Characterization of nanoscale iron and its degradation of 2,4-dichlorophenol

Nanoscale iron was detected by TEM, X-ray diffraction and X-ray photoelectron spectroscopy. It was found that the size of the nanoscale iron particles is in the range of 30–40 nm according to TEM image, and it contains abundant Fe₃O₄ as passivating layers on the surface of the core-shell structure. To improve its performance, dilute HCl was used for the removal of the passivating layers, and the degradation of 2,4-dichlorophenol (2,4-DCP) was measured for the nanoscale iron samples treated and untreated. Experimental results demonstrated that the removal of 2,4-DCP by untreated nanoscale iron is mainly due to the adsorption of 2, 4-DCP by nanoscale iron, and there are no degradation products detected by HPLC in the process. However, excellent dechlorination of 2,4-DCP was gained by HCl-treated nanoscale iron, and 2-chlorophenol, 4-chlorophenol and phenol were detected during the process. It was concluded that dechlorination is the key reaction pathway for the degradation of 2,4-DCP by activated nanoscale iron, and phenol is found to be the main product.     

Catalytic Decomposition of Chlorophenols Using Fiber-supported Cobalt Phthalocyanine

A novel heterogeneous catalyst, viscose fiber-supported cobalt phthalocyanine (Co-TDTAPc-F),was prepared by immobilizing cobalt tetra(2,4-dichloro-1,3,5-triazine)aminophthalocyanine (Co-TDTAPc) on viscose fibers covalently. The oxidative removal of chlorophenols such as 2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6-trichlorophenol was investigated in the catalytic oxidative system of Co-TDTAPc-F/H2O2. Furthermore, more than 98% of these chlorophenols were decomposed in 4h. Phenol, oxalic aci...     

纳米Fe/Ni双金属的制备及其对水中2,4-二氯酚的还原效果

 采用液相还原法制备了纳米Fe/Ni双金属材料,分析了FeCl₂浓度、n（Ni）/n（Fe）和n（NaBH₄）/n（FeCl₂）物质的量之比对制得的Fe/Ni双金属还原水中2,4-二氯酚（2,4-DCP）效果的影响,明确了Fe/Ni对2,4-DCP的还原脱氯途径。结果表明：在FeCl₂浓度为3 mol/L、n（Ni）/n（Fe）=4%,n（NaBH₄）/n（FeCl₂）=1的条件下制备的Fe/Ni双金属对2,4-DCP的去除率接近100%,且其中95%被还原成苯酚。纳米Fe/Ni为球形颗粒,粒径约为50 nm,在自身磁力作用下相互链接为枝状,又通过静电稳定作用分散聚集,形成海绵状多孔结构,BET比表面积为44.8 m²/g。纳米Fe/Ni还原2,4-DCP的途径主要是苯环上的2个C-Cl键依次被加氢还原,先脱去一个氯生成2-氯酚或4-氯酚,再进一步脱氯转化为稳态的苯酚。     

日光/草酸铁络合物/H2O2降解水中2,4-二氯苯酚

以日光作光源 ,Fenton 草酸铁络合物为光氧化剂 ,对水中 2 ,4 -二氯苯酚进行了光氧化降解试验研究。结果表明 :草酸铁络合物 /H2 O2 光氧化降解 2 ,4 -二氯苯酚的速率显著高于Fenton试剂 ,前者的光解初始速率大约是后者的 4倍 ;溶液 pH值对光氧化有很大影响 ,pH值在 3左右 ,2 ,4 -二氯苯酚的光降解脱氯的效果较佳 ,pH超过 4 ,光降解脱氯效率明显下降 ;在晴天和多云日照下草酸铁络合物 /H2 O2 光氧化降解有机物的速率很快 ,在阴天的光解速率相对较慢 ,但效率仍然很高     

