光合产氢细菌优势菌群富集及其产氢实验研究

利用特殊培养基从光照充裕、有机质含量高的猪场粪便排放处的污泥中富集培养光合细菌混合产氢菌群,对该混合菌群的产氢培养基进行优化,并研究混合菌群的产氢特性。实验结果表明,此菌群的最佳产氢培养基配方为:氯化铵0.4g/L,氯化镁0.2g/L,酵母膏0.1g/L,磷酸氢二钾0.5g/L,氯化钠2.0g/L,谷氨酸钠3.5g/L。此菌群以1%的葡萄糖为基质时,产氢时间长达204h,最大产氢量为3.41L/L,最大产氢速率为44.17mL/(L.h),最高氢气含量为46.73%,具有工业化应用价值。     

光合细菌产氢研究进展与问题

化石能源的日益枯竭及其长期使用造成了严重的环境污染,寻找清洁的可再生能源成为当前亟待解决的世界性重大课题。光合细菌产氢以其较高的底物转化效率、较高的光能利用率以及能够灵活利用多种小分子有机酸等特点而成为大规模生物产氢的研究热点。文章从光合细菌产氢机理(主要针对光合单位、固氮酶和氢酶的联合产氢机理)、影响光合细菌产氢的各种物理因素和如何提高光合细菌的产氢量等方面,系统介绍了当前国内外光合细菌产氢的最新研究结果及进展,并对该领域研究存在的主要问题及发展趋势进行了简要评述。     

可见光谱对混合光合细菌产氢和生长特性的影响

分别以不同光源蓝光(400～20nm)、绿光(550～570nm)、黄光(约590nm)、红光(600～700nm)、白光LED(发光二极管多色混合光谱带)和白炽灯(连续光谱)作为产氢光源,对光合细菌产氢和生长的影响进行了对比研究。结果表明,混合光合产氢细菌对吸收峰处的光都有较好的吸收和利用,其中尤以黄色光源最为突出,产氢较稳定且产氢量最大。     

光合细菌光合作用及固氮酶产氢作用研究进展

光合细菌产氢是一种较为理想的生物制氢方式,光合细菌产氢包括细胞的光合作用、固氮作用、碳代谢、氢代谢等过程.文章介绍了光合细菌产氢过程中光合作用与固氮酶产氢作用的机理,论述了近年来光合细菌光合系统结构、光合基因、固氮酶结构、固氮基因的研究现状,分析了光合细菌光合作用、固氮酶产氢作用研究中存在的主要问题,并就其发展方向进行了展望.     

光合细菌产氢系统累积热量对酶活性的影响

研究了外界因素引起累积热量的不同对光合细菌酶活性的影响,结果表明温度为27℃有热量累积的系统固氮酶和放氢酶活性的表达最为显著;光照强度在500～3000lx范围内,有热量累积的系统,固氮酶活性和放氢酶活性都高于无热量累积的系统;10%接种有热量累积的系统固氮酶活性最大为554mmlC2H4/mL菌液/h,放氢酶活性也最大为860nmolH2/mL菌液/h;除葡萄糖浓度为0.5%的放氢酶活性不表达,其它有热量累积的系统固氮酶和放氢酶活性都高于无热量累积的系统,葡萄糖浓度为3.0%有热量累积的系统固氮酶和放氢酶活性最高;不同NW4+浓度,累积热量都有利于固氮酶和放氢酶活性的表达,NH4+浓度为0.4g/L有热量累积的系统酶活性表达最为显著.     

生物质产氢的研究现状与发展

综述了生物质光合产氢和发酵产氢的研究现状,分析了利用生物质产氢技术目前所面临的问题;评述了把生物质产氢与新能源开发,环境保护相结合的应用可能性和前景展望。     

二价铁系离子对混合菌种光合产氢的影响

针对不同浓度的Fe2+、Co2'和Ni2+对混合菌种的光合产氢与生长的影响进行实验研究.结果表明适当浓度的二价铁系离子对产氢及生长具有一定促进作用.Fe2+、Co2+和Ni2+最佳产氢浓度分别为9.00、0.45和0.10wnol/L,而对产氢的影响作用大小顺序为:Fe2+>Ni2+>Co2+.二价铁系离子在适当浓度范围内可提高生长速率,其中Co2+对生长的促进作用最大.由于pH值影响二价铁系离子对产氢酶活性的作用,针对Fe2+浓度在不同初始pH值时对混合菌种光合产氢的影响进行实验研究.结果表明当pH=7.0时,Fe2+ 浓度的变化对产氢的影响最显著.而在本试验范围内,随着pH值偏离7.0,Fe2+浓度的变化对产氢的影响逐渐减小.     

