Ni/Fe双金属降解四氯化碳和四氯乙烯的对比试验

以四氯化碳(CT)和四氯乙烯(PCE)为目标污染物,以批试验方法研究Ni/Fe双金属对CT和PCE的还原性脱氯.结果表明:Ni/Fe双金属可有效去除水中的CT和PCE;Ni/Fe双金属对CT和PCE的降解反应均符合准一级反应动力学方程;在相似的反应条件下,Ni/Fe双金属对CT和PCE脱氯的反应速率常数(kobs)之比为1.48和1.67,说明Ni/Fe双金属对CT的脱氯速率要快于对PCE的脱氯速率;Ni/Fe双金属可对PCE完全脱氯,但对CT脱氯过程中产生少量三氯甲烷(TCM).     

零价铁修复受三氯乙烯污染地下水的实验研究

通过批实验和柱实验研究了三氯乙烯（TCE）初始浓度、四氯乙烯(PCE)等对零价铁去除三氯乙烯的影响，并建立了三氯乙烯降解的反应动力学方程。结果表明：（1）零价铁对TCE具有较好的降解效果，反应符合准一级反应动力学方程，表观反应速率常数随TCE浓度的增加而减小；（2）在铁粉充足的条件下，TCE初始浓度对降解效果影响不显著，且TCE去除率皆可达到90%以上；（3）PCE的存在抑制了TCE的脱氯反应。PCE和TCE共存时，TCE的最大去除率仅为64.2%；TCE脱氯反应的表观反应速率明显降低，反应半衰期由TCE单独存在时的6.8～9.7 h增大到66 h～346.5 h。     

不同共代谢基质下四氯乙烯厌氧生物降解研究

分别用葡萄糖、乳酸盐和醋酸盐作为驯化好的厌氧污泥的共代谢基质 ,对四氯乙烯 ( PCE)的降解进行研究。结果表明 ,PCE是通过还原脱氯发生生物降解的。实验的回归结果表明 ,反应均符合一级动力学方程 ;反应速率常数的大小依次为 k乳酸盐 >k葡萄糖 >k醋酸盐 ;以乳酸盐作为共代谢基质时 ,PCE的降解速率较快 ,在实验条件下乳酸盐是最合适的共代谢基质     

共代谢基质强化微生物修复四氯乙烯污染地下水

针对微生物修复地下水中四氯乙烯(tetrachloroethylene,PCE)周期长的问题,通过添加共代谢基质强化微生物修复技术以提高修复速率。以某污水处理厂的厌氧活性污泥为菌种来源,采用振荡培养法进行PCE高效降解菌群的驯化和筛选,对微生物降解PCE的温度、初始pH和PCE初始浓度3种影响因素进行了条件优化;使用甲醇、乙醇、葡萄糖、酵母浸膏以及乳酸钠作为共代谢基质,研究了不同共代谢基质条件下微生物群落对PCE的降解规律,并建立了反应动力学模型。结果表明:在种水平上,梭状芽孢杆菌Clostridium sp. FCB45是优势菌种;PCE初始浓度为1 mg·L-1,pH在中性,温度为30℃,共代谢基质为酵母浸膏时,微生物群落的降解效果最好,PCE降解率可高达96.75%,降解速率常数最高可达0.327 d-1;添加共代谢基质强化的微生物降解过程全部符合一级反应动力学模型。添加共代谢基质的微生物实验结果表明,添加共代谢基质可以有效缩短微生物修复周期,对污染地下水的原位生物修复具有一定的参考价值。     

