几种印染助剂对壳聚糖稳定纳米铁去除酸性品红的影响

以氯化铁为铁源，硼氢化钠为还原剂，壳聚糖为稳定剂，采用液相还原法制备壳聚糖稳定纳米铁（CS-nZⅥ）；研究了印染废水中常见助剂NaNO₃、Na₂SO₄、NaH₂PO₄、K₂Cr₂O₇、EDTA二钠盐存在下，超声波辅助CS-nZⅥ对酸性品红（AF）降解的影响。结果表明，反应15 min，0.01 g CS-nZⅥ对25 mL、100 mg/L AF的去除率高达99.9%；各种助剂的存在使得纳米铁表面不同程度失活，阻碍反应的进行，使得AF的去除率下降。NaNO₃、K₂Cr₂O₇、EDTA二钠盐与纳米铁发生反应，与AF存在明显的竞争作用。重复利用实验表明，CS-nZⅥ重复利用7次仍具有一定的反应活性。此外，CS-nZⅥ对加标（50 mg/L）实际废水中AF的去除率达到99%以上，表明CS-nZⅥ是一种潜在的环境修复材料。     

微波催化氧化处理正丁酸废水Ni-Co-Ce-O催化剂的制备及表征

采用微波催化氧化处理正丁酸模拟废水，以COD去除率为评价指标，对固相-焙烧法制备的3个系列共45种催化剂进行筛选，通过正交实验对催化剂制备工艺进行优化，并对优选出的催化剂进行XRD和SEM表征。结果表明，NiO+Co₂O₃+CeO₂（Ni∶Co=1∶1、NiO+Co₂O₃/CeO₂=1∶4）为筛选出的最优催化剂；Ni-Co-Ce-O催化剂最优制备条件为Ni：Co摩尔比1∶2、（NiO+Co₂O₃）/CeO₂质量比5%、研磨时间40 min、焙烧温度450℃、焙烧时间3 h，此条件下制备的催化剂催化效能最高，COD去除率达67%。     

Fe3O4/Ag磁性纳米颗粒去除水中的铅离子

采用水相共沉淀法制备小尺寸磁性Fe₃O₄纳米颗粒,以没食子酸作为还原剂和表面修饰剂,还原Ag[(NH₃)₂]⁺制备出Fe₃O₄/Ag磁性纳米颗粒。研究该磁性纳米颗粒对水溶液中铅离子的吸附行为,研究结果表明,pH为7.0,吸附温度30℃时可得到最好的处理效果,铅的去除率可达99.7%以上,Fe₃O₄/Ag颗粒吸附行为符合二级动力学模型(R² > 0.99)。该磁性纳米颗粒经过多次再生处理后,仍具有很好的吸附效果,表明Fe₃O₄/Ag在水处理方面拥有良好的应用前景。     

高岭土负载纳米铁镍双金属去除水中偶氮染料直接耐晒黑G

采用液相还原法制备焙烧高岭土负载纳米铁镍双金属（CK-Fe/Ni）。考察了在不同条件下,如pH、投加量、初始浓度、温度等,对负载型纳米铁镍双金属降解水中偶氮染料直接耐晒黑G的影响及动力学研究。结果表明：在pH=9.49、温度为30℃、负载型纳米铁镍双金属的投加量为1.05 g/L、搅拌速度为60 r/min,经过20 min反应后,负载型纳米铁镍双金属降解水中偶氮染料直接耐晒黑G的去除率达到了99.98%。吸附和电镜表征结果表明,作为载体的焙烧高岭土起着吸附直接耐晒黑G和分散纳米铁镍双金属颗粒的作用导致反应活性提高。降解动力学数据表明,负载型纳米铁镍双金属对直接耐晒黑G的降解过程符合伪一级反应动力学规律,速率常数k随负载型纳米铁镍双金属的投加量的增加而提高,表观活化能为19.72 kJ/mol。最后,利用高岭土负载纳米铁镍双金属对废水处理,结果表明,负载型纳米铁镍双金属在实际废水中对直接耐晒黑G的去除率达到了99.98%。     