纳米Fe/Ni催化降解2,4-二氯酚的机理及过程中参数变化

采用液相还原法制备了纳米Fe/Ni双金属材料,分析了其催化降解2,4-二氯酚的机理、降解过程中Ni的作用及相关参数变化。结果表明,2,4-二氯酚被纳米Fe/Ni降解的主要途径是2,4-二氯酚直接被脱去2个氯原子生成苯酚,此外也可先脱去一个氯原子生成2-氯酚或4-氯酚,然后继续脱氯生成苯酚;纳米Ni可将纳米Fe腐蚀产生的氢气转化为活性氢原子,活性氢原子再对2,4-二氯酚进行脱氯降解。在反应初期,溶液氧化还原电位及溶解氧浓度快速降低,pH及溶解铁浓度急剧升高,随着反应的进行,上述各参数值趋于稳定。     

生物膜电极法降解2,4-二氯苯酚

以2,4-二氯苯酚（2,4-DCP）为目标污染物, 在隔膜式电解槽中研究不同离子交换膜对生物膜电极法处理2,4-DCP的影响. 结果表明: 阴离子交换膜有利于2,4-DCP在生物膜电极上的转化及去除中间产物; 生物膜电极保存的时间越长, 其对2,4-DCP的降解效果越差, 生物膜电极的使用寿命逐渐下降.     

漆酶催化降解氯酚类有机污染物

采用漆酶为催化剂,研究2,4－二氯酚、4－氯酚和2－氯酚的催化降解机理,探讨了反应时间、pH值、反应温度、氯酚浓度以及漆酶浓度对其降解效果的影响和最适降解条件。结果表明,漆酶催化氧化2,4－二氯酚的能力最强,其降解率10h内达到94%,4－氯酚为75%,2－氯酚为69%。2,4－二氯酚发生反应的最适pH值在5.2～6.0之间,4－氯酚在5.5附近,2－氯酚在4.5～5.5之间。漆酶对氯酚的降解率随着漆酶浓度、反应温度的升高而增大,但随着氯酚浓度的升高,不同氯酚的变化趋势并不相同。漆酶降解2,4－二氯酚的反应属于一级反应,反应活化能约为44.8 kJ·mol^-1。另外,利用戊二醛交联壳聚糖制成载体来固定化漆酶,固定化漆酶的活性虽低于自由漆酶,但稳定性明显增强,连续6d用其降解2,4－二氯酚,6h降解率始终在60%以上。     

活性炭对2,4-二氯苯酚的催化臭氧化降解(英文)

研究了粒状活性炭(GAC)对2,4-二氯苯酚(2,4-DCP)臭氧化降解的催化性能。由于活性炭的吸附和催化作用,提高了2,4-DCP的分解。在酸性条件下具有较高的催化臭氧化效率,而酸性和碱性的强弱对2,4-DCP的分解几乎没有影响。活性炭的重复使用实验表明活性炭在臭氧化处理过程中可以得到原位再生,多次使用后其催化活性几乎没有降低。     

2,4,6-三氯苯酚废水处理过程对污泥性能和菌群结构的影响

为考察2,4,6-三氯苯酚（2,4,6-TCP）废水处理过程对污泥性能和菌群结构的影响,利用序批式生物反应器（Sequencing Batch Reactor,SBR）处理2,4,6-TCP模拟废水,通过逐步提高进水2,4,6-TCP浓度（10-50 mg/L）的方式进行试验。结果表明,经10 mg/L 2,4,6-TCP驯化的活性污泥可有效降解进水化学需氧量（Chemical Oxygen Demand,COD）和2,4,6-TCP,提高进水2,4,6-TCP浓度基本不影响污泥性能。当处理不同浓度的进水2,4,6-TCP的SBR处于稳定运行阶段末期时,污泥絮体中多糖和蛋白质含量随进水2,4,6-TCP浓度的提高而升高,脱氢酶（Dehydrogenase,DHA）、过氧化氢酶（Catalase,CAT）和超氧化物歧化酶（Superoxide Dismutase,SOD）的活性同样随进水2,4,6-TCP浓度的提高而升高。经2,4,6-TCP驯化的污泥中降解2,4,6-TCP的功能菌属显著富集,虽然不同浓度的进水2,4,6-TCP和不同的SBR运行阶段影响微生物多样性,但不同污泥中的微生物菌属具有一定的相似性。因此,通过逐步提高进水2,4,6-TCP浓度的方式驯化污泥可实现废水中2,4,6-TCP的有效去除。本研究的实施可为氯酚废水及其他难降解工业废水的处理提供科学指导。     

