纳米钯?铝双金属对水中3-氯酚的脱氯降解研究

采用置换沉积法制备了纳米钯/铝双金属催化剂,氢解还原去除水相中难降解有毒有机物3-氯酚(3-CP),考察了溶液pH、钯负载量、纳米钯/铝双金属投加量、反应温度对脱氯效果的影响并解析相关反应机制。结果表明:(1)初始pH 3.0时,沉积液中93.25%(质量分数,下同)～96.67%的钯可有效负载于铝材上。(2)在pH为3.0、纳米钯/铝双金属投加量为2g/L、钯负载量为1.16%(质量分数)、反应温度为25℃下降解初始摩尔浓度为0.389mmol/L的3-CP,反应终了时脱氯率在99%以上。利用纳米钯/铝双金属降解氯代有机污染物具有高效低耗的优势,在实际应用上具有较好的前景。     

Pd/Fe催化脱氯水中PCE的动力学研究

以GC-MS为分析方法,采用Pd／Fe双金属对水溶液中四氯乙烯（PCE）进行了催化还原脱氯处理,考察了PCE初始浓度、钯含量、Pd／Fe用量和溶液初始pH值等各因素对脱氯效果影响及还原动力学规律。结果表明,Pd／Fe双金属对PCE有较好的还原脱氯效率,反应遵循准一级反应动力学规律,以反应物PCE浓度为参照的反应速率常数K变化范围为0．019min^-1～0．16min^-1,对应的PCE半衰期从6min到36min,揭示反应有可能是在过量的Pd／Fe双金属表面进行。当PCE溶液初始浓度为1mmol／L,投加1．2g钯含量为0．03％的Pd／Fe双金属,在25℃下反应60min,PCE的脱氯率达到95％以上。增大钯含量和Pd／Fe用量可有效提高脱氯率,在初始pH值为弱酸性条件下有利于还原脱氯反应进行。     

钯/铝双金属体系对3-氯酚的脱氯降解

研究了钯/铝双金属体系对水相中3-氯酚的催化脱氯降解效果,通过置换沉积制备了钯/铝双金属颗粒,考察了该双金属颗粒的稳定性以及溶液pH和钯负载量对脱氯效果的影响。结果表明,pH在4.0以下的酸性条件,钯负载量在1.43%时,可实现水相中3-氯酚的有效脱氯,反应30 min后0.389 mmol/L的3-氯酚转化率可达99%以上,产物主要为苯酚,而钯/铝颗粒在重复测试中能保持较好的稳定性,这与铝基材表面自发形成的氧化膜有关。钯/铝材料表征的结果表明,钯颗粒高度分散在铝基材表面,并极大地提高了铝基材的表面积,从而有助于后续的脱氯反应。     

微波辅助光催化降解氯酚类污染物的研究

研究了溶液中4-氯酚(4CP)、2-氯酚(2CP)、4-氯-3-甲基酚(4C3MP)、2,4-二氯酚(2,4-DCP)、2,4,6-三氯酚(2,4,6-TCP)和五氯酚(PCP)的微波辅助光催化降解(MW/PCO).结果表明,6种氯酚(CPs)光降解速率与分子中Cl原子取代的数目、位置等分子结构性质有关,单氯酚比多取代氯酚易光解.MW/PCO降解4CP的主要中间产物为苯酚、氯苯、对苯醌、对苯二酚等,降解PCP的主要中间产物为2,3,5,6-四氯对苯醌、2,3,4,6-四氯对苯二酚、四氯酚.CPs降解的机制是紫外光降解和羟基自由基 (·OH)亲电子加成脱氯过程.     

