木糖厌氧发酵产氢特性研究

以木糖作为厌氧发酵产氢底物,热预处理(100℃,处理20 min)的厌氧颗粒污泥作为接种物,研究了中温条件(37℃)下厌氧发酵产氢特性.结果表明,当反应进行至50 h时,累积产氢量最大,为81.11 mL;乙酸、丁酸和乙醇是液相末端产物中的主要物质,其中乙酸和丁酸的浓度分别为1290 mg/L和1225 mg/L,发酵类型是典型的丁酸型发酵;反应体系的pH值开始降低,最后稳定在4.40左右,形成一个稳定的缓冲体系.     

玉米秸秆预处理对厌氧发酵制氢影响的研究

为提高玉米秸秆的产氢能力,实验研究了蒸汽爆破预处理、硫酸预处理、氢氧化钠预处理、盐酸预处理和酸化(碱化)气爆预处理5种预处理方法对玉米秸秆发酵产氢能力的影响。结果表明,预处理可以将秸秆中相当一部分纤维素和半纤维素水解生成还原糖,其中质量分数为0.8%的H2SO4酸化汽爆预处理对秸秆的水解效果最好。在固-液比1∶10、H2SO4质量分数0.8%、保持微沸状态30min的处理条件下,秸秆的糖含量达到最大值24.57%,最大氢气产量为141mL/g。     

底物质量浓度对玉米秸秆同步糖化生物制氢的影响

利用HAU-M1光合细菌对玉米秸秆同步糖化生物制氢工艺进行实验研究,提出了同步糖化生物制氢工艺中玉米秸秆底物质量浓度与pH值、还原糖质量浓度、氢气体积分数和累积产氢量等因素之间的相关关系,探讨了底物质量浓度对玉米秸秆同步糖化生物制氢工艺的影响规律。实验结果表明:当玉米秸秆底物质量浓度为25g/L时,玉米秸秆同步糖化生物制氢工艺的累积产氢量达到最高,为186mL;当玉米秸秆底物质量浓度为15g/L时,玉米秸秆同步糖化生物制氢工艺的氢气体积分数达到最高,为48%;玉米秸秆同步糖化制氢工艺的产氢高峰期为12~48h,48h后逐渐停止产氢,可为进一步优化和完善以生物质为基质的同步糖化生物制氢工艺理论与技术提供科学参考。     

生物制氢反应系统的启动负荷与乙醇型发酵

采用连续流搅拌槽式反应器(CSTR),以糖蜜废水为底物,研究了COD容积负荷对生物制氢反应系统启动过程中形成的乙醇型发酵产氢能力的影响。研究表明,在污泥接种量不小于6.24 gVSS/L、启动负荷为7.0 kgCOD/m3.d、水力停留时间(HRT)为6 h、系统pH、氧化还原电位(ORP)分别在4.0~4.3、-440~-470mV之间等条件下,可在30 d内完成乙醇型发酵菌群的驯化,实现生物制氢反应系统的快速启动。由不同启动负荷(3.0、7.0、10.0 kgCOD/m3.d)条件下形成的乙醇型发酵菌群,在相同的运行条件下其产氢能力存在着差异。当系统容积负荷为30 kgCOD/m3.d时,由启动负荷为7.0 kgCOD/m3.d条件下驯化形成的乙醇型发酵菌群比由启动负荷为3.0 kgCOD/m3.d条件下驯化形成的乙醇型发酵菌群产氢能力高56%。     

Biohydrogen production from poplar leaves pretreated by different methods using anaerobic mixed bacteria

Leaves are one of the main by-products of forestry. In this study, batch experiments were carried out to convert poplar leaves pretreated by different methods into hydrogen using anaerobic mixed bacteria at 35 °C. The effects of acid (HCl), alkaline (NaOH) and enzymatic (Viscozyme L, a mixture of arabanase, cellulase, β-glucanase, hemicellulase and xylanase) pretreatments on the saccharification of poplar leaves were studied. Furthermore, the effects of acid and enzymatic pretreatment on hydrogen production, together with their corresponding degradation efficiencies for the total reducing sugar (TRS) and metabolites were compared. A maximum cumulative hydrogen yield of 44.92 mL/g-dry poplar leaves was achieved from substrate pretreated with 2% Vicozyme L, which was approximately 3-fold greater than that in raw substrate and 1.34-fold greater than that from substrate pretreated with 4% HCl. The results show that enzymatic pretreatment is an effective method for enhancing the hydrogen yield from poplar leaves.     