Dechlorination of 2,4-dichlorophenol by nickel nanoparticles under the acidic conditions

Metal nanoparticles are effective for remediation of contamination with a range of compounds including chlorinated organics.However,the sorption process of the passivation oxide layers on the metal nanoparticle surfaces may result in incomplete degradation of contaminants.This phenomenon can be prevented by an acidic washing procedure or reaction in an acidic medium.In this paper,nickel nanoparticles manufactured via the carbonyl powder process were analyzed using scanning electron microscopy,transmission electron microscopy,X-ray diffraction and energy-dispersive X-ray spectroscopy.The sorption and degradation of 2,4-dichlorophenol (2,4-DCP) by nickel nanoparticles under acidic conditions was then investigated.Transmission electron microscopy and XRD results showed that the nickel nanoparticles range in size from 10 to 20 nm,and a thin passivation layer of NiO is present on the surface.This oxide layer can be removed by pretreatment washing with acidic solutions.It was indicated that dechlorination was the key reaction pathway for degradation of 2,4-DCP by nickel nanoparticles under acidic conditions.The main degradation products were 4-Chlorophenol,2-Chlorophenol,and Phenol,and among these,Phenol was dominant.The acidic medium promoted degradation by providing an appropriate pH,and H+ may be involved in the reaction.Dechlorination of 2,4-DCP by nickel nanoparticles under the acidic condition follows the second order kinetic model,and the rate constants at 298,306,316 K are 0.02,0.2 and 0.3 (g L h)-1,respectively.     

Sol-gel法固定化漆酶处理氯酚类污染物

以2,4-二氯酚(2,4-DCP)和2,4,6-三氯酚(2,4,6-TCP)为代表,采用Sol-gel法固定化漆酶处理氯酚类污染物.结果表明:底物初始浓度为0.5 mmol/L,固定化漆酶投加量为7 g/L,反应3 h后DCP去除率可达95.3%,而反应2 h后TCP去除率可达99.6%.TCP和DCP去除过程可以用米氏方程描述,其米氏常数Km值分别为11.72和9.97 mmol/L,因此固定化漆酶对TCP的亲和力高于DCP,这导致了在反应时间、初始浓度、固定化酶投加量以及底物共存等因素变化后两者去除效果上的差异.连续48 h的运行数据和酶活损失表明固定化漆酶具有较好的反应稳定性.     

Degradation of organic pollutants by a Co3O4-graphite composite electrode in an electro-Fenton-like system

A novel composite electrode was constructed by pressing together Co3O4 and graphite and it was used as the cathode in an electro-Fenton-like (EFL) system. The poor electron transport characteristic of Co3O4 was overcome by incorporating graphite. In situ electro-catalytic generation of hydroxyl radicals (·OH) occurred at high current efficiencies from pH 2-10, extending the traditional Fenton reaction pH range. Cyclic voltammetry and AC impedance spectrometry were used to characterize the composite electrode. The ability of the EFL system to degrade organic compounds was investigated using sulforhodamine B (SRB) and 2,4-dichlorophenol (2,4-DCP) as probes. Decoloration of SRB (1.0×10-5 mol/L) was complete (100%) in 150 min and SRB was effectively degraded from pH 2-10. The decomposition of SRB was studied using Fourier transform infrared spectroscopy (FT-IR) and total organic carbon (TOC) analysis and results indicated that the final degradation products were carbon dioxide, carboxylic acids and amines. The EFL system also decomposed 2,4-DCP and the degradation was 98.6% in 240 min. Electro-catalytic degradation of SRB occurs by a ·OH mechanism. After 5 times reused, the degradation rate of SRB did not significantly slow down. The electrode shows excellent potential for use in advanced oxidation processes (AOPs) used to treat persistent organic pollutants (POPs) in wastewater.     