羧甲基纤维素改性纳米钯铁双金属去除水中2,4-二氯苯酚的影响因素及机理

利用液相还原法制备了纳米零价铁(nZVI)、纳米钯铁双金属(Pd/Fe)、羧甲基纤维素(CMC)改性nZVI(CMC-Fe)和CMC改性钯铁双金属(CMC-Pd/Fe)4种铁基纳米材料，并用扫描电子显微镜(SEM)和X射线衍射仪(XRD)对其进行了表征。研究了这4种材料对水中2,4-二氯苯酚(2,4-DCP)的表观去除率，考察了铁基纳米材料投加量、Pd负载量、溶液初始pH及污染物浓度等因素对CMC-Pd/Fe去除2,4-DCP的影响，并探讨了可能的作用机理。结果表明，在4种材料中，CMC修饰的CMC-Pd/Fe的分散性最好，粒径明显小于未用CMC修饰的nZVI和Pd/Fe。4种材料对2,4-DCP的表观去除率为CMC-Pd/Fe>CMC-Fe>Pd/Fe>nZVI。随着CMC-Pd/Fe投加量和Pd负载量的增加，CMC-Pd/Fe对2,4-DCP的表观去除率增大，而随着2,4-DCP浓度的升高，CMC-Pd/Fe对2,4-DCP的表观去除率下降。当溶液初始pH=3、5和7时，CMC-Pd/Fe对2,4-DCP的表观去除率分别为94.34%、99.50%和96.62%;...     

维生素B_(12)协同纳米Fe/Cu双金属对五氯酚的催化降解与机理

针对水中含氯有机物的脱氯降解,制备了Fe/Cu双金属纳米颗粒,并引入维生素B12,研究铜负载率和维生素B12的剂量对以五氯酚为典型污染物的脱氯效果。结果表明:维生素B12和纳米零价铜能够有效提升五氯酚的脱氯速率及脱氯程度,脱氯率从4.52%增加到78.55%,降解产物从四氯酚进一步降解为苯酚。实验发现增加铜负载率可使双金属比表面积增大,催化活性位增多;增加维生素B12浓度可促进体系电子传递,使体系还原反应活性提升。铜负载率和维生素B12浓度过大均会使体系反应速率减缓甚至抑制。实验优化铜负载率为10%(质量分数),维生素B12浓度为20 mg·L~(-1)。探讨纳米零价铜和维生素B12的催化机理,以期对降解含氯有机物提供可操作性的参考。     

改性沸石承载纳米Fe/Ni对水中2,4-二氯苯酚的去除

将通过液相还原法制备的纳米铁/镍(Fe/Ni)颗粒承载于改性沸石表面制得负载型复合材料,纳米Fe/Ni在改性沸石表面具有良好的分散性。复合材料对2,4-二氯苯酚(2,4-DCP)的去除包括吸附和降解两个过程,脱氯降解是主要过程。实验结果表明,25℃时,0.6 g的复合材料对20 mg·L~(-1)的2,4-DCP去除效果达到80%,在酸性条件下,复合材料的去除效果未见明显差异,碱性环境会影响2,4-DCP的去除效果。降解产物苯酚被吸附在材料表面,避免了对水环境的二次污染。     

声电协同氧化氯酚的实验研究

采用超声波-电催化联合技术处理2-氯酚(2-CP)和4-氯酚(4-CP),探讨了电催化氧化和超声氧化的协同效应,考察了影响声电联合降解氯酚化合物的条件因数.结果表明,超声波-电催化联合技术处理效率明显优于电催化氧化技术,2-CP和4-CP的增强因子f分别为1.325和1.509.高电流密度有助于氯酚降解,2-CP和4-CP的表观反应速率常数随电流密度上升分别增加了1.28×10-5 s-1和1.82×10-5 s-1;高pH值也有利于氯酚降解,pH为9.08时,2-CP和4-CP的表观反应速率常数分别为9.22×10-5 s-1和11.02×10-5 s-1;高电解质浓度促进了2-CP的降解,而对4-CP的降解影响不大,2-CP表观反应速率常数从7.70×10-5 s-1上升到16.03×10-5 s-1.总之,超声波-电催化联合技术能够协同降解氯酚.     

紫外光与超声波耦合对氯酚水溶液的降解研究

选择超声波(US)、紫外光(UV)、紫外光与超声波耦合(UV/US)3种方式对不同位置取代基的单氯酚和不同数目取代基的氯酚进行降解研究。结果表明,UV、US、UV/US对取代基位置不同的单氯酚的降解率大小均为3-氯酚4-氯酚2-氯酚;UV、UV/US对不同取代基数量的氯酚的降解率大小为2-氯酚2,4-二氯酚2,4,6-三氯酚,US单独作用下的降解率大小为2,4,6-三氯酚2,4-二氯酚2-氯酚;UV与US的耦合呈现出较优的协同效应,且耦合降解均以US的降解作用占主导;UV、US、UV/US对氯酚的降解均符合表观一级反应动力学。     

