联合生物制氢方法及发展趋势

为了在生物制氢过程中最大限度提高产氢量和产氢速率,增大底物的利用率以及更好地发挥菌种间的协同作用,联合生物制氢技术成为近年来人们关注的焦点。综述了目前国内外几种联合生物制氢方法的研究现状。并从产氢机理的角度对几种联合制氢技术进行了分析比较,重点强调光合发酵和暗发酵联合生物制氢技术具有广泛的发展前景,并指出其存在的问题和未来的发展趋势。     

Effect of initial bacteria concentration on hydrogen gas production from cheese whey powder solution by thermophilic dark fermentation

Dark fermentative hydrogen gas production from cheese whey powder solution was realized at 55°C. Experiments were performed at different initial biomass concentrations varying between 0.48 and 2.86 g L^?1 with a constant initial substrate concentration of 26 ± 2 g total sugar (TS) per liter. The highest cumulative hydrogen evolution (633 mL, 30°C), hydrogen yield (1.56 mol H₂ mol^?1 glucose), and H₂ formation rate (3.45 mL h^?1) were obtained with 1.92 g L^?1 biomass concentration. The specific H₂ production rate decreased with increasing biomasss concentration from the highest value (47.7 mL g^?1 h^?1) at 0.48 g L^?1 biomass concentration. Total volatile fatty acid concentration varied beetween 10 and 14 g L^?1 with the highest level of 14.2 g L^?1 at biomass concentration of 0.48 g L^?1 and initial TS content of 28.4 g L^?1. The experimental data were correlated with the Gompertz equation and the constants were determined. The most suitable initial biomass to substrate ratio yielding the highest H₂ yield and formation rate was 0.082 g biomass per gram of TS. © 2012 American Institute of Chemical Engineers Biotechnol. Prog., 28: 931–936, 2012     

Techno‐economic evaluation of a two‐step biological process for hydrogen production

An integrated biological process for the production of hydrogen based on thermophilic and photo‐heterotrophic fermentation was evaluated from a technical and economic standpoint. Besides the two fermentation steps the process also includes pretreatment of the raw material (potato steam peels) and purification of hydrogen using amine absorption. The study aimed neither at determining the absolute cost of biohydrogen nor at an economic optimization of the production process, but rather at studying the effects of different parameters on the production costs of biohydrogen as a guideline for future improvements. The effect of the key parameters, hydrogen productivity and yield and substrate concentration in the two fermentations on the cost of the hydrogen produced was studied. The selection of the process conditions was based mainly on laboratory data. The process was simulated by use of the software Aspen Plus and the capital costs were estimated using the program Aspen Icarus Process Evaluator. The study shows that the photo‐fermentation is the main contributor to the hydrogen production cost mainly because of the cost of plastic tubing, for the photo‐fermentors, which represents 40.5% of the hydrogen production cost. The costs of the capital investment and chemicals were also notable contributors to the hydrogen production cost. Major economic improvements could be achieved by increasing the productivity of the two fermentation steps on a medium‐term to long‐term scale. © 2009 American Institute of Chemical Engineers Biotechnol. Prog., 2010     

Clostridium paraputrificum M-21发酵制氢培养条件研究

利用类腐败梭状芽孢杆菌M-21(Clostridium paraputn M-21),在37℃、150r／min条件下发酵制氢,以葡萄糖为碳源,蛋白胨为氮源,lmol的葡萄糖可以产生1．05mol的氢气,最终所产气体中有70％H2和30％c02(体积百分数)。最优初始pH范围为7．0—7．5,少量乙酸的存在对氢气的生成有促进作用,若大量存在,会严重抑制茵的生长。在C／N质量比为1．0时,所产氢气体积最多,1g葡萄糖可产生75mL Hz(常温常压)。在高温83℃下对种茵预处理30s促进孢子的萌发,会缩短发酵产氢的时间。以淀粉为碳源,所产氢气体积略微高于葡萄糖,1g淀粉可产生78mL H2(常温常压);以蔗糖为碳源,所产氢气体积略微低于葡萄糖,1g蔗糖可产生72mL H2(常温常压)。该茵不能降解利用羧甲基纤维素,木质素磺酸钠,及纸浆等。     

Biohydrogen production by dark fermentation of glycerol using Enterobacter and Citrobacter Sp

Glycerol is an attractive substrate for biohydrogen production because, in theory, it can produce 3 mol of hydrogen per mol of glycerol. Moreover, glycerol is produced in substantial amounts as a byproduct of producing biodiesel, the demand for which has increased in recent years. Therefore, hydrogen production from glycerol was studied by dark fermentation using three strains of bacteria: namely, Enterobacter spH1, Enterobacter spH2, and Citrobacter freundii H3 and a mixture thereof (1:1:1). It was found that, when an initial concentration of 20 g/L of glycerol was used, all three strains and their mixture produced substantial amounts of hydrogen ranging from 2400 to 3500 mL/L, being highest for C. freundii H3 (3547 mL/L) and Enterobacter spH1 (3506 mL/L). The main nongaseous fermentation products were ethanol and acetate, albeit in different ratios. For Enterobacter spH1, Enterobacter spH2, C. freundii H3, and the mixture (1:1:1), the ethanol yields (in mol EtOH/mol glycerol consumed) were 0.96, 0.67, 0.31, and 0.66, respectively. Compared to the individual strains, the mixture (1:1:1) did not show a significantly higher hydrogen level, indicating that there was no synergistic effect. Enterobacter spH1 was selected for further investigation because of its higher yield of hydrogen and ethanol. © 2012 American Institute of Chemical Engineers Biotechnol. Prog., 2013     

