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.     

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.     

Non-thermal production of pure hydrogen from biomass: HYVOLUTION

The objectives and methodology of the EU-funded research project HYVOLUTION devoted to hydrogen production from biomass are reviewed.The main scientific objective of this project is the development of a novel two-stage bioprocess employing thermophilic and phototrophic bacteria, for the cost-effective production of pure hydrogen from multiple biomass feedstocks in small-scale, cost-effective industries. Results are summarised of the work on pretreatment technologies for optimal biodegradation of energy crops and bio-residues, conditions for maximum efficiency in conversion of fermentable biomass to hydrogen and CO₂, concepts of dedicated installations for optimal gas cleaning and gas quality protocols, as well as innovative system integration aimed at minimizing energy demand and maximizing product output.The main technological objective is the construction of prototype modules of the plant which, when assembled, form the basis of a blueprint for the whole chain for converting biomass to pure hydrogen. A brief outline is presented of the progress made towards developing reactors for thermophilic hydrogen production, reactors for photoheterotrophic hydrogen production and equipment for optimal gas cleaning procedures.     

发酵生物制氢反应器的产氢菌生物强化作用研究

将发酵产氢菌Ethanoligenens sp. B49投加到连续流搅拌槽式反应器（CSTR）的活性污泥中,以糖蜜废水为底物,进行强化活性污泥产氢效能的研究.对生物强化前和生物强化后反应系统的产氢能力、发酵产物组成和pH值进行了对比分析.结果表明,在COD容积负荷为12 kg/(m³·d)条件下,投加产氢菌可显著提高反应系统的产氢能力并改善发酵产物组成.反应系统的比产氢速率从强化前的3.6 mmol/(kg·d)提高到强化后的5.7 mmol/(kg·d),是生物强化前的1.5倍.生物强化前,反应系统液相发酵产物乙醇、乙酸和丙酸的平均浓度分别为6.8、 5.3和4.8　mmol/L,生物强化后乙醇、乙酸和丙酸的平均浓度分别为10.5、 7.5和1.7 mmol/L,其中乙醇型发酵目的产物乙醇和乙酸在总发酵产物中的比例从生物强化前的72.0%提高为强化后的86.8%.生物强化作用使出水pH值从4.5～4.7下降为4.3.产氢菌的生物强化作用有助于反应器在低负荷运行期迅速形成产氢能力较高的乙醇型发酵.     

pH5条件下生物制氢反应器的启动及运行特性

采用连续流搅拌槽式反应器(CSTR),以糖蜜废水为底物,探讨了pH5条件下生物制氢反应器的启动和运行特性.结果表明,保持反应器内pH为5,污泥接种量为6g/L、COD启动负荷为7.0kg/(m³·d)、水力停留时间(HRT)为6h等条件,可在30d内完成产氢发酵菌群的驯化.此时系统氧化还原电位(ORP)稳定在-460mV～-480mV之间,系统呈现明显的混合酸发酵特性.其液相末端发酵产物比例分布相当,乙酸、乙醇、丁酸、丙酸和戊酸含量分别占发酵产物总含量的36%,33%,18%,13%.没有占绝对优势的发酵产物.气相中的氢气含量30%～35%,其最大产氢能力为1.3m³/(m³·d).生物制氢反应器混合酸发酵稳定运行期各种产酸发酵细菌处于均势地位,以球菌和杆菌为主.     

Biological hydrogen production from organic wastewater by dark fermentation in China: Overview and prospects

Biological hydrogen production by dark fermentation is an important part of biological hydrogen production technologies. China is a typical developing country that heavily relies on fossil fuels; thus, new, clean, and sustainable energy development turns quite urgent. It is delightful that Chinese government has already drawn up several H₂ development policies since 1990s and provided financial aid to launch some H₂ development projects. In this paper, the research status on dark fermentative hydrogen production in China was summarized and analyzed. Subsequently, several new findings and achievements, with some of which transformed into scale-up tests, were highlighted. Moreover, some prospecting coupling processes with dark fermentation of hydrogen production were also proposed to attract more research interests in the future.     

Life cycle assessment of hydrotreated vegetable oil from rape,oil palm and Jatropha

