富含中孔与酸性基团的生物质炭的制备与吸附性能

以棉秆基生物质纤维为原料,采用磷酸一步活化法制备了同时富含中孔与含氧酸官能团的新型高比表面棉秆纤维基生物质活性炭,分析了浸渍比、炭化温度及保温时间等操作参数对活性炭纤维组成、得率、孔结构及表面官能团含量的影响,测定了制得的棉秆纤维基活性炭对水中对Pb(Ⅱ)与对硝基苯胺的等温吸附性能,并初步探讨了其吸附机制.结果表明,棉秆纤维基生物质炭孔结构与含氧酸基团因制备条件不同有较大变化,实验条件下制备的棉秆基活性炭纤维产率、中孔孔容与比表面的最大值分别为35.5%、0.91 cm3·g-1、1731 m2·g-1;在3∶2的浸渍比,600℃活化90 min的工艺条件下,制备的样品ACF-01的总孔孔容达1.02 cm3·g-1,比表面积为1 731 m2·g-1,微、中孔比例分别为66%与31%,中孔集中在5 nm以内,富含含氧酸官能团.样品ACF-01对水中Pb(Ⅱ)与对硝基苯胺的Langmuir最大吸附量分别为123 mg·g-1和427 mg·g-1,吸附性能远高于微孔孔容相近的商业活性炭纤维ACF-CK,这表明活性炭ACF-01的中孔和含氧酸官能团在吸附过程中发挥了重要作用.     

高比表面植物基活性炭吸附水中对硝基苯胺的性能及影响因素

以互花米草与棉秆为原料,以KOH为活化剂,制备了2种低成本高比表面微孔植物基活性炭SA-AC和CS-AC,通过静态实验研究了其对水溶液中对硝基苯胺的吸附特性,测定了溶液pH值、吸附剂剂量、溶液温度对吸附的影响,并探讨了等温吸附行为及其热力学性质.结果表明,在KOH与炭化料的质量比(剂料质量比)为3∶1、活化温度为800℃、活化时间为1.5 h条件下,活化制备的互花米草活性炭SA-AC和棉秆活性炭CS-AC的比表面积分别为2 825 m2.g-1和2 135 m2.g-1,微孔容积分别为1.192 cm3.g-1和1.011 cm3.g-1,对水溶液中对硝基苯胺的Langmuir最大吸附量分别为719和716 mg.g-1,远高于商业活性炭ST1300.溶液pH值和温度对吸附有较大影响,在低温及中性条件下有利于制备活性炭对水溶液中对硝基苯胺的吸附.Freundlich与Redlich-Peterson模型能很好地描述对硝基苯胺在2种活性炭上的吸附行为;热力学研究表明,吸附标准吉布斯自由能变ΔG0与标准焓变ΔH0均为负值,表明对硝基苯胺在这2种活性炭上的吸附属于自发的放热吸附过程;吸附标准熵变ΔS00,说明对硝基苯胺在活性炭表面上的迁移比在溶液中受到了更大的限制.     

KOH活化法制备牛粪活性炭的研究

以牛粪为原料,采用KOH活化法制备活性炭,并考察了浸渍比、活化剂浓度、活化时间和活化温度等不同制备条件对牛粪活性炭样品性能的影响.实验结果表明,在浸渍比1∶4、KOH质量分数35%、活化时间60min、活化温度700℃条件下制备的活性炭性能最佳,制得的活性炭比表面积为979.8m2·g-1,碘吸附值可达796.37mg·g-1,亚甲基蓝吸附值可达150.30mg·g-1.最后,将制备的牛粪活性炭应用于对Cr(Ⅵ)的吸附,研究了最佳工艺条件下制备的活性炭吸附Cr(Ⅵ)的适宜条件.结果表明,在投加量为8g·L-1时、吸附时间90min、pH值为5和较低温度的适宜条件下,自制牛粪活性炭对Cr(Ⅵ)的吸附量最大.     