Conversion of food waste into hydrogen by thermophilic acidogenesis

Conversion of food waste into hydrogen by thermophilic acidogenesis was investigated as a function of organic loading rate (OLR), hydraulic retention time (HRT) and pH in a continuous stirred tank reactor. In order to identify hydrogen-producing microorganisms, denaturing gradient gel electrophoresis (DGGE) of the polymerase chain reaction (PCR) – amplified V3 region of 16S rDNA analysis was conducted at each tested pH. The conversion of food waste into hydrogen was strongly influenced by the operational conditions. The hydrogen production was increased as OLR increased up to 8gVSl^-1d^-1, but drastically decreased at 10gVSl^-1d^-1. The yield of hydrogen was decreased from 2.2 to 1.0mol-H₂/mol-hexose consumed as HRT decreased from 5 to 2days. More carbohydrates in the food waste were decomposed at longer HRT, 76–90%, at HRT of 2–5days. The hydrogen production peaked at pH 5.5±0.1 and significantly decreased at pH 5.0±0.1. The biogas produced was composed of hydrogen and carbon dioxide, but no methane was detected at all tested conditions. The hydrogen contents in the gas produced were more than 55% (v/v) and not sensitive to all tested conditions. The optimum operational condition for continuous hydrogen production from the food waste was obtained at 8gVSl^-1d^-1, 5 days HRT and pH 5.5±0.1 where the hydrogen production rate, content, yield and the efficiency of carbohydrate decomposition were 1.0l H₂/l-d, 60.5% (v/v), 2.2mol-H₂/mol-hexose consumed and 90%, respectively. The hydrogen production was related with the concentration of total organic acids (TOA) which was strongly dependent on that of butyrate indicating that the reaction was mainly butyrate fermentation. The hydrogen-producing microorganism of Thermoanaerobacterium thermosaccharolyticum that involved in acetate/butyrate fermentation, was detected with strong intensity at all tested pHs by denaturing gradient gel electrophoresis (DGGE) of the polymerase chain reaction (PCR) – amplified V3 region of 16S rDNA analysis and sensitive to the tested pHs. The experimental results indicated that effective hydrogen production from the food waste could be obtained continuously by thermophilic acidogenesis at proper operational condition.     

厌氧发酵法生物制氢的研究现状和发展前景

氢气是一种理想的能源,具有转化率高、可再生和无污染等优点。与传统制氢方法相比,生物制氢技术的能耗低,对环境无害,其中的厌氧发酵生物制氢已经越来越受到人们的重视。本文主要介绍了厌氧发酵生物制氢技术的方法和机理,分析了生物制氢的可行性,结合国内外研究现状提出了未来的发展方向。     

Studies on Changes of Protein by Dye Sensitized Photooxidation

Photooxidation products of amino acid residues of lysozyme were identified as kynurenine and 3-oxykynurenine from tryptophan, alanine from histidine, methionine sulfoxide and methionine sulfone from methionine, cysteic acid from cystine, glutamic acid from arginine and serine from tyrosine by isolating peptides in tryptic hydrolysate, although the yield of each product did not always reach 100%.

Higher intensity of incident rays caused breakage of peptide chain, the mechanism of which was divided into two steps; the first predominated at the earlier stage of illumination with oxidation of tryptophan, the second predominated at the later stage of illumination accompaning the formation of amide and α-keto acid groups.

Carbonyls and peroxides liberated during illumination were also determined.     

Demonstration of hydrogenase electrode operation in a bioreactor

This work describes the first step towards combination of the bioreactor with a starch-degrading microbial consortium and hydrogenase electrode (HE) in one unit for electricity generation. For this purpose, the bioreactor for microbial fermentation was designed with a set of electrodes (pH-sensor, Ag|AgCl reference electrode, Pt-electrode, and HE) inside the bioreactor. Potentials of all electrodes and H₂ accumulation were monitored in the system under the precise pH control. Results obtained with the hydrogen-producing microbial consortium indicated that HE generates the potential equal to the H₂|2H⁺ equilibrium potential. Furthermore, HE was able to catalyze the current generation (200 μA) by consuming H₂ gas produced in the microbial consortium from starch. After 220 h of operation, HE retained at least 81% of the initial activity. Calculations of carbon balance indicated that fermentation products were similar in microbial cells without HE and with HE generating the current due to H₂ consumption.     

暗发酵-光发酵两阶段联合生物制氢技术研究进展

随着能源紧缺的日益加剧,以及化石燃料燃烧引起的环境问题逐渐突显,氢能作为一种清洁可再生能源越来越受到青睐。生物制氢与热化学及电化学制氢相比其反应条件温和、低耗、绿色,是一项非常有应用前景的技术。生物制氢从广义上可以分为暗发酵和光发酵产氢两种,其中暗发酵微生物可以利用有机废弃物产生氢气以及有机酸等副产物,光合细菌在光照和固氮酶的作用下可以将暗发酵产生的有机酸继续用于产氢,因此两种发酵产氢方式相结合可以提高有机废物的资源化效率。将近年来暗发酵-光发酵两阶段生物制氢技术进行整理分析,从其产氢机理、主要影响因素、暗发酵-光发酵产氢结合方式(两步法、混合培养产氢)几个方面进行阐述,最后指出该技术面临的挑战。