臭氧氧化法处理焦化废水生化出水的反应动力学简

对臭氧氧化去除焦化废水生化出水COD的反应动力学及其影响因素进行了实验研究，结果表明，在臭氧投加量为8.50 mg/min，反应温度为20℃和初始pH为10.61条件下，对COD的降解符合表观一级反应动力学模型，其相关系数R²=0.9991，表观反应速率常数k_Abs=1.01×10^-3 s^-1。该条件下，臭氧氧化对COD的降解主要来源于高活性羟基自由基的强氧化作用。在不同的臭氧投加量（4.25~12.75 mg/min）、不同的反应温度（10~40℃）和不同的初始pH（3.76~12.53）下，COD的降解也同样遵循一级反应动力学规律。随着臭氧投加量的增大，COD降解的表观反应速率常数从（0.554×10^-3） s^-1增加到（1.06×10^-3） s^-1；随着反应温度的升高，表观反应速率常数从（0.427×10^-3） s^-1增加到（1.40×10^-3） s^-1，温度越高反应速率提高的幅度却越小；在初始pH3.76~10.61范围内，表观反应速率常数从（0.218×10^-3） s^-1增加到（1.01×10^-3） s^-1，在初始pH为12.53时表观反应速率常数下降到（0.857×10^-3） s^-1。     

不同共代谢基质对四氯乙烯的厌氧生物降解研究

用驯化好的厌氧污泥对葡萄糖、乳酸盐和醋酸盐作为电子供体时四氯乙烯(PCE)的降解进行研究。实验结果表明,PCE是通过还原脱氯发生生物降解的。实验的回归结果表明,反应均符合一级动力学反应速率,常数的大小依次为k乳酸>k葡萄糖>k醋酸。表明乳酸盐作为电子供体时PCE的降解速率较快,说明在实验条件下乳酸盐是最合适的电子供体。并且在整个实验过程中由共代谢基质提供的电子供体不是PCE降解的限制因素。     

粉煤灰沸石负载Ce3+/TiO2光催化降解水中的菲和荧蒽

以钛酸四丁酯为前驱体，粉煤灰合成沸石为载体，采用溶胶-凝胶方法，在低温条件下制备了稀土铈掺杂的TiO₂光催化剂。利用SEM-EDS、XRD、FTIR对催化剂进行了分析和表征。以高压汞灯为灯源，对多环芳烃菲、荧蒽的降解进行了研究。实验考查了稀土铈掺杂质量分数、催化剂用量、溶液pH、目标物初始质量浓度等因素对光催化降解的影响，研究了其光降解动力学。结果表明，当稀土铈含量为0.5%，催化剂用量为3 g/L，pH偏碱性时，催化效果最佳。光催化反应符合Langmuir-Hinshelwood 动力学规律，菲、荧蒽的降解过程符合一级反应动力学，反应速率常数分别为0.0126 min^-1，0.0099 min^-1。     

自养反硝化菌对硝酸盐氮去除动力学及影响因素研究

为更经济有效地去除污水中的硝酸盐，从兼性污泥中分离获得6株能氧化单质硫和还原硝酸盐的自养反硝化菌。根据各菌株的降解曲线筛选出优势菌种N-I，并研究影响菌株N-I降解性能的环境因素，如pH、温度、碳源及硝酸盐的降解动力学。实验表明，菌株N-I对硝酸盐的降解符合一级反应动力学方程，反应的半衰期t_1/2为1.42 h，反应速率常数为0.488 h^-1。最佳反应pH=7，最佳反应温度为30℃，最佳NaHCO₃浓度为大于或等于2.5 g/L。     

UASB反应器对芳香族化合物反硝化降解特性研究

以苯、联苯和萘为模型化合物，研究了上流式厌氧污泥床反应器(UASB)在反硝化连续流运行条件下对含上述污染物废水的处理效果，并以葡萄糖为补充碳源，考察了COD/NO^-₃-N(简称C/N)比对有机物反硝化降解特性的影响。研究结果表明，当进水COD浓度约为900 mg/L，苯、联苯和萘总浓度约为60 mg/L，NO^-₃-N为20～60 mg/L时，UASB反应器能够在硝酸盐还原条件下稳定去除废水中有机污染物，其中COD平均去除率可达到85%，苯、萘和联苯平均去除率分别为90%、81%和71%。3种芳香烃反硝化降解速率顺序为苯>萘>联苯。 C/N比对苯的降解影响不十分显著，在C/N为5～30范围内，苯的去除率稳定在87%～92%；萘和联苯去除率受C/N影响较大，在C/N比为15时萘和联苯的去除率均达到最大，分别为82%和77%。     