城市垃圾焚烧渗沥液中Ca2+对厌氧EGSB处理效果的影响简

研究了城市生活垃圾焚烧厂渗沥液中Ca²⁺对厌氧颗粒污泥膨胀床反应器（EGSB）处理效果的影响，并采用静态实验方法考察了Ca²⁺对厌氧颗粒污泥产甲烷活性的影响。实验结果表明，进水COD为17 000 mg/L的条件下，当Ca²⁺浓度低于6 000 mg/L时，EGSB对COD去除率达93%以上；当Ca²⁺浓度高于6 000 mg/L时，COD去除率随运行时间明显下降，并在污泥中形成大量沉淀。静态实验结果表明，废水中低浓度Ca²⁺促进了厌氧颗粒污泥的产甲烷活性，但高浓度Ca²⁺明显抑制了其产甲烷活性，这是导致高Ca²⁺浓度条件下EGSB对COD去除率降低的主要原因。研究表明，颗粒污泥产甲烷活性恢复程度随Ca²⁺浓度增加而减弱。     

共存物质对重金属絮凝剂 MCC 除镉性能的影响简

为进一步拓展天然高分子絮凝剂壳聚糖的应用范围，以壳聚糖、L-半胱氨酸为原料，通过酰胺化反应制备一种具有重金属捕集功能的高分子重金属絮凝剂-2-氨基-3-巯基丙酰壳聚糖（MCC），研究了水体中常见的阴阳离子、有机配位剂及浊度对MCC除镉性能的影响，探讨了絮体形貌与絮体分形维数及絮凝除镉效果间的关系。结果表明，Na⁺、Cl^-、NO₃^-、F^-、SO₄^2-的存在对MCC除Cd²⁺均有促进作用，Ca²⁺表现为明显的抑制作用；低浓度的EDTA对除镉有促进作用，随着EDTA浓度的增大，逐渐转为抑制作用；低浓度的腐殖酸对MCC去除Cd²⁺有显著的促进作用；在一定范围内，浊度可促进 MCC对Cd²⁺的去除；絮体间空隙越多，絮体分形维数越小，除镉效果越好。     

阴极负载不同催化剂对天然水体中沉积物微生物燃料电池运行特性的影响

考察了阴极负载Co₃O₄和MnOOH对天然水体中沉积物微生物燃料电池（SMFC）产电性能和SMFC对沉积物中有机质去除率的影响。实验结果表明，SMFC阴极负载Co₃O₄和MnOOH后，体系的输出电压由483 mV增大到549 mV和534 mV；相应体系的内阻由206 Ω显著降低到99 Ω和128 Ω，最大功率密度（Pmax）由3.3 mW/m²增大到9.1 mW/m²和6.6 mW/m²。此外，SMFC体系的电流密度与沉积物中烧失量（LOI）、易氧化有机质（ROOM）去除率呈线性关系，并且阴极负载Co₃O₄和MnOOH可以促进阳极沉积物中有机质的去除。     

酸度对好氧颗粒污泥生物吸附含铅废水影响的研究

为了有效地控制铅污染，利用序批式反应器（sequencing batch reactor,SBR）培养的以醋酸钠为碳源的好氧颗粒污泥作为吸附剂，进行生物吸附含铅废水的效能和机理的研究。通过考察酸度、接触时间和Pb²⁺初始浓度等因素的影响，验证好氧颗粒污泥吸附模型，并利用不同的脱附剂，进一步解析其生物吸附的Pb²⁺。实验结果表明, 酸度是影响好氧颗粒污泥生物吸附Pb²⁺的关键因素，当初始pH为5时，好氧颗粒污泥对含铅废水生物吸附效果最好。对低浓度（0～20 mg/L）含铅废水， 10 min后可快速达到吸附平衡。好氧颗粒污泥对Pb²⁺的实测饱和吸附量为101.97±9.00 mg/g，符合朗缪尔（Langmuir）模型。好氧颗粒污泥生物吸附Pb²⁺的过程，伴随着pH值的升高和K⁺、 Ca²⁺、 Mg²⁺的释放，此现象揭示离子交换作用是好氧颗粒污泥生物吸附Pb²⁺的机理之一。此外，脱附剂HNO₃、EDTA和CaCl₂能实现Pb²⁺的回收和好氧颗粒污泥的重复利用。     