铅在棉秆基活性炭上的吸附动力学与热力学

以棉秆与棉秆纤维为原料,利用磷酸活化法制备了低成本的高比表面微孔棉秆基活性炭,通过静态实验研究了活性炭对水溶液中铅的吸附特性,测定了溶液pH值、吸附时间、溶液温度对吸附的影响,探讨了吸附动力学、热力学及吸附机制.根据低温液氮(N2/77K)吸附测定数据,以BET方程、BJH法及H-K法对活性炭孔结构进行了表征,以Boehm滴定、FTIR、零电荷点pHPZC测定及元素分析定量表征活性炭表面含氧官能团.结果表明,以棉秆和棉秆纤维为原料制备的活性炭的比表面积分别为1570和1731m2·g-1,含氧酸官能团含量分别为1.43和0.83mmol·g-1,均高于商业活性炭ST1300.静态吸附实验表明,棉秆基活性炭对铅有较大的吸附容量和吸附效率,最大吸附量超过120mg·g-1,溶液pH对吸附有较大的影响,吸附量随时间增大而增大,在5min内可达饱和吸附量的80%;吸附动力学数据符合假二级方程,Freundlich方程能更好地描述等温吸附行为;热力学研究表明,吸附吉布斯自由能(ΔG0)0,而焓变(ΔH0)0,说明吸附为吸热的自发反应过程,升温有利于吸附,离子交换可能在吸附过程中起了重要作用.     

高比表面积铜藻基活性炭的制备及工艺优化

以铜藻为原料,在对其进行元素含量、生化组成分析的基础上,分别采用ZnCl2活化法和H3PO4活化法制备活性炭,并以活性炭得率、碘吸附值、焦糖脱色率为指标,采用正交法考察了升温速率、活化温度、浸渍比(活化剂/铜藻质量比)等因素的影响,得到最佳工艺条件.同时,采用扫描电镜(SEM)、Brunauer-Emmet-Tller(BET)比表面积等方法分析活性炭特征.结果表明,铜藻原料粒度对制得的活性炭性能影响显著,106～180μm的颗粒较为适合.ZnCl2活化法制得的活性炭吸附性能明显优于H3PO4活化法;ZnCl2活化法的最佳工艺条件为:升温速率10℃.min-1、活化温度600℃、活化时间2h、浸渍比4,在保证活性炭得率超过30%的基础上,制备的活性炭比表面积为2314.58m2.g-1,碘吸附值为835.3mg.g-1,焦糖脱色率为110%,性能明显优于其他大型海藻原料所制备的活性炭,是陆地传统活性炭原料的有效补充.     

聚丙烯塑料-锯末干混合制备高介孔率柱状活性炭

以聚丙烯塑料和梧桐锯末为原材料,无水K2CO3为活化剂,采用干混合法制备高介孔率柱状活性炭.通过单因素实验,探究了塑料含量、盐料比、活化温度及活化时间对活性炭吸附亚甲基蓝(MB)性能的影响.结果表明:当塑料含量为20%、盐料比为2.5、活化温度为950℃、活化时间为80 min时,所制备的活性炭具有较高的MB吸附量(322.9 mg·g-1).所制备的活性炭具有发达的微观孔隙结构,其比表面积达到1461.99m2·g-1,平均孔径为3.23 nm,总孔容为1.04 cm3·g-1,其中,介孔孔容为0.80 cm3·g-1,介孔率超过70%,充分说明该方法可制备优质高介孔率柱状活性炭.     

真菌预处理优化制备微介多级孔炭及其吸附甲苯的研究

提出采用黄孢原毛平革菌对生物质前体物进行预处理的制备策略,从而研发孔结构可调的多级孔炭材料模板.选用荷叶作为生物质原材料,探讨菌种投加量、培养时间对多级孔炭材料前驱体的影响,并采用水蒸气物理活化法,分析活化温度和活化时间对炭材料比表面积、孔径分布和表面官能团的综合作用.最后,通过Raman、XRD、BET、FTIR、TGA、SEM、EA等手段表征其物理化学性质,并考察真菌预处理对炭材料的甲苯吸附性能的影响.结果表明,在生物质荷叶质量30 g、菌种投加量4 mL、培养时间7 d、活化温度800℃、活化时间90 min条件下制备的微介多级孔炭材料,在含有较多介孔的前提下比表面积可达937 m~2·g~(-1),总孔容为0.68 cm~3·g~(-1).动态模拟吸附实验发现,经预处理的炭材料在甲苯浓度905 mg·m~(-3)下对其饱和吸附容量为304 mg·g~(-1),是未经真菌调控荷叶吸附容量的1.83倍,吸附性能的提升主要归因于比表面积、孔容及表面酸性基团增大的作用.经真菌预处理调控的炭材料对甲苯的吸附符合Langmuir吸附等温线,属于单分子层吸附.     