光合产氢混合菌群的碳源代谢实验研究

以红螺菌科光合产氢混合菌群为研究对象,通过血清瓶培养实验,研究不同碳源对光合细菌生长和产氢过程的影响。结果表明:光合细菌能有效利用乙酸和丁酸快速增殖和产氢,其中以乙酸最佳,促使光合产氢混合菌群增殖的最佳乙酸浓度为80mmol/L,最佳产氢浓度为40mmol/L。光合产氢混合菌群利用乳酸增殖产氢的能力较低,而乙醇则对其表现为抑制效应。     

利用乙酸光合细菌产氢的研究

通过间歇批次实验研究了不同乙酸浓度对光合细菌产氢速度、底物转化率、能量回收率等方面的影响,同时对氮源浓度进行了优化。研究结果表明:最佳的乙酸浓度为40mmol/L,在此条件下最大产氢速度、底物转化率和能量转化率分别为1.17mL/L、1.09mol-H_2/mol acetate和27.3%。当乙酸浓度为40mmol/L时,最佳的氮源浓度为8～9mmol/L。     

固定化光合细菌处理有机废水过程产氢的研究——Ⅱ.红假单胞菌菌株D利用有机物光产氢的特性

应用固定化细胞技术,研究红假单胞菌菌株D(Rhodopseudomonas sp.D)利用有机物光产氢的过程特性,发现以琼脂包埋的固定化细胞,在以苹果酸作为基质的条件下,光照培养120h,总产氢量达到119.5ml,产氢速率为19.92ml(1·h)~(-1)。与悬浮细胞相比,产氢能力提高90％,而且光产氢持续时时延长。菌体菌龄、颗粒内生物量、光照强度、光照/黑暗时间、基质初始pH以及基质浓度均影响产氢过程。试验还证实除苹果酸外,废水中常见污染物如葡萄糖、乳酸、丙酸也是良好的产氢基质。本实验结果表明用光合细菌处理有机废水同时回收氢能的可能性。     

Effect of extrinsic lactic acid on fermentative hydrogen production

In this paper we report the effect of extrinsic lactic acid on hydrogen production from a starch-containing medium by a mixed culture. Study of the effect of addition of four metabolites, namely ethanol, lactic acid, butyric acid and acetic acid illustrated that lactic acid had a positive effect on both the maximum hydrogen production and hydrogen production rate. The addition of 10 mM lactic acid to a batch containing starch increased the hydrogen production rate and hydrogen production yield from 4.31 to 8.23 mL/h and 5.70 to 9.08 mmol H₂/g starch, respectively. This enhancement in hydrogen production rate and yield was associated with a shift from acetic acid and ethanol formation to formation of butyric acid as the predominant metabolite. The increase in hydrogen production yield was attributed to the increase in the available residual NADH for hydrogen production. When lactic acid was used as the sole carbon source, no significant hydrogen production was observed.     

Effect of furans and linoleic acid on hydrogen production

The effects of furans (furfural and 5-hydroxymethylfurfural (HMF)) on hydrogen (H₂) production using mixed anaerobic cultures were evaluated by conducting batch experiments. Two mixed anaerobic cultures (culture A and B) fed furans plus glucose and treated with and without linoleic acid (LA) at pH 5.5 were maintained at 37 °C. In the LA inhibited cultures A and B fed 0.75 g L⁻¹ furfural and 0.25 g L⁻¹ HMF, the maximum H₂ yields observed were 1.89 ± 0.27 mol mol⁻¹ glucose and 1.75 ± 0.22 mol mol⁻¹ glucose, respectively. In cultures with maximum H₂ yields, Clostridium sp. and Flavobacterium sp. were dominant. Acetate, butyrate and ethanol were the major soluble metabolites detected in cultures A and B whereas propionate was also dominant in culture B. A canonical correspondence analysis based on the byproducts and the relative abundance of the terminal-restriction fragments revealed less variation between cultures treated with LA and low correlation value between the factors and the species composition.     