溶液中阴离子和腐殖酸对UV/H2O2降解2,4-二氯酚的影响

研究了UV/H2O2工艺对2,4-二氯酚(2,4-DCP)的去除效果和水中阴离子、腐殖酸对该工艺降解2,4-DCP的影响.结果表明:UV/H2O2工艺可以有效地去除水中2,4-DCP,光降解过程符合一级反应动力学模型;在H2O2投加量为8 mg/L、1个30 W低压汞灯照射下,2,4-DCP在蒸馏水和自来水中反应速率常数分别为0.023 2、0.016 2 min-1;NO-3、Cl-、HCO-3对2,4-DCP光降解有抑制作用,当3种阴离子摩尔浓度为0.5、10.0、20.0 mmol/L时,对2,4-DCP光降解的抑制程度为HCO-3＞NO-3＞Cl-;腐殖酸在低浓度时,促进光降解反应进行,在高浓度时,2,4-DCP的光降解受到抑制.自来水中的反应速率常数低于蒸馏水中的反应速率常数是由于水中多种阴离子和腐殖酸影响的结果.     

超声波/纳米铁协同降解氯代苯酚的试验

通过间歇试验对超声波/纳米铁协同降解氯代苯酚(CPs)废水进行了研究,结果表明,超声波/纳米铁协同对CPs的降解率明显高于单纯超声波和单纯纳米铁的降解率;协同体系、单纯超声波和单纯纳米铁降解CPs均符合准一级反应动力学,协同体系的降解速率较单纯超声波提高了5.1~5.6倍,较单纯纳米铁提高了17.7~21倍,并且比它们的几何迭加值高4倍以上;氯代苯酚降解的准一级速率常数和降解率满足以下规律:PCP>2,4,5-TCP>2,4-DCP>3-CP;探讨了混合废水的降解:在混合废水体系中,结构易裂解的优先降解,然后为浓度高的优先降解。     

Reductive transformation of 2,4-dichlorophenoxyacetic acid by nanoscale and microscale Fe3O4 particles

Reductive transformation of 2,4-dichlorophenoxyacetic acid (2,4-D) by nanoscale and microscale Fe₃O₄ was investigated and compared. Disappearance of the parent species and formation of reaction intermediates and products were kinetically analyzed. Results suggest that the transformation of 2,4-D followed a primary pathway of its complete reduction to phenol and a secondary pathway of sequential reductive hydrogenolysis to 2,4-dichlorophenol (2,4-DCP), chlorophenol (2-CP, 4-CP) and phenol. About 65% of 2,4-D with initial concentration of 50 μ M was transformed within 48 h in the presence of 300 mg L^?1 nanoscale Fe₃O₄, and the reaction rates increased with increasing dosage of nanoscale Fe₃O₄. The decomposition of 2,4-D proceeded rapidly at optimum pH 3.0. Chloride was identified as a reduction product for 2,4-D in the magnetite–water system. Reductive transformation of 2,4-D by microscale Fe₃O₄ was slower than that by nanoscale Fe₃O₄. The reactions apparently followed pseudo-first-order kinetics with respect to the 2,4-D transformation. The degradation rate of 2,4-D decreased with the increase of initial 2,4-D concentration. In addition, anions had a significant adverse impact on the degradation efficiency of 2,4-D.     

Contribution of free radicals to chlorophenols decomposition by several advanced oxidation processes

The chemical decomposition of aqueous solutions of various chlorophenols (4-chlorophenol (4-CP), 2,4-dichlorophenol (2-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and 2,3,4,6-tetrachlorophenol (2,3,4,6-TeCP)), which are environmental priority pollutants, is studied by means of single oxidants (hydrogen peroxide, UV radiation, Fenton's reagent and ozone at pH 2 and 9), and by the Advanced Oxidation Processes (AOPs) constituted by combinations of these oxidants (UV/H2O2 UV/Fenton's reagent and O3/UV). For all these reactions the degradation rates are evaluated by determining their first-order rate constants and the half-life times. Ozone is more reactive with higher substituted CPs while OH* radicals react faster with those chlorophenols having lower number of chlorine atoms. The improvement in the decomposition levels reached by the combined processes, due to the generation of the very reactive hydroxyl radicals. in relation to the single oxidants is clearly demonstrated and evaluated by kinetic modeling.     

