污泥基活性炭去除水中重金属离子效能与动力学研究

以城市污泥为主要原料制备了污泥基活性炭(SAC),考察了其对重金属离子的吸附去除效能和吸附动力学规律.并选择了2种商品活性炭(煤质炭,MAC和椰壳炭,YAC)作为对比,以初始浓度为50mg/L的Cu(II),Pb(II),Cd(II),Cr(VI)4种重金属离子为去除对象,分别进行了3种活性炭的表面理化性质分析及其对4种重金属离子的吸附试验.结果表明,SAC的比表面积和微孔容积仅为YAC和MAC的1/3~1/2,吸附速率也相对较慢,但其对Cu(II),Pb(II),Cr(VI),Cd(II)的平衡吸附量却远大于2种商品活性炭,分别为9.9,8.9,8.2,5.4mg/g,说明SAC表面的高酸性基团含量对重金属离子的吸附起到了关键作用;Langmuir与Freundlich吸附等温模型均能较好地拟合SAC对Cu(II)和Pb(II)的吸附,SAC对Cr(VI)的吸附过程更符合Langmuir模型,而SAC对于Cd(II)的吸附过程用Langmuir与Freundlich两个模型均不能较好地拟合,说明SAC表面缺少能够与Cd(II)发生反应的结合位点.     

酸碱改性活性炭及其对甲苯吸附的影响

分别用酸溶液(H_2SO_4、HNO_3、H_3PO_4)和碱溶液(NaOH或NH_3·H_2O)浸渍方法对活性炭进行改性,并对酸改性活性炭进行碱溶液二次改性处理,通过表征改性前后活性炭BET比表面积、孔结构、表面官能团等理化特征和测定其对甲苯蒸气的饱和吸附量,研究了影响活性炭吸附甲苯蒸气的关键因素.结果表明,酸改性使BET比表面积、微孔面积、微孔容积减少、表面酸性官能团增加,而碱改性呈现相反的理化特征变化.活性炭理化特征的变化可能与改性溶液的酸碱性、氧化还原性有关,并且这种相反的变化直接关系到活性炭对甲苯蒸气的吸附.3种酸改性的活性炭对甲苯蒸气饱和吸附量相对于原活性炭减少9.6%~20.0%,而两种碱改性的活性炭则增加29.2%~39.2%.相关性分析显示甲苯吸附量与BET比表面积、微孔面积、微孔容积正相关,而与表面酸性官能团负相关;多元回归分析进一步表明微孔容积和酸性官能团数量是影响活性炭甲苯吸附的关键因素.二次改性活性炭甲苯吸附量与表面含氧酸性官能团拟合结果则表明,—COOH、C＝O和—OH都对活性炭甲苯吸附能力有影响,其中—COOH影响较大.研究结果表明有效提高活性炭对甲苯吸附能力,改性宜以提高活性炭微孔容积和减小活性炭表面酸性官能团数量,特别是—COOH数量为目标导向.     

秸秆污泥基活性炭的制备及吸附H2S的实验研究

以市政污泥和玉米秸秆的混合物为原材料,KOH为活化剂,制备了秸秆污泥基活性炭(AC).实验考察了秸秆与污泥用量比例,以及活化剂用量对秸秆污泥基活性炭物化特性的影响.结果显示,m(污泥)∶m(秸秆)∶m(KOH)为3∶7∶2的条件下,制备的活性炭C372以微孔为主,微孔率达到0.59,比表面积达到369.271 m2·g-1.该活性炭的穿透硫容与饱和硫容均最高,分别为5.82 mg·g-1(以H2S计)和7.00 mg·g-1(以H2S计),活性炭表面内酯基的存在不利于其对硫化氢的吸附.SEM和BET表征分析显示,随着秸秆在污泥中比例的增加,活性炭比表面积增大,对H2S的吸附量提高.活性炭C372具有较好的再生性能,二次再生后其穿透硫容与饱和硫容均能恢复55%以上.     