UV—C辐照降解水中2，4，6-三氯酚

采用uV—C辐照降解水中2,4,6-三氯酚（2,4,6-TCP）,考察了UV光强、2,4,6-TCP初始浓度、反应液pH值、水中阴离子和阳离子对降解效果的影响．结果表明：UV—C辐照降解2,4,6-TCP符合拟一级反应动力学,在光强为142“W·cm^（-2）,2,4,6-TCP初始浓度为1mg·L^（-1）条件下,辐照120min后2,4,6-TCP的去除率达到76．89％．通过增大紫外光强和减小2,4,6-TCP初始浓度,可提高反应速率和2,4,6-TCP去除率．碱性条件更利于Uv_c辐照降解2,4,6-TCP．水中各种离子的存在对2,4,6-TCP的光解速率有较大的影响,其中SO。”,HCO3-,CO3^（2-）和Fe^（3＋）对反应起促进作用,Fe^（3＋）促进效果最明显．     

非线性Kalman滤波同时测量难分辨双组分有机氯酚混合体系

提出了邻氯苯酚与2,4_二氯苯酚混合体系非线性吸光度表示式．非线性吸光度由2组分各自对吸光度的贡献和由于混合而导致的2组分各自贡献的改变以及交互作用项3部分构成．依据该式,利用非线性Kalman滤波法处理了42组邻氯苯酚与2,4_二氯苯酚的标准混合溶液在260～300nm区间的紫外光谱数据,在混酚的标准溶液中酚的质量浓度均在0．1～15mg／L范围内．利用偏最小二乘法,将其制作成扩展Kalman滤波标准工作系数矩阵．通过对非线性吸光度关系式Taylor级数展开进行线性化处理,得到其向量函数的Jacobi矩阵,从而完成了非线性Kalman滤波器的设置．回收实验显示,扩展Kalman滤波同时测量邻氯苯酚与2,4-二氯苯酚双组分体系是准确、稳定的．     

Pd修饰Ti电极上2-氯酚的电催化还原

采用循环伏安法和交流阻抗法研究了碱性水溶液中Pd修饰Ti电极对2-氯酚（2-CP）的电催化还原特性,考察了Pd的沉积时间和甲酸钠对2-CP脱氯效率的影响。研究表明：2-CP在还原过程中属准可逆反应,且由电荷传质与扩散过程混合控制,Pd沉积300s时的催化性能最好,甲酸钠能够促进2-CP的脱氯反应。     

苯、氯苯及酚、氯酚对大鳞副泥鳅（ParamisgurnusdabryanusSauvage）鱼苗的急性毒性效应

为扩充水生生物的毒性试验材料，用人工催产的方法在不同的季节获得大鳞副泥鳅鱼苗，并用苯、氯笨、酚、氯酚对其进行静止式急性毒性试验，４８小时苯，氯苯，１．３－二氯苯，１．４－二氯苯及六氮苯的ＬＣ＿（５０）值分别为１５６．７、１２．２７、４．９５及２．０７ｍｇ／Ｌ．酚、３－氯酚，２．４－二氯酚的毒性分别为３６．５、１４．２２．７８及０．１ｍｇ／Ｌ，与其它鱼类现有毒性试验资料比较，其敏感性基本相似，在全年中可代替其它鱼类进行急性毒性试验。     

