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.     

高比表面生物质炭的制备、表征及吸附性能

以废弃生物质互花米草与棉秆为原料,采用KOH活化制备了高比表面积微孔生物质活性炭.研究了原料类别、浸渍比、炭化温度及保温时间对炭组成与吸附性能的影响,利用氮气吸附、X-射线衍射、红外光谱FT-IR、扫描电子显微镜SEM等技术对活性炭表面物化性质进行了分析,并通过BET方程、DFT密度函数理论及Horvath-Kawazoe方程对比表面积与孔分布进行了表征测定.结果表明,氢氧化钾活化制备互花米草与棉秆活性炭的适宜条件为浸渍比3:1、活化温度800℃、活化时间1.5 h.在此条件下制得的互花米草活性炭与棉秆活性炭的得率为16.36%和11.22%,BET比表面积高达2 825 m2.g-1和2 135 m2·g-1,孔容积分别为1.374 mg·g-1和1.038 cm3·g-1;孔径分布狭窄,95%的孔集中在3 nm以内.该条件下制备的互花米草与棉秆活性炭吸附性能好,对碘的吸附值分别为1 797 mg·g-1和1 251 mg·g-1,亚甲基蓝吸附值为495 mg·g-1和478mg·g-1,均超过了国家水处理用活性炭一级品标准;2种生物质炭样品对水中2,4-二硝基苯酚的Langmuir最大吸附量分别为932 mg.g-1、747 mg·g-1,均优于普通活性炭与活性炭纤维.     

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.     

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.     

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.     

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.     

响应面法优化制备污泥基活性炭

利用响应面法进行试验设计,选定炭化温度、升温速率、炭化停留时间及保护气体流量为影响因素,对利用污水厂二次污泥制备污泥基活性炭的工艺条件进行优化.通过响应面法得到了污泥基活性炭的碘吸附值与4种因素之间的非线性回归方程,确定了制备污泥基活性炭的最优工艺条件为:炭化温度530℃、升温速率17℃·min-1、炭化停留时间22 min、保护气体流量280 m L·min-1.在最优条件下,制备的污泥基活性炭碘吸附值为675.9 mg·g-1,比表面积为639.5 m2·g-1,平均孔径为4.1 nm,中孔孔径为3~5 nm;羧基、内酯基和酚羟基含量分别为1.625、0.125和0.375 mmol·g-1,更适合吸附大分子污染物和金属离子.     

亚临界水解预处理稻草秸秆制备活性炭及表征

通过以稻草秸秆的亚临界预处理中产生的残渣作为实验材料,以氯化锌作为活化剂制备具有吸附性能的活性炭,研究了活化温度,活化时间,浸渍时间以及浸渍比等4个因素对生成活性炭的性能影响,设计正交实验制备活性炭.以低温液氮吸附测定活性炭的比表面积和孔容、孔径分布,以扫描电子显微镜(SEM)观测活性炭表面形貌,并以亚甲基蓝(MB)作为吸附质,研究了活性炭对亚甲基蓝的吸附动力学和吸附等温线.结果表明,活化温度900℃,活化时间60 min,浸渍比1∶5,浸渍时间12 h,当氯化锌质量分数为20%时,制得相应活性炭的碘值为1 122.79 mg.g-1,亚甲基蓝吸附值为136.50 mg.g-1.亚甲基蓝在活性炭上的吸附基本符合Langmuir方程,且准二级动力学模型能很好地描述活性炭对亚甲蓝的吸附过程;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.     

活化温度对竹柳基活性炭性能及其制备过程中副产物组成的影响

以一种常见的环境修复材料竹柳为原料来制备竹柳基活性炭(WAC),考察了不同活化温度(400、450、500、550、600℃和650℃)对WAC性质及其除污染性能的影响,同时评估了制备过程中气态和液态副产物的生成规律与利用潜能.结果表明,随着活化温度的升高,WAC产率下降,热解油产率上升,而热解气产率相对稳定.六组WAC均具有较高的比表面积(BET),最高可达1526 m2·g-1,但BET值随活化温度的升高呈下降趋势;WAC的碘吸附值和亚甲基蓝吸附值最高可达1122.25 mg·g-1和415.50 mg·g-1,对重金属Pb2+和硝基苯的最大吸附量分别为9.20mg·g-1和4.21 mmol·g-1.WAC制备过程中热解气主要组分为H2、CH4、CO和CO2,随活化温度升高,H2和CH4含量上升,CO2含量下降,热解气的总燃烧热值升高.热解油的组分较为复杂,杂环类、烷烃类、烯烃类和有机酸类有机物含量较高,且随活化温度变化明显,在活化温度为650℃时,热解油的燃烧热最大.     

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.     

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.