天然高分子吸附剂研究——羧甲基交联壳聚糖树脂的合成及吸附特性

以壳聚糖为原料，经乙二醇双缩水甘油醚交联后，与氯乙酸反应，合成了羧甲基交联壳聚糖树脂，并研究了其对Ｃｕ＾２＋、Ｎｉ＾２＋，Ｃｏ＾２＋的静态吸附性能，结果表明，该树脂对上述３种金属离子均具有良好的吸附性能，其吸附容量分别达２．２５，１．９８和１．８１ｍｍｏｌ·ｇ＾－１。     

改性壳聚糖重金属生物质吸附剂的制备及表征

为改善壳聚糖的耐酸性及对Pb(Ⅱ)的吸附容量,将壳聚糖与丙烯酰胺接枝,再与戊二醛进行交联,制备出了壳聚糖改性聚合物(G-CAM)。研究了制备条件对接枝率和接枝效率的影响,结果表明,在T=70℃;单体浓度(m壳聚糖:m丙烯酰胺)为1:3;引发剂浓度为0.10g;接枝反应时间为4h时,可制得较为满意的接枝壳聚糖产物。对交联剂的用量通过耐酸性实验和Pb2+吸附实验进行了考察,结果表明,当m壳聚糖:m丙烯酰胺=1:3(m壳聚糖=1g)时,交联剂戊二醛的加入量为0.6mL,得到的产物制备成的吸附剂不但有较好的耐酸性,而且对Pb(Ⅱ)吸附效果最佳。经吸附剂再生实验,G-CAM对Pb(Ⅱ)的吸附量变化幅度小于1%,可重复使用。     

羧基淀粉接枝聚合物的制备及其在重金属离子废水处理中的应用

本文研究了玉米淀粉经环氧氯丙烷交联制成高交联淀粉后,以Ge~(4+)为引发剂,把丙烯腈接枝到高交联淀粉上,通过碱皂化作用将腈基转化为羧基制备羧基淀粉接枝聚合物(ISC)的方法。并研究了ISC在含重金属离子废水处理方面的应用。     

改性壳聚糖的制备及其对水中酞酸酯的吸附

以柠檬醛化学改性壳聚糖,制备柠檬醛交联壳聚糖树脂。采用红外光谱(IR)、X射线衍射(XRD)、扫描电镜(SEM)、比表面测定及孔径分析方法表征柠檬醛交联壳聚糖树脂的结构。在25℃,pH为7条件下,考察柠檬醛交联壳聚糖树脂对3种酞酸酯(PAEs)邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二丁酯(DBP)和邻苯二甲酸2-乙基己酯(DEHP)的吸附性能,剖析吸附机理。研究结果表明,壳聚糖对DMP、DEHP和DBP的吸附容量分别为92、113和87 mg/g,而柠檬醛交联壳聚糖树脂对DMP、DEHP和DBP的吸附容量分别为147、166和190 mg/g,柠檬醛交联壳聚糖树脂对3种PAEs的吸附效果明显提高,吸附动力学均满足一级动力学方程。经吸附剂再生实验,柠檬醛交联壳聚糖树脂对PAEs的脱附率达到96.5%~97.1%,可重复使用。     

壳聚糖接枝共聚物在污泥脱水中的应用研究

以壳聚糖为原料,通过接枝共聚反应分别合成壳聚糖-AM-DMDAAC,壳聚糖-AM,壳聚糖-AA三种不同类型的天然改性高分子絮凝剂.对活性污泥脱水性能的研究结果表明,与其它两种壳聚糖接枝共聚物相比,壳聚糖-AM-DMDAAC阳离子型接枝共聚物是适合污泥脱水的良好絮凝剂.对于100 mL污泥,当污泥pH值为6.00,投药量为20 mg/L,真空度0.05 MPa下,阳离子型壳聚糖接枝共聚物真空抽滤1 min的滤液体积可达到70 mL,抽滤 5 min 后,可将污泥含水率从95.4%降低到86.4%,脱水效果优于其它几种常用的污泥脱水剂.     