长角血蜱性信息素生物合成的激素调控

用气相色谱和高效液相色谱分别对长角血蜱雌蜱盾窝腺中性信息素２，６－二氯酚含量和整体蜕皮激素２０－羟基蜕皮酮含量进行了测定。结果表明，雌蜱２，６－ＤＣＰ生物合成开始于由若早蜕出后５ｄ，之后其含量增加并在盾窝腺中沉积，吸血前后达到高峰，吸血后３ｄ开始下降，但吸血后３－５ｄ内保持在一恒定水平，此期内２，６－ＤＣＰ释放以吸引雄蜱，吸血后７ｄ即交配后含量急剧下降，饱血后下降为零。     

介孔SiO2固定化漆酶降解2,4DCP

以M-NH2-SiO2为载体,戊二醛为交联剂制备固定化漆酶,研究2,4-DCP(2,4-二氯苯酚)浓度、溶液酸度、温度对固定化漆酶降解2,4-DCP的影响.结果表明,固定化漆酶降解2,4-DCP最佳条件为:当2,4-DCP质量浓度为5mg.L-1,溶液pH为5.5,温度为30℃时,降解去除率为42.28%.固定化漆酶具有最大活性时的溶液pH值相比于自由酶的最佳pH向碱性偏移;与自由漆酶相比,固定化漆酶有良好的稳定性和重复使用性.     

粉末活性炭吸附2,4,6三氯酚的性能研究

针对粉末活性炭PAC吸附2,4,6-三氯酚(2,4,6-TCP)的性能进行了研究.考察了PAC炭种、投加量和温度3因素对2,4,6- TCP吸附效果的影响;建立了吸附动力学、等温吸附线以及吸附热力学模型;研究了PAC与预氧化联用技术对2,4,6- TCP的协同去除作用.结果表明,上述3个因素对2,4,6-TCP吸附效果影响均显著,其中PAC投加量的影响最大,PAC炭种其次,温度的影响最小.PAC可以快速有效地吸附水中的2,4,6-TCP,快速吸附期在前20 rmin,吸附容量可达到80％以上.拟二级动力学模型和Freundlich吸附等温线模型可分别较好地描述PAC对2,4,6-TCP的吸附行为.PAC吸附2,4,6-TCP的过程为自发、放热以及熵减的过程.PAC与预氧化联用技术可以提高对2,4,6-TCP的处理效果.     

A gas chromatography/mass spectrometry method for the simultaneous analysis of 50 phenols in wastewater using deconvolution technology

Phenolic compounds exist widely in the influents and effluents of sewage treatment plants (STPs) and most are un-regulated. In this study, a gas chromatography-mass spectrometry (GC-MS) method for the simultaneous analysis of 50 phenolic compounds in wastewater was developed. Deconvolution technology was used to identify contaminants that are covered by co-extracted materials. A mass spectral library containing all 50 silylated phenolic compounds was first established and used for deconvolution. Twelve typical phenolic compounds were selected to optimize the sample preparation procedures. Solid-phase extraction using a C18 cartridge coupled with an HLB cartridge was used for pre-concentration and dichloromethane was used for elution. The solutes were derivatized and analyzed by GC-MS. The blank and matrix spike recoveries ranged from 57.46% to 136.4% and 47.87% to 114.8%, respectively. Method detection limits ranged from 3.64 to 97.64 ng L⁻¹. The relative standard deviations of all the recovery experiments were lower than 13.6%. The instrument limits of quantification ranged from 0.7 to 87.7 pg. The method has been applied to analyze the influents and effluents of 5 Chinese STPs. Except for regulated phenolic compounds (phenol and 2,4,6-trichlorophenol), three un-regulated phenolic compounds, including 2-chlorophenol, 2,5-dichlorophenol and 2,4-dichloro-3-ethyl-6-nitrophenol were identified in the effluent wastewater. The detected concentrations of un-regulated phenolic compounds could possibly cause environmental effects, indicating that immediate attention is required to prevent complications.