不同共代谢基质对四氯乙烯的厌氧生物降解研究

用驯化好的厌氧污泥对葡萄糖、乳酸盐和醋酸盐作为电子供体时四氯乙烯（PCE）的降解进行研究.实验结果表明,PCE是通过还原脱氯发生生物降解的.实验的回归结果表明,反应均符合一级动力学反应速率,常数的大小依次为k乳酸＞k葡萄糖＞k醋酸.表明乳酸盐作为电子供体时PCE的降解速率较快,说明在实验条件下乳酸盐是最合适的电子供体.并且在整个实验过程中由共代谢基质提供的电子供体不是PCE降解的限制因素.     

Kinetics and mechanism of oxidation of tetrachloroethylene with permanganate

The kinetics, reaction pathways and product distribution of oxidation of tetrachloroethylene (PCE) by potassium permanganate (KMnO4) were studied in phosphate-buffered solutions under constant pH, isothermal, completely mixed and zero headspace conditions. Experimental results indicate that the reaction is first-order with respect to both PCE and KMnO4 and has an activation energy of 9.3+/-0.9 kcal/mol. The second-order rate constant at 20 degrees C is 0.035+/-0.004 M(-1) s(-1), and is independent of pH and ionic strength (I) over a range of pH 3-10 and I approximately 0-0.2 M, respectively. The PCE-KMnO4 reaction may proceed through further oxidation and/or hydrolysis reaction pathways, greatly influenced by the acidity of the solution, to yield CO2(g), oxalic acid, formic acid and glycolic acid. Under acidic conditions (e.g., pH 3), the further oxidation pathway will dominate and PCE tends to be directly mineralized into CO2 and chloride. Under neutral (e.g., pH 7) and alkaline conditions (e.g., pH 10), the hydroxylation pathway dominates the reaction and PCE is primarily transformed into oxalic acid prior to complete PCE mineralization. Moreover, all chlorine atoms in PCE are rapidly liberated during the reaction and the rate of chloride production is very close to the rate of PCE degradation.     

Experimental determination of the kinetic rate law for the oxidation of perchloroethylene by potassium permanganate

Flushing soils contaminated with trichloroethylene (TCE) and perchloroethylene (PCE) with a permanganate (MnO₄⁻) solution has been shown to reduce the solvent content of the soil. Experiments were performed to quantify the rate at which KMnO₄ oxidizes aqueous solutions of PCE over a range of concentrations. In a series of homogeneous reactors, aqueous phase PCE concentrations were monitored over time in nine experimental trials with excess oxidant concentrations ranging from 5 to 30 g/l. Analysis of the data was performed to quantify the oxidation reaction order with respect to PCE and KMnO₄ and the reaction rate constant. The reaction between PCE and KMnO₄ was determined to be first-order with respect to both PCE and KMnO₄ with an overall specific reaction rate coefficient of 2.45±0.65 M⁻¹ min⁻¹.     

Cosolvent-enhanced chemical oxidation of perchloroethylene by potassium permanganate

A laboratory study was conducted to examine cosolvent-enhanced in-situ chemical oxidation (ISCO) of perchloroethylene (PCE) using potassium permanganate (KMnO4). The conceptual basis for this new technique is to enhance permanganate oxidation of dense non-aqueous phase liquids (DNAPLs) with the addition of a cosolvent, thereby increasing DNAPL solubility while avoiding mobilization. Among 17 cosolvent candidates screened, tertiary butyl alcohol (TBA) and acetone were the most stable in the presence of KMnO4, both of which increased PCE aqueous solubility significantly, and therefore are suitable to be used as cosolvent in this study. Batch experiments indicated that the second-order rate constant for PCE oxidation by potassium permanganate was 0.043+/-0.002 M(-1) s(-1) in the purely aqueous (no cosolvent) solution. In the presence of 20% cosolvent (volume fraction=fc=0.2), the rate constant decreased to 0.036+/-0.003 M(-1) s(-1) with TBA and to 0.031+/-0.002 M(-1) s(-1) with acetone. However, in the presence of free-phase PCE, chloride ion concentration from PCE oxidation in acetone/water solutions (fc=0.2) was about twice that in aqueous solutions, indicating that the increase in PCE solubility more than compensated for the decrease in reaction rate constant, such that the oxidation efficiency of PCE was increased with cosolvent. A complete chlorine mass balance was observed in the aqueous system, whereas approximately 70% was obtained in TBA/water or acetone/water (fc=0.2). In soil columns containing residual DNAPL and subjected to isocratic flushing with step-wise increases in f(c) cosolvent, TBA at fc=0.2 resulted in PCE mobilization, whereas acetone at fc相似文献   