壳聚糖联合碱改性粉煤灰对重金属离子的吸附特性

采用浸渍法将壳聚糖负载在经NaOH改性的粉煤灰上，制备了联合改性的粉煤灰。随粉煤灰上壳聚糖负载量的增加，粉煤灰对Pb²⁺和Cd²⁺的吸附率均提高。当负载壳聚糖的质量分数为8%，吸附温度为30℃，吸附时间为120 min时，粉煤灰对Pb²⁺的吸附率最高（为98.9%），对Cd²⁺的吸附率也最高（为91.5%）。其吸附行为符合Freundlich等温吸附模型，但表现为2个线性区。粉煤灰负载壳聚糖的改性机理是粉煤灰与带正电荷的壳聚糖的化学键合作用。     

低温条件下BAF+SPD组合工艺对滇池入湖河水的脱氮效果

为缓解湖泊富营养化问题，需进一步降低入湖河流氮的含量。针对滇池流域新运粮河的低C/N水质特征，研究了冬季低温条件下的微曝气生物滤池（BAF）及固相反硝化（SPD）组合异位脱氮工艺。结果表明，BAF+SPD组合工艺启动挂膜阶段，约3周后，NH₄⁺-N的去除率达80%以上，而反硝化细菌增殖相对缓慢，约5周后，NO₃^--N的去除率达80%以上；稳定运行的低温阶段，除降雨时间外，NH₄⁺-N平均去除率达80%，出水NH₄⁺-N浓度<1 mg/L；NO₃^--N平均去除率达到85%以上，出水NO₃^--N浓度<1 mg/L；TN平均去除率达80%以上，出水TN浓度<2 mg/L，主要水质指标达到国家地表水Ⅴ类标准。     

Dechlorination of chlorinated hydrocarbons by bimetallic Ni/Fe immobilized on polyethylene glycol-grafted microfiltration membranes under anoxic conditions

In this study, the dechlorination of chlorinated hydrocarbons including trichloroethylene (TCE), tetrachloroethylene (PCE) and carbon tetrachloride (CT) by bimetallic Ni/Fe nanoparticles immobilized on four different membranes was investigated under anoxic conditions. Effects of several parameters including the nature of membrane, initial concentration, pH value, and reaction temperature on the dechlorination efficiency were examined. The scanning electron microscopic images showed that the Ni/Fe nanoparticles were successfully immobilized inside the four membranes using polyethylene glycol as the cross-linker. The agglomeration of Ni/Fe were observed in poly(vinylidene fluoride), Millex GS and mixed cellulose ester membranes, while a relatively uniform distribution of Ni/Fe was found in nylon-66 membrane because of its hydrophilic nature. The immobilized Ni/Fe nanoparticles exhibited good reactivity towards the dechlorination of chlorinated hydrocarbons, and the pseudo-first-order rate constant for TCE dechlorination by Ni/Fe in nylon-66 were 3.7-11.7 times higher than those in other membranes. In addition, the dechlorination efficiency of chlorinated hydrocarbons followed the order TCE > PCE > CT. Ethane was the only end product for TCE and PCE dechlorination, while dichloromethane and methane were found to be the major products for CT dechlorination, clearly indicating the involvement of reactive hydrogen species in dechlorination. In addition, the initial rate constant for TCE dechlorination increased upon increasing initial TCE concentrations and the activation energy for TCE dechlorination by immobilized Ni/Fe was 34.9 kJ mol⁻¹, showing that the dechlorination of TCE by membrane-supported Ni/Fe nanoparticles is a surface-mediated reaction.     

Removal of trichloroethylene from water by cellulose acetate supported bimetallic Ni/Fe nanoparticles

In this study, cellulose acetate (CA) supported Ni/Fe nanoparticles were prepared and the ability of these nanoparticles to remove trichloroethylene (TCE) from water was studied. The effects of TCE reduction by the nanoparticles and sorption by the CA support were accounted for separately in the model. CA supported post-coated Ni/Fe nanoparticles were used to investigate the effect of metal particle composition on the observed reduction rate constant. The results show that the metal mass normalized observed reduction rate constant was proportional to the Ni content in the post-coated Ni/Fe nanoparticles in the range of 0-14.3 wt.%. This constant reached a maximum between 14.3 and 21.4 wt.% and decreased with further increase in Ni content. CA supported co-reduced Ni/Fe bimetallic nanoparticles gave poorer performance compared to CA supported post-coated Ni/Fe bimetallic nanoparticles at the same Ni content in Ni/Fe nanoparticles.     

