生物载体强化的连续流生物制氢反应器的运行特性

在连续流搅拌槽式反应器(CSTR)中填加比重为1.54 g/cm³,粒径小于2mm的多孔物质,以糖蜜废水为底物利用活性污泥制取氢气.考察了填加生物载体后生物制氢反应器连续流稳定运行的系统特性.研究表明,投加生物载体能够扩大产氢细菌的活性范围,提高系统的抗冲击负荷能力和耐低pH值的能力,增加系统稳定性,并且可使系统在低HRT下保持较高的生物量.此连续流生物制氢反应系统的最佳发酵类型为乙醇型发酵,适宜的pH值范围为3.8～4.4,气相中的氢气含量约为40%～57%,最大产氢速率为0.37L/(g·d).降低pH值可抑制厌氧发酵过程中出现的产甲烷菌群,加速产氢反应器的启动.     

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.     

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).     

利用有机质发酵产氢的影响因素与应用前景

煤、石油等化石能源的紧缺,使得氢气等可再生能源的开发与利用备受关注.生物制氢技术由于在获得清洁能源氢气的同时,还使得大量有机废弃物得到处理或净化,从而使得该技术成为当前研究的热点.总结了发酵产氢的微生物种类及产氢基质,阐述了不同有机物种类的发酵产氢机理,综述了温度、pH值、金属离子、气相条件及氧化还原电位等生态因子对发酵产氢的影响,并论述了生物制氢技术的发展方向和应用前景.     

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.     

有机废水处理生物制氢技术

研究了利用有机废水发酵作用制取廉价氢气技术,并研制出厌氧活性污泥高效生物制氢反应器。以白脱糖、糖蜜和淀粉为供氢体,最大产氢能力达10.4m³H₂/m³反应器·d,发酵气中仅含48％H2和52％CO₂。该项技术已具有进一步开发价值。     

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.     

不同底物MEC产氢潜力的研究

微生物电解池(microbial electrolysis cells,MEC)制氢技术是在传统发酵制氢中引入电解协助,克服了传统发酵制氢体系的热力学限制,使发酵末端产物挥发性有机酸能进一步转化为氢气,从而提高制氢效率。为考察不同底物MEC制氢的可行性,实验采用单池MEC反应器,在恒温35℃和电解电压为1.0 V下,以厌氧活性污泥为接种物,研究了挥发性有机酸(乙酸钠、丙酸钠和丁酸钠)、糖类化合物(葡萄糖、蔗糖和淀粉)的MEC产氢潜力。比较了Modified Gomperts模型获得各底物的动力学参数,氢气产率,及实验过程中电流,产氢潜力及能源转化率值。实验结果表明,酸挥发性有机酸与糖类化合物都能够在电解协助下产生氢气,乙酸钠、丙酸钠和丁酸钠的产氢潜力分别为40、26、48 m L/g,而葡萄糖、蔗糖和淀粉的产氢潜力分别为104、87、75 m L/g;葡萄糖、蔗糖、淀粉为底物时较乙酸钠、丙酸钠、丁酸钠更容易被降解利用产氢。     

发酵制氢微生物与高效发酵途径的研究进展

近年来发酵生物制氢技术在国内外备受关注,如何确保稳定、持续、高效的产氢效率和产氢速率成为生物制氢研究的重要方向。文章结合国内外最新研究进展,从微生物发酵产氢的菌种种类、复合方式、固定方法,以及发酵制氢途径等方面进行阐述如何提高产氢效率和产氢速率,并对生物发酵制氢在未来的发展方向进行了分析和展望。     