A life cycle assessment of hydrotreated vegetable oil (HVO) biofuel was performed. The study was commissioned by Volvo Technology Corporation and Volvo Penta Corporation as part of an effort to gain a better understanding of the environmental impact of potential future biobased liquid fuels for cars and trucks. The life cycle includes production of vegetable oil from rape, oil palm or Jatropha, transport of the oil to the production site, production of the HVO from the oil, and combustion of the HVO. The functional unit of the study is 1 kWh energy out from the engine of a heavy-duty truck and the environmental impact categories that are considered are global warming potential (GWP), acidification potential (AP), eutrophication potential (EP) and embedded fossil production energy. System expansion was used to take into account byproducts from activities in the systems; this choice was made partly to make this study comparable to results reported by other studies. The results show that HVO produced from palm oil combined with energy production from biogas produced from the palm oil mill effluent has the lowest environmental impact of the feedstocks investigated in this report. HVO has a significantly lower life cycle GWP than conventional diesel oil for all feedstocks investigated, and a GWP that is comparable to results for e.g. rape methyl ester reported in the literature. The results show that emissions from soil caused by microbial activities and leakage are the largest contributors to most environmental impact categories, which is supported also by other studies. Nitrous oxide emissions from soil account for more than half of the GWP of HVO. Nitrogen oxides and ammonia emissions from soil cause almost all of the life cycle EP of HVO and contribute significantly to the AP as well. The embedded fossil production energy was shown to be similar to results for e.g. rape methyl ester from other studies. A sensitivity analysis shows that variations in crop yield and in nitrous oxide emissions from microbial activities in soil can cause significant changes to the results.     

有机废弃物氢发酵制备生物氢气的研究

在批式培养实验中以有机废弃物为原料,通过厌氧生物发酵制备生物氢气研究了菌种来源、有机废弃物种类对产氢能力的影响,以及生物氢发酵过程中液相组成的变化以活性污泥为菌种来源,以淀粉为底物,在30L改进的UASB反应器中进行了放大实验,生物气中氢气浓度达40%～51%,CO₂浓度为49%～60%,且没有检测到甲烷气体,生物气经碱液吸收后氢气纯度大于97%持续产氢时间超过120d.     

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.     

F/M及HRT对果蔬垃圾厌氧发酵产氢的影响

通过中温半连续厌氧消化实验,考察了果蔬垃圾在不同食微比(0.5、0.75、1.0和1.5)及不同水力停留时间(2、3和4d)下的产氢性能.结果表明,当食微比较低(0.5和0.75)时,各水力停留时间下均不适宜连续产氢,且在水力停留时间为3 d和4 d时容易产生大量甲烷;当食微比较高(1.0和1.5)时,可以实现稳定连续产氢,发酵过程中几乎无甲烷产生.当食微比及水力停留时间分别为1.0及3 d时可获得最佳连续产氢效率,其最高容积产氢量和平均容积产氢量分别为451m L·(L·d)~(-1)和(186±29)m L·(L·d)~(-1),最高挥发性固体产氢率和平均挥发性固体产氢率(以VS计)分别为133 m L·g~(-1)和(27±5)m L·g~(-1),氢气含量可达20%~30%.     

不同pH下糖蜜废水的厌氧产酸发酵类型及微生物群落结构解析

为寻求厌氧产酸发酵反应器的适宜控制参数和微生物学机制,以ACR(厌氧接触式发酵制氢反应器)为试验平台,通过分阶段调控反应器的pH,考察不同pH下ACR系统的产酸发酵类型和产氢性能,并采用聚合酶链式反应-变性梯度凝胶电泳(PCR-DGGE)技术对微生物群落结构进行了解析.以糖蜜废水为基质,以城市污水厂剩余污泥为种泥,在污泥接种量(以MLVSS计)为3.58 g/L、进水ρ(COD_Cr)为5 000 mg/L、HRT为12 h条件下,分别考察了系统在pH为6.0～6.5、5.5～6.0、5.0～5.5、4.5～5.0条件下的运行特性.结果表明,在pH为4.5～5.0时,系统中以Ethanoligenens harbinense YUAN-3为代表的产氢菌群占优,呈现典型的乙醇型发酵特征,活性污泥表现出的产氢性能最佳,其氢气转化率和污泥的比产氢速率分别为1.9 mol/mol和7.8 mmol/(g·d).在pH为5.5～6.5、5.0～5.5的条件下,Clostridium tyrobutyricum strain A1-3、Propionibacterium sp.B2M2分别成为优势菌群,系统分别呈现出丁酸型发酵、混合酸发酵类型.研究显示,随着pH的改变,系统内的产酸发酵菌群随之发生更迭,在不同pH控制水平下形成不同的顶级微生物群落结构,进而使得系统呈现出不同发酵类型和产氢性能.      

荧光原位杂交技术解析发酵产氢细菌群落结构

应用荧光原位杂交(FISH)技术,研究了连续流搅拌槽式(CSTR)发酵制氢反应器中2种产氢发酵类型的菌群组成和发酵类型转化过程中的菌群种类和数量变化及其对产氢速率、生物量和发酵产物的影响.结果表明,梭菌属和肠杆菌科在决定产氢发酵类型方面有重要作用.以梭菌为优势种群的乙醇型发酵比以肠杆菌为优势种群的丁酸型发酵具有更佳的产氢能力.实验结果能够与生物发酵系统常规监测指标形成很好的印证.     