An improved UV/Fe3+ process by combination with electrocatalysis for p-nitrophenol degradation

p-nitrophenol (PNP) was investigated as a model pollutant under the improved UV/Fe3+ process by combination with electrocatalysis. In the individual UV/Fe3+ process, PNP degradation rate was dependent on Fe(III) concentration and decreased during degradation due to the depletion of ferric ion and thus it was very difficult to reach the quick mineralization of organics. These drawbacks could be significantly overcome in the modified UV/Fe3+ process, and synergetic effects for PNP and COD removal were observed at two investigated Fe(III) concentrations. The enhancements on the degree of conversion for PNP and COD in presence of 0.5 mM Fe(III) were 184% and 242%, respectively, and PNP of initial concentration of 1.0 mM could be completely removed within 1 h. Thus such a process would be very attractive to the rapid mineralization of the biorefractory compounds for wastewater treatment. The possible reasons for the synergetic effects were the electrochemical regeneration of ferric ion and the role of the oxygen that formed on the anode. Based on degradation intermediates identification and synergetic effect probe, a general reaction pathway for PNP degradation in the improved process was proposed.     

金属纳米材料在厌氧条件下对脱氮副球菌反硝化作用的影响

以脱氮副球菌YF1为实验菌株,研究纳米Fe0和纳米Fe/Ni 2种金属纳米材料对菌体生长及其反硝化作用的影响。实验结果表明:添加纳米材料到反应体系中会降低实验菌株的生长量和生物反硝化作用,纳米Fe/Ni对实验菌株的毒性比纳米Fe0大。在含硝态氮初始浓度为100 mg/L的反硝化培养基中接种脱氮副球菌,于30℃培养20 h,脱氮率为89.47%,而菌+1 000 mg/L纳米Fe/Ni的体系脱氮率仅为64.33%;菌+1 000 mg/L纳米Fe0体系的脱氮率为76.36%。不同体系的反硝化过程均可采用零级动力学模型进行拟合(相关系数R2>0.92)。这2种金属纳米材料对实验菌株的生长量及其反硝化作用的影响程度,与体系的pH和温度有较大关系。     

羟丙基壳聚糖纳米微粒的制备及其对Ni2+的吸附研究

通过在碱性条件下将羟丙基引入到壳聚糖分子上,再利用离子凝胶法制备羟丙基壳聚糖(HCS)纳米微粒.结果表明,HCS溶液的质量浓度为0.8～2.0 mg/mL、多聚磷酸钠(TPP)的质量浓度为0.4～1.5 mg/mL时,均可以生成HCS纳米微粒.粒径分布表明,HCS纳米微粒主要粒径约为200～300 nm,粒径分布较窄....     

Fate of a stilbene-type fluorescent whitening agent (DSBP) in the presence of Fe(III) aquacomplexes: from the redox process to the photodegradation

The behaviour of 4,4′-bis(2-sulfostyryl)biphenyl (DSBP), a fluorescent whitening agent, was investigated in the presence of Fe(III) aquacomplexes at room temperature. In the dark, a two-step reaction was observed when adding Fe(III) to a solution of DSBP: an initial fast redox reaction between DSBP and the monomeric species Fe(OH)²⁺ and a slower reaction leading to the coagulation of oxidised DSBP and iron. This phenomenon is due to the formation of a complex or an ion-pair between Fe(II) and/or Fe(III) with oxidised DSBP and it probably occurs by charge neutralisation in our experimental conditions. The precipitation of DSBP depends on the initial concentration in Fe(OH)²⁺ and is achieved for a ratio [Fe(OH) ²⁺]/[DSBP] of 5 approximately. Under irradiation at 365 nm, a complicated behaviour was observed: a complexation of iron by oxidised DSBP favoured by irradiation and a degradation of DSBP induced by an intramolecular electron transfer in the complex or by a photoredox of Fe(OH)²⁺ species generating OH radicals in the supernatant. The complete degradation of DSBP is reached four times faster in the presence of Fe(III) with respect to the direct photolysis of DSBP alone. Moreover, the total mineralization of DSBP obtained in less than 120 h upon irradiation at 365 nm is only observed in the presence of the ferric ions, enlightening the efficiency of the method involving Fe(III) and UV irradiation.     