活性炭孔结构和表面化学性质对吸附硝基苯的影响

通过对活性炭HNO3氧化及随后的N2:气氛中热处理,研究了活性炭性质对其吸附硝基苯性能的影响.以低温液氮(N2/77K)吸附测定活性炭的比表面积和孔容、孔径分布,以SEM观测活性炭表面形貌,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变化.结果表明, HNO3氧化可以显著改变活性炭表面化学性质,增加活性炭表面酸性含氧官能团数量,对活性炭孔隙结构影响不大.随后N2:气氛中热处理可以造成活性炭表面酸性含氧官能团分解,外表面积增大,微孔烧蚀为中孔.硝基苯在活性炭上的吸附基本符合Langmuir方程,改性后活性炭对硝基苯的吸附容量明显改变, ACNO-T、ACraw、ACNO吸附容量分别为1011.31、483.09、321.54 mg·g-1.较大的外表面积、适宜数量的中孔以及较少的酸性含氧官能团是ACNO-T对硝基苯表现出较高吸附容量的主要原因.     

MnO2改性累托石/污泥生物炭复合材料的制备及其对Pb(Ⅱ)和Cd(Ⅱ)吸附特性研究

为提高累托石/污泥生物炭复合材料的吸附特性,在通过混合热解法制备的累托石/污泥生物炭复合材料的基础上,利用氧化还原反应制备得到MnO_2改性的累托石/污泥生物炭复合材料,对改性前后的复合材料进行了表征和吸附特性研究。结果表明:MnO_2改性的累托石/污泥生物炭复合材料的比表面积以及微孔和介孔的数量远高于未改性的复合材料,改性复合材料中的MnO_2是无定形的且材料表面含有丰富的含氧官能团;改性后的复合材料对Pb(Ⅱ)和Cd(Ⅱ)的吸附量远高于未改性的复合材料,其吸附过程受pH值的影响较大;该改性复合材料对Pb(Ⅱ)和Cd(Ⅱ)的吸附动力学和等温线分别符合Elovich模型和Langmuir等温线方程,其吸附热力学分析结果表明该改性复合材料对Pb(Ⅱ)和Cd(Ⅱ)的吸附过程是自发的吸热过程,且混乱度增加。可见,MnO_2改性的累托石/污泥生物炭复合材料是一种具有潜力的重金属吸附剂。     

活性炭纤维的改性及对Cu~(2+)吸附性能影响的研究

采用硝酸、磷酸、磷酸二氢铵和硝酸铜水溶液对聚丙烯腈基活性炭纤维(PAN-ACF)进行浸渍改性,制备了4种改性活性炭纤维(ACF1-ACF4)。测定了改性活性炭纤维表面含氧酸性官能团、零电荷点、比表面积和孔容,评价了改性纤维对铜离子的吸附性能。结果表明改性后活性炭纤维表面含氧酸性官能团明显增加,其零电荷点相应降低,比表面积和微孔孔容增大。改性活性炭纤维对Cu2+的吸附容量显著提高,其中ACF2吸附性能最佳,其吸附容量从改性前的4.80 mg/g增加到17.32 mg/g,提高了3.6倍。     

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.     

污泥基活性炭的制备、表征及其应用

以城市生活污水厂脱水车间污泥为原料,采用化学活化法(ZnCl2为活化剂)在活化剂浓度为45%、活化温度为600℃、浸渍温度为45℃、活化时间为50min条件下制备污泥基活性炭。对污泥基活性炭进行了孔结构、扫描电镜(SEM)、红外光谱(FTIR)、XRD等表征分析。结果表明:该条件下制备出的污泥基活性炭碘吸附值为427.51mg/g,比表面积为329.48m2/g,大孔、中孔、微孔容积分别为0.19,0.12,0.15cm3/g。平均孔径为3.953nm。将其应用于生活污水处理,考察了污泥基活性炭投加量、pH、吸附时间对其吸附性能的影响。     

污泥制备活性炭过程中重金属含量的变化趋势

对采集的两类污泥(城市污泥、制药污泥)及其制备的活性炭进行消解处理,采用火焰原子吸收法对消解液中重金属的含量进行测定,初步探讨了污泥资源化过程中重金属的变化规律。研究结果表明:两类污泥中重金属的含量变化范围很大,其中Zn含量最高,最高值达2859.4mg/kg,其次为Cu、Pb、Cr,Cd最少;除Cr元素外,城市污泥中重金属元素Zn、Cu、Pb、Cd含量普遍高于制药污泥;由污泥烧制的活性炭中重金属含量明显减少,表明污泥烧制成活性炭后Cu、Cr、Pb、Cd更加稳定。     

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.