多壁碳纳米管结构对复合光催化剂催化效果的影响

采用溶胶凝胶法制备了多壁碳纳米管负载纳米TiO₂的复合光催化剂（TiO₂/MWCNTs），以偶氮类染料甲基橙为目标污染物，在自制的光催化反应器上进行了光催化降解反应实验。主要研究同一甲基橙初始浓度（C₀)下，多壁碳纳米管不同管长和管径对复合光催化剂催化效果的影响。结果表明：该降解反应可用一级反应动力学方程描述，反应速率常数k随着多壁碳纳米管管长和管径的增大而增大；与纯纳米TiO₂相比，复合光催化剂对甲基橙的降解率提高了6％～18％，反应速率常数为前者的1.19～2.11倍；采用复合光催化剂的甲基橙光降解溶液自行沉降分离效果较好，静止沉降60 min后达到沉降平衡，剩余浊度为8.5 NTU，下降了90.6％。     

Quantification of potassium permanganate consumption and PCE oxidation in subsurface materials

A series of laboratory scale batch slurry experiments were conducted in order to establish a data set for oxidant demand by sandy and clayey subsurface materials as well as to identify the reaction kinetic rates of permanganate (MnO(4)(-)) consumption and PCE oxidation as a function of the MnO(4)(-) concentration. The laboratory experiments were carried out with 31 sandy and clayey subsurface sediments from 12 Danish sites. The results show that the consumption of MnO(4)(-) by reaction with the sediment, termed the natural oxidant demand (NOD), is the primary reaction with regards to quantification of MnO(4)(-) consumption. Dissolved PCE in concentrations up to 100 mg/l in the sediments investigated is not a significant factor in the total MnO(4)(-) consumption. Consumption of MnO(4)(-) increases with an increasing initial MnO(4)(-) concentration. The sediment type is also important as NOD is (generally) higher in clayey than in sandy sediments for a given MnO(4)(-) concentration. For the different sediment types the typical NOD values are 0.5-2 g MnO(4)(-)/kg dry weight (dw) for glacial meltwater sand, 1-8 g MnO(4)(-)/kg dw for sandy till and 5-20 g MnO(4)(-)/kg dw for clayey till. The long term consumption of MnO(4)(-) and oxidation of PCE can not be described with a single rate constant, as the total MnO(4)(-) reduction is comprised of several different reactions with individual rates. During the initial hours of reaction, first order kinetics can be applied, where the short term first order rate constants for consumption of MnO(4)(-) and oxidation of PCE are 0.05-0.5 h(-1) and 0.5-4.5 h(-1), respectively. The sediment does not act as an instantaneous sink for MnO(4)(-). The consumption of MnO(4)(-) by reaction with the reactive species in the sediment is the result of several parallel reactions, during which the reaction between the contaminant and MnO(4)(-) also takes place. Hence, application of low MnO(4)(-) concentrations can cause partly oxidation of PCE, as the oxidant demand of the sediment does not need to be met fully before PCE is oxidised.     