生物制氢和氢能发电

本文阐述了光发酵生物制氢技术和厌氧发酵生物制氢技术制氢的机理以及光合–发酵杂交技术的优势。采用生物制氢技术有利于减少环境污染,节约不可再生能源,应该成为未来能源制备技术的发展方向。随着氢能规模化、工业化生产,借助于氢的输送成本低,损失小的输电优势。氢与燃料电池相结合可提供一种高效、清洁、无传动部件、无噪声的发电技术。氢能发电技术将不断发展和日趋成熟并逐步获得广泛应用。     

Enhanced biohydrogen production from leather fleshing waste co-digested with tannery treatment plant sludge using anaerobic hydrogenic batch reactor

Efficient conversion of leather solid waste into bio-hydrogen was evaluated using anaerobic hydrogenic activity in a batch reactor. Major performance indicators such as pH, total solids, volatile solids, chemical oxygen demand, specific hydrogen yield and degradation efficiency of the crude organic matter was investigated for the possibility of optimizing the bio-hydrogen potential. The optimum waste mixing ratio was found to be in LF:S:HS (2:1:1) with a pH of 5.5 at 37°C with a removal rate of 92.3% volatile solids and the cumulative bio-hydrogen yield increased from 41 ml in the control to 323 mL, proving to be 8 times higher. This study proved to increase the efficiency of material and energy, and is definitely more economical for the waste utilization.     

Effect of fermentation conditions on biohydrogen production from lipid-rich food material

Among the basic components of organic materials, such as carbohydrate, protein, and lipid, the hydrogen yield of carbohydrate fermentation has been reported to be significantly higher than that of lipid. This study used lard as a model organic matter for lipid and investigated its H₂ production potential in batch anaerobic fermentation experiments under various combinations of stirring and CO₂-scavenging conditions. A significant increase in the hydrogen yield was observed in both CO₂-scavenging and stirring conditions; the CO₂-scavenging condition yield was 2.9 times higher than the stirring condition (116.7 and 40.3 mL H₂/g volatile solid [VS], respectively), which was much greater than reported previously. A maximal hydrogen yield of 185.8 mL H₂/g VS was obtained in the presence of both CO₂-scavenging and stirring, and the H₂ content of the total biogas was as high as 99% (v/v). In addition, there was less H₂ and more CH₄ production in the absence of CO₂-scavenging and/or stirring, which suggests that the consumption of H₂ and CO₂ for methanogenesis was the major mechanism of the poor hydrogen yield from lipid. The volatile fatty acids in all the tests consisted primarily of valeric (47.2–54.9%) and propionic acids (26.6–30.3%), and higher concentrations of these acids remained in the fermentation liquid without CO₂ removal. These results suggest that lipid-rich food waste is a potential source for H₂ production if the fermentation process is optimized to minimize the partial pressure of CO₂ and H₂ and restrain the activities of H₂-consuming bacteria.     

Batch fermentative hydrogen production utilising sago (Metroxylon sp.) starch processing effluent by enriched sago sludge consortia

Sago starch processing effluent (SSPE) is an ideal bio-resource that can be utilised as a substrate for fermentative reactions due to its relatively high organic content. Annually in Malaysia, about 2.5 million tonnes of effluent are generated from the processing of sago starch. In this study, the potential use of SSPE as a substrate for fermentative hydrogen production was confirmed under all the experimental conditions studied. The maximum hydrogen production and volumetric hydrogen production rate were 575 mL H₂/L SSPE and 57.54 mL H₂/hr.L SSPE, respectively, from cultures with an initial pH of 7 and substrate concentration of 11 g soluble carbohydrate/L SSPE. The final soluble metabolites were comprised mainly of acetate (24–43%), butyrate (4–20%), propionate (1–7%) and ethanol (44–66%), suggesting an acetic acid-ethanol type fermentation pathway.     

Enhanced hydrogen production from lipid-extracted microalgal biomass residues through pretreatment

Energy recovery from lipid-extracted microalgal biomass residues (LMBRs) plays a significant role in the sustainable development of the microalgal biodiesel industry. Different methods were used to pretreat LMBRs to improve their solubilization and anaerobic hydrogen production abilities. The pretreatment methods studied included thermal (100 °C and 121 °C), alkaline and thermo-alkaline pretreatments (combinations of alkaline and thermal pretreatments). The results showed that thermo-alkaline pretreatments resulted in remarkable improvements of LMBR solubilization, which led to an increase in hydrogen yield. The highest hydrogen yield of 45.54 mL/g-volatile solid (VS) was achieved from LMBRs pretreated by the thermo-alkaline pretreatment at 100 °C, which was approximately three-fold higher than the yield from untreated LMBRs. The results of this study proved that thermo-alkaline pretreatment at 100 °C is an effective method to improve LMBR solubilization and increase the hydrogen production from LMBRs.     