Controllable hydrogen production from NaBH4 hydrolysis promoted by acetic acid

Numerous catalysts have been widely investigated for accelerating hydrogen production from NaBH₄ hydrolysis. However, these catalysts are usually complicated in structures, costly in fabrication, and hazardous for environment. In this work, cheap and environment-friendly acetic acid, CH₃COOH, is employed to promote NaBH₄ hydrolysis to produce hydrogen in a considerable rate. The experimental results demonstrate that the addition of suitable amount of CH₃COOH into NaBH₄ solutions stabilized with NaOH could dramatically accelerate the hydrolysis reaction. Additionally, the start/stop of NaBH₄ hydrolysis could be controlled by adding acid or base into the solution to realize “go-as-you-please” on-site hydrogen production.     

甲酸催化反应制取氢气

以甲酸为原料制取氢气,考察了镍作为甲酸制氢催化剂活性组分的可行性以及镁和镧作为助催化剂的抗析碳作用.利用溶胶凝胶法制备了不同活性组分的催化剂,通过活性测试得出最佳的催化剂组成(质量分数):氧化镍11.7%,氧化镁1.0%,氧化镧1.5%.利用正交实验得出甲酸催化制氢的适宜条件:水酸质量比为1.4,液空速36h-1,床层温度270℃.将一氧化碳的两段变换用于甲酸制氢,达到了降低一氧化碳浓度,提高氢纯度的目的.     

农村秸秆与粪便发酵产氢的研究

选取10种常见的农业有机废弃物:稻草、玉米秆、小麦秆、大麦秆、蚕豆秆、黄豆秆等秸秆以及猪粪、牛粪、鸡粪、马粪等粪便作为原料,采用批量发酵工艺,控制发酵料液的pH值在适宜范围内,进行厌氧发酵产氢的研究.试验结果表明,在厌氧条件下,采用批量发酵工艺,控制发酵温度为25℃左右,以农作物秸秆、畜禽粪便为原料,以沼气发酵后的厌氧活性污泥为天然产氢菌种的来源,以乳酸调控发酵料液pH值为4.5～5.5,可以获得洁净能源--氢气.     

Photo-electro-chemical chlorination of cuprous chloride with hydrochloric acid for hydrogen production

In this paper, a new photochemical cell is developed and analyzed for copper disproportionation within the Cu–Cl water splitting cycle. In the disproportionation step, cuprous chloride reacts with hydrochloric acid to generate cupric chloride and hydrogen gas. In past literature, it has been demonstrated that this reaction can be conducted electrochemically at 24 bars and 100 °C. This reaction is attractive because it generates compressed hydrogen. Consequently, the work required to compress hydrogen from standard pressure – to 350 bars for example – reduces approximately by 95%. To conduct this reaction electrochemically, the process requires electricity input. Rather than using an external supply, the method proposed in this paper drives the reaction 2CuCl(aq) + 2HCl(aq) → 2CuCl₂(aq) + H₂(g) with photonic energy derived from solar radiation. The photochemical cell comprises one photochemical and one electrochemical reactor separated by a proton conducting membrane. The electrochemical reactor is a half electrolysis cell where CuCl liquid is disproportionated with hydrochloric acid by releasing protons, according to 2CuCl(aq) + 2HCl(g) → 2CuCl₂(aq) + 2H⁺ + 2e⁻. The electrons are transferred to the second reactor by an electron-conducting media, consisting of electrodes and an external circuit. In the photochemical reactor, there are supramolecular complexes dissolved in dimethylformamide that generate multi-electrons at active sites under the influence of solar radiation and catalyze water reduction according to 2H₂O + 2e⁻ → H₂(g) + 2OH⁻. Gaseous hydrogen is collected from above the second reactor, while hydroxyl ions combine with the protons that cross the PEM to supply water according to 2OH⁻ + 2H⁺ → 2H₂O. The overall process is assisted electrically by a dye sensitized solar cell. An optical system including solar concentration, spectral splitting and an optical fibre is developed for enhanced solar energy absorption to supply thermally and electrically the Cu–Cl cycle with energy input. This paper examines the feasibility and expected efficiency of the photochemical disproportionation cell and describes the potential benefits of the thermo-photochemical water splitting process, in contrast to conventional thermochemical water splitting.     

