N比对嗜酸细菌X-29产氢能力及其酶活性的影响

C/N比影响细菌的物质和能量代谢,为了提高产氢细菌的产氢效能,通过间歇产氢实验和酶活性分析方法,分析了在不同C/N比下嗜酸产氢细菌X-29的产氢能力以及氢化酶和乙醇脱氢酶的活性表达情况.研究结果表明,C/N比对产氢细菌的代谢及其相关酶的表达有显著的影响.虽然在不同C/N比下单位生物量的液相末端发酵产物差异不大,但是产氢能力存在显著的差异,当C/N比为14时产氢细菌X-29具有最大累积产氢量2 210.9mL/g.在不同C/N比下氢化酶的表达活性不同,氢化酶活性随着发酵的进行达到高峰后迅速降低,氢化酶的表达周期较短.乙醇脱氢酶活性随着代谢进程逐渐升高后而趋于平稳,不同C/N比时表达活性差异较小,表达周期较长.在C/N比为14时,氢化酶和乙醇脱氢酶的活性最高,分别为2.8μmol·(min·mg)^-1和33.2μmol·(min·mg)^-1.     

新型氨化菌丝体吸附剂的制备及吸附典型内分泌干扰物的研究

以产黄青霉(Penicillium chrysogenum)菌丝体为原料,通过2步化学反应将含有大量氨基的聚乙烯亚胺(PEI)嫁接到菌丝体表面,优化反应条件,得到最佳的氨化菌丝体吸附剂.该氨化吸附剂的等电点为pH 10.2,是一种表面带正电荷的菌丝体吸附剂,能有效吸附水中的阴离子内分泌干扰物五氯酚钠(PCP)、2,4二氯苯氧乙酸(2,4-D)和全氟辛烷磺酸钾(PFOS).3种污染物的吸附等温线符合Langmuir方程,15℃时最大吸附量分别为342.9、234.1、1725.6 mg/g.热力学计算表明,3种污染物的吸附均是自发发生的,2,4-D和PFOS的吸附是吸热反应,而PCP是放热反应.     

催化裂化装置硫化氢腐蚀问题及防治对策

阐述了H2S对设备的腐蚀机理,具体分析了催化裂化装置MIP-CGP技术改造后硫分布的新情况,从选材、工艺防腐、表面防腐、焊接质量控制和检测技术等方面提出了防硫化氢腐蚀的对策措施.     

不同产酸发酵菌群产氢能力的对比与分析

重点对乙醇型发酵菌群和丙酸型发酵菌群的产气及产氢能力进行了对比研究,并对发酵菌群由丙酸型演替为乙醇型过程中的产氢速率变化进行了分析.在有机负荷相同的条件下,乙醇型发酵菌群表现出较高的产氢速率和比产氢速率,最大产氢速率为14.99L/d,最大比产氢速率为3586.45mmol/(kg·d).而丙酸型发酵菌群产氢速率和比产氢速率都较低,分别为3.62L/d,196.46mmol/(kg·d)生物制氢反应器在运行中维持乙醇型发酵更有利于获得较高的氢气产量,应尽量避免丙酸型发酵的发生.