Solid-state anaerobic fermentation of spent mushroom compost for volatile fatty acids production by pH regulation

To enhance volatile fatty acid (VFA) production from spent mushroom compost (SMC), the effect of pH from 4.0 to 12.0 was investigated in this study. The results indicated that higher VFA concentration was achieved under alkaline condition compared to acid condition and control. The maximal VFA concentration was 3479.59 mg/L at a pH of 10.0, which was 50.63% higher than the control without pH control. Acetate accounted for more than 50% of total VFAs in all pH values. The NH₄⁺-N and PO₄^3?-P release was in range of 19.56–27.12 mg/g VS and 3.47–15.76 mg/g VS, respectively. Furthermore, the Logistic-based model could well explained the VFA production in this study. Therefore, alkaline fermentation can be considered a promising technology for VFA production from SMC and the optimal pH should be selected as 10.0.     

Evaluation of pretreatment methods on harvesting hydrogen producing seeds from anaerobic digested organic fraction of municipal solid waste (OFMSW)

In order to harvest high-efficient hydrogen producing seeds, five pretreatment methods (including acid, heat, sonication, aeration and freeze/thawing) were performed on anaerobic digested sludge (AS) which was collected from a batch anaerobic reactor for treating organic fraction of municipal solid waste. The hydrogen production tests were conducted in serum bottles containing 20 gVS/L (24.8 g COD/L) mixture of rice and lettuce powder at 37 °C. The experimental results showed that the heat and acid pretreatment completely repressed the methanogenic activity of AS, but acid pretreatment also partially repressed hydrogen production. Sonication, freeze/thawing and aeration did not completely suppress the methanogen activity. The highest hydrogen yields were 119.7, 42.2, 26.0, 23.0, 22.7 and 22.1 mL/gVS for heated, acidified, freeze/thawed, aerated, sonicated and control AS respectively. A pH of about 4.9 was detected at the end of hydrogen producing fermentation for all tests. The selection of an initial pH can markedly affect the hydrogen producing ability for heated and acidified AS. The higher initial pH generated higher hydrogen yield and the highest hydrogen yield was obtained with initial pH 8.9 for heated AS.     

Continuous fermentative hydrogen production from cheese whey wastewater under thermophilic anaerobic conditions

Hydrogen (H₂) production from cheese processing wastewater via dark anaerobic fermentation was conducted using mixed microbial communities under thermophilic conditions. The effects of varying hydraulic retention time (HRT: 1, 2 and 3.5 days) and especially high organic load rates (OLR: 21, 35 and 47 g chemical oxygen demand (COD)/l/day) on biohydrogen production in a continuous stirred tank reactor were investigated. The biogas contained 5–82% (45% on average) hydrogen and the hydrogen production rate ranged from 0.3 to 7.9 l H₂/l/day (2.5 l/l/day on average). H₂ yields of 22, 15 and 5 mmol/g COD (at a constant influent COD of 40 g/l) were achieved at HRT values of 3.5, 2, and 1 days, respectively. On the other hand, H₂ yields were monitored to be 3, 9 and 6 mmol/g COD, for OLR values of 47, 35 and 21 g COD/l/day, when HRT was kept constant at 1 day. The total measurable volatile fatty acid concentration in the effluent (as a function of influent COD) ranged between 118 and 27,012 mg/l, which was mainly composed of acetic acid, iso-butyric acid, butyric acid, propionic acid, formate and lactate. Ethanol and acetone production was also monitored from time to time.To characterize the microbial community in the bioreactor at different HRTs, DNA in mixed liquor samples was extracted immediately for PCR amplification of 16S RNA gene using eubacterial primers corresponding to 8F and 518R. The PCR product was cloned and subjected to DNA sequencing. The sequencing results were analyzed by using MegaBlast available on NCBI website which showed 99% identity to uncultured Thermoanaerobacteriaceae bacterium.     

Simultaneous analysis of carbohydrates and volatile fatty acids by HPLC for monitoring fermentative biohydrogen production

The production of biohydrogen through anaerobic fermentation has received increasingly attention and has great potential as an alternative process for clean fuel production in the future. The monitoring of the stages of anaerobic fermentation provides relevant information about the bioprocess. The objective of this study is to propose a novel methodology for simultaneous analysis of sucrose, glucose, fructose and volatile fatty acids (VFAs), such as, acetic, propionic, isobutyric and butyric during anaerobic fermentation by using high-performance liquid chromatography (HPLC). The following chromatographic conditions were optimized: column Aminex HPX-87H, mobile phase consisting of H₂SO₄ 0.005 mol/L, flow rate of 1.0 mL/min and temperature of 55 °C. Sucrose, glucose and fructose were analyzed by refractive index detector (RI) while acetic, propionic, isobutyric and butyric acids were analyzed by ultraviolet (UV) detection at 210 nm. Some analytical parameters of validation, such as, linearity, selectivity, repeatability, intermediate precision, limit of detection and quantification, accuracy and robustness were evaluated. The proposed methodology was successfully applied in the determination of substrates and metabolites during different stages of biohydrogen production.     