新型重金属捕集剂NBMIPA处理含铜汞废水

研究了以间苯二甲酰氯和巯基乙胺盐酸盐为原料合成的重金属捕集剂NBMIPA对单一Cu2＋、Hg2＋电镀废水的捕集性能。结果研究表明,NBMIPA对Cu2＋和Hg2＋的捕集性能优良,NBMIPA投加量越大,捕集性能越高;NBMIPA对pH具有较宽适应性。NBMIPA对于单一含铜废水可无需调pH,投加捕集剂量为废水中含量的4～5倍（摩尔比）,静置后其上层清夜中所含Cu2＋为0.38 mg/L,Cu2＋的去除率可达99.5%以上;当NBMIPA的投加量（摩尔比）是Hg2＋的3.5～4.5倍时,Hg2＋的去除率达到99.83%,残余Hg2＋浓度为0.032 mg/L。     

水热炭化餐厨垃圾制备纳米铁/炭复合材料

以餐厨垃圾中有机组分作为碳源,通过添加铁盐水热炭化制备铁/炭纳米复合材料。考察了不同铁盐(Fe-SO4,FeCl3,Fe(NO3)3)对餐厨垃圾水热炭化物的形貌,以及氮、磷元素的迁移转化的影响;并研究了负载铁的物理、化学性质。实验结果表明,铁盐在水热炭化过程中促进了餐厨垃圾转化生成多种纳米结构。铁的价态是影响复合物形貌的主要影响因素:三价铁离子对大分子有机物的水解和炭化过程有催化作用,从而促进壳核式结构的纳米线及微米球复合物的生成;而亚铁离子则导致可溶性有机物炭化形成空心纳米球结构。负载铁的化学形态主要受阴离子的影响:硝酸铁体系中铁主要以氢氧化物形式沉积、其他阴离子体系则以磷酸盐为主要形态负载。     

矸石基X型分子筛对水中Co2+、Cu2+、Cd2+和Cr3+的去除

以煤矸石为原料,采用碱熔后水热合成法制备X型分子筛并进行XRD、SEM、BET和Zeta电位分析。研究其对水中Co2+、Cu2+、Cd2+和Cr3+4种离子的吸附性能,包括吸附等温线、吸附动力学以及初始金属离子浓度、pH值对吸附性能的影响。所合成的矸石基X型分子筛的BET比表面积为676.02 m2/g,微孔孔容为0.263 cm3/g。吸附实验表明,矸石基X型分子筛能有效去除上述4种离子,同时实现煤矸石的资源化和金属离子的去除。4种离子的平衡吸附量均随初始浓度的增大而增大,相同条件下平衡吸附量的大小顺序为Cd2+>Cr3+>Cu2+>Co2+。准二级动力学模型能很好地描述4种离子的吸附动力行为。Langmuir模型对Co2+、Cu2+和Cd2+吸附的拟合较Freundlich模型高,说明其主要表现为物理吸附过程。4种离子的吸附速率均由液膜扩散和颗粒内扩散共同控制。     

Fe3O4/SDS磁性纳米颗粒吸附水体中的Cd2+和Zn2+

一种新型纳米固相萃取吸附剂,由阴离子表面活性剂十二烷基磺酸钠(SDS)包裹在Fe3O4磁性纳米颗粒表面形成,用于吸附水溶液中的重金属离子。研究了吸附过程的主要影响因素(如SDS浓度、溶液pH等)以及解吸过程的最佳条件,并对其机理进行了初步的探讨。研究结果表明,共沉淀法制备的Fe3O4颗粒粒径分布均匀,平均粒径约为54 nm;SDS浓度为300 mg/L时,Fe3O4/SDS磁性纳米颗粒吸附Cd2+和Zn2+的能力最强;在一定浓度范围内,Fe3O4/SDS体系对Cd2+和Zn2+的吸附平衡数据符合Langmuir吸附等温方程,饱和吸附量分别为22.42 mg/g和13.95 mg/g。最终结果表明,Fe3O4/SDS磁性纳米颗粒具有较强磁分离能力和较好的吸附效果。