Fe和Fe2+对混合细菌产氢发酵的影响

在研究Fe粉剂量和Fe²⁺浓度对混合细菌产氢发酵的影响基础上,确定Fe和Fe²⁺促进混合细菌产氢能力的最佳阈值,并对乙醇型发酵菌群在不同Fe粉和Fe²⁺浓度下的产氢量和最大比产氢速率进行考察和对比.结果表明,Fe粉和Fe²⁺对乙醇型发酵菌群的产氢能力均有明显的促进作用.以葡萄糖为底物,投加Fe²⁺试验中,Fe²⁺浓度200mg/L获得最大产氢量143.7mL/g,较对照组提高32%;Fe²⁺浓度50mg/L获得单位VSS最大比产氢速率21.2 mL/(h·g),较对照组提高33%.投加单质Fe试验中,Fe粉剂量1000mg/L获得最大产氢量156.1mL/g,较对照组提高44%;Fe粉剂量500mg/L获得单位VSS最大比产氢速率23.5mL/(h·g),较对照组分别提高47%.单质Fe浓度高于50mg/L时,对发酵菌群产氢的促进作用要优于同浓度下的Fe²⁺.同时对混合细菌中铁的全量和形态分布进行了考察.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Oxidation of As(Ⅲ) by potassium permanganate

The oxidation of As(Ⅲ) with potassium permanganate was studied under conditions including pH, initial As(Ⅲ) concentration and dosage of Mn(Ⅶ). The results have shown that potassium permanganate was an effective agent for oxidizing of As(Ⅲ) in a wide pH range. The pH value of tested water was not a significant factor affecting the oxidation of As(Ⅲ) by Mn(Ⅶ). Although theoretical redox analyses suggest that Mn(Ⅶ) should have better performance in oxidization of As(Ⅲ) within lower pH ranges, the experimental results show that the oxidation efficiencies of As(Ⅲ) under basic and acidic conditions were similar, which may be due to the adsorption of As(Ⅲ) on the Mn(OH)2 and MnO2 resulting from the oxidation of As(Ⅲ).     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Chlorobenzenes in waterweeds from the Xijiang River （Guangdong section） of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes (CBs) in both water and waterweeds collected from 4 stations in the Xijiang River (Gangdong section) of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs (∑CBs) in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ∑ CBs in waterweeds ranged from 13.53×102 μg/g to 38.27×102μg/g dry weight (dw). There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs(DCBs), whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip (bioconcentration factor) of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was: Fengkai County ＜ Yunan County ＜Yun'an County ＜ Gaoyao County according to the ∑CBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River.     

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process

Degradation of 2,4-dichlorophenol(2,4-DCP)was studied in a novel three-electrode photoelectrocatalytic(PEC)integrative oxidation process,and the factors influencing the degradation rate,such as applied current,flow speed of O_2,pH,adscititious voltage and initial 2,4-DCP concentration were investigated and optimized.H_2O_2 was produced nearby cathode and Fe~(2 )continuously generated from Fe anode in solution when current and O_2 were applied,so,main reactions,H_2O_2-assisted TiO_2 PEC oxidation and E-Fenton reaction,occurred during degradation of 2,4-DCP in this integrative system.The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process,while it was only 31% in E-Fenton process and 46% in H_2O_2-assisted TiO_2 PEC process.So,it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect.By the investigation of pH,it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.     

Effect of copper on the degradation of pesticides cypermethrin and cyhalothrin

The influence of coexisting copper (Cu) ion on the degradation of pesticides pyrethroid cypermethrin and cyhalothrin in soil and photodegradation in water system were studied.Serial concentrations of the pesticides with the addition of copper ion were spiked in the soil and incubated for a regular period of time,the analysis of the extracts from the soil was carried out using gas chromatography (GC).The photodegradation of pyrethroids in water system was conducted under UV irradiation.The effect of Cu~(2 ) on the pesticides degradation was measured with half life (t_(0.5)) of degradation.It was found that a negative correlation between the degradation of the pyrethroid pesticides in soil and Cu addition was observed.But Cu~(2 ) could accelerate photodegradation of the pyrethroids in water.The t_(0.5) for cyhalothrin extended from 6.7 to 6.8 d while for cypermethrin extended from 8.1 to 10.9 d with the presence of copper ion in soil.As for photodegradation,t_(0.5) for cyhalothrin reduced from 173.3 to 115.5 rain and for cypermethrin from 115.5 to 99.0 min.The results suggested that copper influenced the degradation of the pesticides in soil by affecting the activity of microorganisms.However, it had catalyst tendency for photodegradation in water system.The difference for the degradation efficiency of pyrethroid isomers in soil was also observed.Copper could obviously accelerate the degradation of some special isomers.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.