Modern Biomass Conversion Technologies

This article gives an overview of the state-of-the-art of key biomass conversion technologies currently deployed and technologies that may play a key role in the future, including possible linkage to CO₂ capture and sequestration technology (CCS). In doing so, special attention is paid to production of biofuels for the transport sector, because this is likely to become the key emerging market for large-scale sustainable biomass use. Although the actual role of bio-energy will depend on its competitiveness with fossil fuels and on agricultural policies worldwide, it seems realistic to expect that the current contribution of bio-energy of 40–55 EJ per year will increase considerably. A range from 200 to 300 EJ may be observed looking well into this century, making biomass a more important energy supply option than mineral oil today. A key issue for bio-energy is that its use should be modernized to fit into a sustainable development path. Especially promising are the production of electricity via advanced conversion concepts (i.e. gasification and state-of-the-art combustion and co-firing) and modern biomass derived fuels like methanol, hydrogen and ethanol from ligno-cellulosic biomass, which can reach competitive cost levels within 1–2 decades (partly depending on price developments with petroleum). Sugar cane based ethanol production already provides a competitive biofuel production system in tropical regions and further improvements are possible. Flexible energy systems, in which biomass and fossil fuels can be used in combination, could be the backbone for a low risk, low cost and low carbon emission energy supply system for large scale supply of fuels and power and providing a framework for the evolution of large scale biomass raw material supply systems. The gasification route offers special possibilities to combine this with low cost CO₂ capture (and storage), resulting in concepts that are both flexible with respect to primary fuel input as well as product mix and with the possibility of achieving zero or even negative carbon emissions. Prolonged RD&D efforts and biomass market development, consistent policy support and international collaboration are essential to achieve this.     

不同底物种类对厌氧发酵产氢的影响

在批式培养试验中以人工配置的废水为原料,以厌氧消化污泥作为天然产氢菌源,通过厌氧生物发酵制备生物氢气,研究了不同底物葡萄糖、蔗糖、麦芽糖、木糖、乳糖对产氢能力的影响,以及生物制氢发酵过程中液相组成的变化,并对产氢动力学和细菌生长动力学进行了分析.结果表明,5种底物中最佳的底物是葡萄糖,氢气含量、累积产氢量和氢气产量最高可达到49.52%、67.21 L/mol、3.23 mol/mol.发酵产氢代谢产物以丁酸和乙酸为主,乙酸的含量占到26.76%～40.49%,丁酸的含量占到37.60%-58.07%.并含有部分丙酸和乙醇,属于丁酸型发酵.丁酸/乙酸比值可作为衡量氢气产生效率的一个指标,比值越大产氢量越高.实验中氧化还原电位均在-300 mV以下,以厌氧为主.Gompertz模型能够很好地拟合其产氢过程和产氢菌生长过程.     

新兴污染物对剩余污泥厌氧发酵产氢的影响研究

厌氧发酵产氢是污泥资源化利用的一种重要途径,然而污水处理过程中新兴污染会通过各种途径转移至污泥中,影响污泥的后续处理。总结了抗生素、表面活性剂、工业添加剂、溴系阻燃剂（BFR）4种新兴污染物在污泥中的污染现状,阐述了新兴污染物对污泥发酵产氢的影响,并揭示了相关作用机制。同时,分析了新兴污染物在污泥发酵体系的降解转化规律。最后,对今后污泥中新兴污染物的研究做了展望,以利于污泥的资源化利用。     

连续流生物制氢反应器乙醇型发酵的运行特性

采用连续流搅拌槽式反应器(CSTR),利用厌氧活性污泥,在制糖废水产酸发酵过程的同时制取氢气.探讨了生物制氢反应器连续流稳定运行的工程控制参数.研究表明,在污泥接种量为15g/L、温度为35℃±1℃、COD容积负荷为40kg/(m³·d)、HRT为4h、系统pH、氧化还原电位(ORP)分别在4.6～4.9、-450～-470mV等条件下,可以实现连续流生物制氢反应系统乙醇型发酵的高效稳定运行.此时,液相末端发酵产物中乙醇和乙酸的含量占挥发酸总含量的80%以上,COD去除率22%～26%,气相中的氢气含量约为40%～58%,最大产氢能力为7.63m³/(m³·d).     

污泥与不同pH值渗滤液联合厌氧发酵产氢分析

以污泥与垃圾焚烧厂渗滤液为原料,通过小瓶批式试验,考察了垃圾渗滤液的添加量以及渗滤液初始pH对联合厌氧消化产氢的影响。结果表明:未添加污泥的渗滤液本身也可以在厌氧发酵过程中产氢。而污泥与垃圾渗滤液联合厌氧发酵,当渗滤液初始pH为5.20时,添加90%的渗滤液体系产氢量最大,为201.58 mL,最大产氢速率也最高,为9.56 mL/h;当初始渗滤液pH为4.47时,最大产氢量出现在渗滤液添加剂量为60%的样品,为57.73 mL,随后减小,但最大产氢速率在添加40%的渗滤液达到峰值,为5.11 mL/h。     

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.     

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.