壳聚糖乙酸酯冠醚对金属离子的吸附性能研究

利用壳聚糖Ｃ２位上活泼氨基与苯甲醛进行反应,制得了Ｓｃｈｉｆｆ碱苯甲醛壳聚糖（简称ＣＴＢ）,再将合成的二苯并１６－冠－５氯代乙酸酯冠醚接枝到ＣＴＢ上,得到壳聚糖－苯并１６－冠－５乙酸酯冠醚（简称ＴＣＢＣ）,使其在酸性条件下脱去苯甲醛,制得壳聚糖－二苯并１６－冠－５－乙酸酯冠醚（简称ＣＴＣＥ）。经元素分析、红外光谱分析表征了其结构。并研究了ＣＴＢＣ和ＣＴＣＥ对Ｐｂ＾２＋、Ｃｕ＾２＋、Ｃｒ＾３＋、Ｎｉ     

交联改性壳聚糖的制备及其对Ni2+的吸附性能

以壳聚糖为原料,甲醛为预交联剂,戊二醛为交联剂,通过反相乳液聚合法制备了改性壳聚糖吸附剂.通过正交试验考察了交联反应条件对改性壳聚糖吸附Ni2+性能的影响,得出的最佳交联条件为:甲醛用量1 mL,反应温度70℃,戊二醛用量2 mL,反应时间2h.在最佳条件下制备的交联壳聚糖对Ni2+的吸附量达1.98 mmol/g.对吸附Ni2+后的交联壳聚糖分别用0.1 mol/L盐酸和0.1 mol/L氢氧化钠溶液进行脱附,结果表明用0.1 mol/L氢氧化钠溶液脱附效果较好.     

诺氟沙星吸附剂生物炭-壳聚糖复合微球的制备优化

为了提高生物炭-壳聚糖复合微球对NOR（诺氟沙星）的吸附能力,以复合微球对NOR的吸附量为指标,考察了生物炭与壳聚糖质量比、壳聚糖脱乙酰度、戊二醛用量、交联时间、交联速率及生物炭热解温度对复合微球吸附NOR的影响,并由均匀试验确定复合微球的最佳制备条件.结果表明,生物炭与壳聚糖质量比、壳聚糖脱乙酰度、戊二醛用量、交联时间、交联速率及生物炭热解温度对复合微球吸附NOR具有明显影响.制备复合微球的关键影响因素是生物炭热解温度、戊二醛用量和交联速率.吸附NOR的复合微球最佳制备条件:生物炭热解温度为300℃、生物炭与壳聚糖质量比为5:1、壳聚糖脱乙酰度为77%、戊二醛用量为80 mL、交联速率为150 r/min、交联时间为3 h.此时,复合微球对NOR的吸附量为9.51 mg/g,且具有较高的耐酸溶性和机械强度.研究显示,复合微球能够高效吸附NOR,并且吸附后容易分离,具有修复水体污染的潜力.      

端烯丙基苯并15-冠-5接枝壳聚糖对金属离子的吸附性能

将３’－端烯丙基苯并１５－冠－５和４’－端烯丙基苯并１５－冠－５接枝到壳糖或交联壳聚糖上,合成了４种新新型的壳聚糖冠醚,并研究了这４种壳聚糖冠醚对Ｐｄ＾２＋、Ｃｕ＾２＋、Ｈｇ＾２＋的静态吸附性能。结果表明,这４种吸附剂对Ｐｄ＾２＋具有良好的吸附性能,并能在Ｃｕ＾２＋和Ｈｇ＾２＋共存的条件下选择吸附Ｐｄ＾２＋。     

铅模板交联壳聚糖对Pb(Ⅱ)的吸附性能

研究了脱乙酰度、粒度和溶液pH值等因素对壳聚糖吸附铅离子性能的影响,得到了最佳吸附条件为壳聚糖脱乙酰度100%和溶液pH值6.5.在该条件下,壳聚糖与铅离子作用后,用戊二醛交联,然后用盐酸洗脱铅离子,合成了铅交联壳聚糖模板树脂.探讨了交联剂量对交联壳聚糖吸附性能的影响以及铅模板交联壳聚糖对金属离子的吸附性能.结果表明,在CHO/NH₂为0.75:1时合成交联壳聚糖树脂对铅离子有最大吸附量,并且该树脂对铅离子和铜离子有较高的选择性,在酸性条件下不会发生软化和溶解,重复使用性良好.     

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.     

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.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

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.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.