Semi-methanolysis reaction of potassium borohydride with phosphoric acid for effective hydrogen production

The methanol and water solvents were used for the production of hydrogen from potassium borohydride. In addition, phosphoric acid was selected as the green catalyst so that this semi-methanolysis reaction would be more effective for the first time. The semi-methanolysis of potassium borohydride is investigated depend on potassium borohydride, phosphoric acid concentrations and temperatures. The maximum normalized hydrogen production rate obtained from this semi-methanolysis reaction with 1 M phosphoric acid as a catalyst was 5779 ml min ^?1 g^?1. In addition, this semi-methanolysis reaction was completed in 5 s. Kinetic studies have been carried out with the power law kinetic model. The activation energy obtained for this semi-methanolysis reaction is 1.45 kJ mol^?1.     

Improved hydrogen production via thermophilic fermentation of corn stover by microwave-assisted acid pretreatment

A microwave-assisted acid pretreatment (MAP) strategy has been developed to enhance hydrogen production via thermophilic fermentation of corn stover. Pretreatment of corn stover by combining microwave irradiation and acidification resulted in the increased release of soluble substances and made the corn stover more accessible to microorganisms when compared to thermal acid pretreatment (TAP). MAP showed obvious advantages in short duration and high efficiency of lignocellulosic hydrolysis. Analysis of the particle size and specific surface area of corn stover as well as observation of its cellular microstructure were used to elucidate the enhancement mechanism of the hydrolysis process by microwave assistance. The cumulative hydrogen volume reached 182.2 ml when corn stover was pretreated by MAP with 0.3 N H₂SO₄ for 45 min, and the corresponding hydrogen yield reached 1.53 mol H₂/mol-glucose equivalents converted to organic end products. The present work demonstrates that MAP has potential to enhance the bioconversion efficiency of lignocellulosic waste to renewable biofuel.     

Catalytic steam reforming of acetic acid for hydrogen production

A variety of supported metal catalysts were tested under conditions of steam reforming of acetic acid (HAc), which was selected as a model compound for pyrolysis oil. The influence of several parameters on catalytic activity and selectivity were examined, including catalyst composition, i.e. nature of the metal and the carrier, reaction temperature and time on stream. The metallic phase of such catalysts was comprised of various metals, such as Pt, Pd, Rh, Ru and Ni, which were supported on metal oxides carriers, such as _Al2O3${\mathrm{Al}}_2{\mathrm{O}}_3$, _La2O3/_Al2O3${\mathrm{La}}_2{\mathrm{O}}_3/{\mathrm{Al}}_2{\mathrm{O}}_3$, MgO/_Al2O3$\mathrm{MgO}/{\mathrm{Al}}_2{\mathrm{O}}_3$ and _CeO2/_Al2O3${\mathrm{CeO}}_2/{\mathrm{Al}}_2{\mathrm{O}}_3$. It was found that Ni-based and Ru-based catalysts present high activity and selectivity toward hydrogen production. Ru catalysts supported on _La2O3/_Al2O3${\mathrm{La}}_2{\mathrm{O}}_3/{\mathrm{Al}}_2{\mathrm{O}}_3$ and MgO/_Al2O3$\mathrm{MgO}/{\mathrm{Al}}_2{\mathrm{O}}_3$ carriers, showed good long-term stability as a function of time on stream. However, Ni catalysts were not as stable as Ru catalysts. The amount of carbon deposited on each catalyst was estimated, and it was found that it depends strongly on the nature of the catalyst.     

Recent progress in hydrogen production from formic acid decomposition

Formic acid, as the simplest carboxylic acid which can be obtained as an industrial by-product, is colorless, low toxicity, and easy to transport and storage at room temperature. Recently, Formic acid has aroused wide-spread interest as a promising material for hydrogen storage. Compared to other organic small molecules, the temperature for formic acid decomposition to produce hydrogen is lower, resulting in less CO toxicant species. Lots of catalysts on both homogeneous catalysts and heterogeneous were reported for the decomposition of formic acid to yield hydrogen and carbon dioxide at mild condition. In this paper, the recent development of mechanism and the material study for both homogeneous catalysts and heterogeneous catalysts are reviewed in detail.