Effect of metal ions and humic acid on the dechlorination of tetrachloroethylene by zerovalent iron

The dechlorination of tetrachloroethylene (PCE) by zerovalent iron (Fe(0)) in the presence of metal ions and humic acid was investigated. In the absence of metal ion and humic acid, 64% of the initial PCE was dechlorinated after 125 h with the production of ethane and ethene as the major end products. The dechlorination followed pseudo-first-order kinetics and the normalized surface rate constant (k(SA)) for PCE dechlorination was (3.43+/-0.61)x10(-3)lm(-2)h(-1). Addition of metal ions enhanced the dechlorination efficiency and rate of PCE, and the enhancement effect followed the order Ni(II)>Cu(II)>Co(II). The k(SA) for PCE dechlorination in the presence of metal ions were 2-84 times higher than that in the absence of metal ions. X-ray photoelectron spectroscopy (XPS) showed that Cu(II) and Ni(II) were reduced by Fe(0) to zerovalent metals, and resulted in the formation of bimetallic system to accelerate the dechlorination reaction. On the contrary, humic acid out-competed the reactive sites on iron surface with PCE, and subsequently decreased the dechlorination efficiency and rate of PCE by Fe(0). However, the reactivity of Fe(0) for PCE dechlorination in the presence of metal ions and humic acid increased by a factor of 3-161 when compared to the iron system containing humic acid alone. Since humic acid and metal ions are the most often found co-existing compounds in the contaminated aquifers with chlorinated hydrocarbons, results obtained in this study is useful to better understand the feasibility of using Fe(0) for long-term application to the remediation of contaminated sites.     

Amendment of hydroxyapatite in reduction of tetrachloroethylene by zero-valent zinc: its rate enhancing effect and removal of Zn(II)

The effects of hydroxyapatite (HAP) on dechlorination of tetrachloroethylene (PCE) by zero-valent zinc (ZVZ) were examined in batch systems. PCE was primarily transformed to trichloroethylene by ZVZ, with 1,2-trans-dichloroethylene representing a minor product. Dechlorination of PCE was accelerated by the presence of HAP, and the pseudo-first order rate constants increased with increasing amount of HAP. Zn(II), mostly generated from oxidative dissolution of ZVZ by PCE, was effectively removed from the solution by HAP. Ion substitution, coprecipitation, and adsorption are proposed as the possible mechanisms for Zn(II) removal. These reactions appeared to occur simultaneously and the contribution of each reaction to overall removal of Zn(II) was primarily dependent on HAP loading at constant ZVZ loading. The results indicate that the use of HAP in combination with conventional zero-valent metals is promising in that it can achieve both degradation of organic contaminants and stabilization of inorganic contaminants.     

Batch reactor kinetic studies on the reductive dechlorination of chlorinated ethylenes by tetrakis-(4-sulfonatophenyl)porphyrin cobalt

Tetrakis-(4-sulfonatophenyl)porphyrin cobalt was identified as a highly-active reductive dechlorination catalyst for chlorinated ethylenes. Through batch reactor kinetic studies, degradation of chlorinated ethylenes proceeded in a step-wise fashion with the sequential replacement of Cl by H. For perchloroethylene (PCE) and trichloroethylene (TCE), the dechlorination products were quantified and the C₂ mass was accounted for. Degradation of the chlorinated ethylenes was found to be first-order in substrate. Dechlorination trials with increasing catalyst concentration showed a linearly increasing pseudo first-order rate constant which yielded rate laws for PCE and TCE degradation that are first-order in catalyst. The dechlorination activity of this catalyst was compared to that of another water-soluble cobalt porphyrin under the same reaction conditions and found to be comparable for PCE and TCE.     

一株产絮酵母菌废菌体对Cd2+的吸附特性

将一株产絮酵母菌(编号B-02号)发酵后的废菌体制成生物吸附剂,研究该生物吸附剂对废水中Cd2+的生物吸附特性。结果表明:(1)pH值对Cd2+会产生较大的影响,偏酸性(pH=4～6)条件利于吸附;该吸附剂对Cd2+吸附速率较快,8～10 min就可达到吸附平衡;(2)吸附剂的吸附动力学符合二级动力学模型,吸附Cd2+的实验数据对Langmuir等温式的拟合情况良好,吸附剂吸附Cd2+的最大吸附量为70.752 mg/g。用0.5 mol/L HNO3对吸附Cd2+的酵母菌进行解吸,解吸率可达89.7%。