磷酸水热预处理制备高比表面积高介孔率活性炭

以锯末为原材料,采用磷酸水热预处理后活化的工艺制备高介孔率活性炭,以比表面积和孔容为评价标准,通过单因素实验探究了酸料比、活化温度、活化时间对活性炭比表面积及总孔容的影响规律,验证了该工艺的可行性.最优条件下所制备的活性炭比表面积为2579 m~2·g~(-1),介孔率达到96.6%,充分说明磷酸水热预处理工艺能够显著提高活性炭介孔孔容占比.亚甲基蓝(MB)吸附实验数据与Redlich-Peterson模型拟合度较好,样本活性炭对MB的吸附为单分子层吸附,最大单层吸附量为618.35 mg·g~(-1),接近于实验测试值632.79 mg·g~(-1),表明该方法制备的活性炭具有良好的MB吸附性能.     

炭化温度对废旧布袋制备活性炭性能的影响及其表征

以水泥厂废旧除尘布袋为原料,KOH为活化剂制备了活性炭.利用热重分析法(TG-DTG)对废旧布袋热解过程进行分析;重点考察了不同炭化温度(400、450、500、550和600℃)对废旧布袋制备活性炭的产率及活性炭的碘吸附值和亚甲基蓝吸附值的影响;同时采用N2吸附等温线对最佳工艺条件制备的活性炭孔隙结构进行了表征.研究结果表明,500℃为最佳炭化温度.最佳炭化温度下制备的活性炭,碘吸附值、亚甲基蓝吸附值和产率分别为1350.72 mg·g-1、97.5 mg·g-1和20.16%.活性炭比表面积高达1228.51 m2·g-1,总孔容达0.7134 cm3·g-1,孔径分布以微孔居多,N2吸附等温线为I型.     

壳聚糖改性污泥活性炭的脱硫脱硝性能

用壳聚糖改性污泥活性炭,测试分析了改性污泥活性炭的脱硫脱硝性能.同时,用N2吸脱附法、电子扫描电镜、傅立叶变换红外光谱及X衍射等技术对改性污泥活性炭进行了表征,研究了改性条件对污泥活性炭脱硫脱硝性能的影响,探讨壳聚糖改性提高污泥活性炭脱硫脱硝性能的机理.结果表明,壳聚糖颗粒物能够较为均匀地分布于污泥活性炭的表面,壳聚糖与污泥活性炭结合良好,孔径也明显减小.壳聚糖与污泥活性炭是通过化学键结合的.改性时间与改性温度均可改变污泥活性炭的BET比表面积和孔容,但改性温度对BET比表面积和孔容的影响更为显著.具有最优孔结构的样品A3的BET比表面积、总孔容及中孔容分别为168.76m·2g-1、0.084cm·3g-1及0.041cm·3g-1.与污泥活性炭相比,改性污泥活性炭的脱硫脱硝性能优于污泥活性炭,这是由于壳聚糖中含氮与含氧官能团,丰富了污泥活性炭表面脱硫脱硝活性基团的种类与数量,利于SO2与NO的吸附氧化;通过适当控制改性条件,也可显著地增加BET比表面积和中孔容,以提高SO2与NO气体的物理吸附,从而提高其脱硫脱硝性能.     

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.     

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.     

Simultaneous removal of ammonium and phosphate by zeolite synthesized from coal fly ash as influenced by acid treatment

Zeolite synthesized from fly ash （ZFA） without modification is not efficient for the purification of NH4＋ and phosphate at low concentrations that occur in real effluents, despite the high potential removal capacity. To develop an effective technique to enhance the removal efficiency of ammonium and phosphate at low concentrations, ZFA was modified with acid treatment and the simultaneous removal of ammonium and phosphate in a wide range of concentration was investigated. It was seen that when compared with untreated ZFA, only the treatment by 0.01 mol/L of H2SO4 significantly improved the removal efficiency of ammonium at low initial concentrations. The behavior was well explained by the pH effect. Treatment by more concentrated H2SO4 led to the deterioration of the ZFA structure and a decrease in the cation exchange capacity. Treatment by 0.01 mol/L H2SO4 improved the removal efficiency of phosphate by ZFA at all initial P concentrations, while the treatment by concentrated H2SO4 （≥0.9 mol/L） resulted in a limited maximum phosphate immobilization capacity （PIC）. It was concluded that through a previous mild acid treatment （e.g. 0.01 mol/L of H2SO4）, ZFA can be used in the simultaneous removal of NH4＋ and P at low concentrations simulating real effluent.