Biohydrogen production from cornstalk wastes by anaerobic fermentation with activated sludge

An anaerobic fermentation process to produce hydrogen from cornstalk wastes was systematically investigated in this work. Batch experiments numbered series I, II and III were designed to investigate the effects of acid pretreatment, enzymatic hydrolysis (enzymatic temperature, enzymatic time and enzymatic pH) on hydrogen production by using the natural sludge as inoculant. A maximum cumulative H₂ yield of 126.22 ml g⁻¹-CS (Cornstalk, or 146.94 ml g⁻¹-TS, Total Solid) and an average H₂ production rate of 9.58 ml g⁻¹-CS h⁻¹ were obtained from fermentation cornstalk with a concentration of 20 g/L and an initial pH of 7.0 at 36 °C through an optimal pretreatment process. The optimal process was that the substrate was soaked with an HCl concentration of 0.6 wt% at 90 °C for 2 h, and subsequently enzymatic hydrolysis for 72 h at 50 °C and pH 4.8 before fermentation. The biogas consisted of only H₂ and CO₂. In addition, the fermentation system was the typical ethanol-type fermentation according to ethanol and acetate as the main liquid by-products.     

Hydrogen production from agricultural waste by dark fermentation: A review

The degradation of the natural environment and the energy crisis are two vital issues for sustainable development worldwide. Hydrogen is considered as one of the most promising candidates as a substitute for fossil fuels. In this context, biological processes are considered as the most environmentally friendly alternatives for satisfying future hydrogen demands. In particular, biohydrogen production from agricultural waste is very advantageous since agri-wastes are abundant, cheap, renewable and highly biodegradable. Considering that such wastes are complex substrates and can be degraded biologically by complex microbial ecosystems, the present paper focuses on dark fermentation as a key technology for producing hydrogen from crop residues, livestock waste and food waste. In this review, recent findings on biohydrogen production from agricultural wastes by dark fermentation are reported. Key operational parameters such as pH, partial pressure, temperature and microbial actors are discussed to facilitate further research in this domain.     

Effects of pH value and substrate concentration on hydrogen production from the anaerobic fermentation of glucose

A series of batch experiments were conducted to investigate the effects of pH and glucose concentrations on biological hydrogen production by using the natural sludge obtained from the bed of a local river as inoculant. Batch experiments numbered series I and II were designed at an initial and constant pH of 5.0–7.0 with 1.0 increment and four different glucose concentrations (5.0, 7.5, 10 and 20 g glucose/L). The results showed that the optimal condition for anaerobic fermentative hydrogen production is 7.5 g glucose/L and constant pH 6.0 with a maximum H₂ production rate of 0.22 mol H₂ mol⁻¹ glucose h⁻¹, a cumulative H₂ yield of 1.83 mol H₂ mol⁻¹ glucose and a H₂ percentage of 63 in biogas.     

Hydrogen production from alcohol distillery wastewater containing high potassium and sulfate using an anaerobic sequencing batch reactor

In this study, the feasibility of hydrogen production from alcohol distillery wastewater containing high potassium and sulfate was investigated using an anaerobic sequencing batch reactor (ASBR). The seed sludge taken from an anaerobic tank treating the distillery wastewater was boiled for 15 min before being fed to the ASBR. The ASBR system was operated under different feed chemical oxygen demand (COD) values and different COD loading rates at a mesophilic temperature of 37 °C, a controlled pH at 5.5, and a cycle time of 6 cycles per day. When the studied ASBR was operated under the best conditions (providing a maximum hydrogen production efficiency) of a feed COD of 40,000 mg/l, a COD loading rate of 60 kg/m³ d, and a hydraulic retention time of 16 h, the produced gas was found to contain 34.7% H₂ and 65.3% CO_2, without any methane being detected. Under these best conditions, the specific hydrogen production rate (SHPR) of 270 ml H₂/g MLVSS d (or 3310 ml H₂/l d), and hydrogen yield of 172 ml H₂/g COD removed, were obtained. When the feed COD exceeded 40,000 mg/l, the process performance in terms of hydrogen production decreased because of the potassium and sulfate toxicity.