Effect of metal ions on decomposition of chlorinated organic substances by ozonation in acetic acid

The objective of this study is to find metal ions that enhance the ozone decomposition of chlorinated organic substances in acetic acid. Although the pseudo-first order degradation rate constant for 2,4-DCP by ozone in acetic acid in addition of Ca2+, Mg2+, Al3+ and Fe2+ were almost the same as that with no metal ion, the degradation rate in addition of Mn2+ and Fe3+ were 2.4 and 4.5 times as high as that with no metal ion, respectively. The presence of Fe3+ enhanced the degradation of 2,4-DCP by ozone in acetic acid because Fe3+-phenolate complex which have high reactivity with ozone was produced by the reaction between 2,4-DCP and Fe3+ in acetic acid.     

Degradation of chlorophenols in aqueous media using UV XeBr excilamp in a flow-through reactor

2-Chlorophenol (2-CP), 4-chlorophenol (4-CP) and 2,4-dichlorophenol (2,4-DCP) at initial concentrations of 10, 20, 50 and 100mg l(-1) were degraded in aqueous media by direct UV photolysis using dielectric barrier discharge XeBr( *) excilamp (283nm) in a flow-through photoreactor. The pseudo-first order rate constants were highest and half-life times were lowest for 4-CP. The rates of photolysis under the experimental conditions increased in the order: 2-CP<2,4-DCP<4-CP. The intermediates of photolysis were identified by GC-MS and HPLC. The evolution of hydroquinone and p-benzoquinone as major intermediates of 4-CP photolysis was monitored.     

Aerobic granulation for 2,4-dichlorophenol biodegradation in a sequencing batch reactor

Development of aerobic granules for the biological degradation of 2,4-dichlorophenol (2,4-DCP) in a sequencing batch reactor was reported. A key strategy was involving the addition of glucose as a co-substrate and step increase in influent 2,4-DCP concentration. After operation of 39d, stable granules with a diameter range of 1-2mm and a clearly defined shape and appearance were obtained. After granulation, the effluent 2,4-DCP and chemical oxygen demand concentrations were 4.8mgl(-1) and 41mgl(-1), with high removal efficiencies of 94% and 95%, respectively. Specific 2,4-DCP biodegradation rates in the granules followed the Haldane model for substrate inhibition, and peaked at 39.6mg2,4-DCPg(-1)VSS(-1)h(-1) at a 2,4-DCP concentration of 105mgl(-1). Efficient degradation of 2,4-DCP by the aerobic granules suggests their potential application in the treatment of industrial wastewater containing chlorophenols and other inhibitory chemicals.     

Adsorption of phenols by papermill sludges

In this paper we studied the sorption capacity of paper mill sludges for phenols. Phenol, 2-chlorophenol (2-CP), 3-chlorophenol 3-CP). 4-chlorophenol (4-CP), 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2.4-dichlorophenol (2,4-DCP), 3,4-dichlorophenol (3,4-DCP) 3,5-dichlorophenol (3,5-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) were chosen for the sorption tests. Kinetic experiments showed that substituted-phenol sorption on papermill sludge was rapid (equilibrium was reached after 3 h); conversely, the time taken by the phenol to reach equilibrium conditions was 260 h. Experimental data showed that particle diffusion was involved in the sorption process but was not the only rate-limiting mechanism; several other mechanisms were involved. The adsorption isotherms showed the following order of retention capacity of papermill sludge: 2-NP = 4-NP < < 2-CP < phenol < 4-CP < or = 3-CP < 2,4 DCP<3,4 DCP=2,4,5 TCP<3,5 DCP. In all cases the experimental data showed a good fit with the Hill equation. which is mathemratically equivalent to the Langmuir-Freundlich model obtained by assuming that the surface is homogeneous, and that the adsorption is a cooperative process influenced by adsorbate-adsorbate interactions.     

Hydrodechlorination of polychlorinated biphenyls in contaminated soil from an e-waste recycling area,using nanoscale zerovalent iron and Pd/Fe bimetallic nanoparticles

Soil pollution by polychlorinated biphenyls (PCBs) arising from the crude disposal and recycling of electronic and electrical waste (e-waste) is a serious issue, and effective remediation technologies are urgently needed. Nanoscale zerovalent iron (nZVI) and bimetallic systems have been shown to promote successfully the destruction of halogenated organic compounds. In the present study, nZVI and Pd/Fe bimetallic nanoparticles synthesized by chemical deposition were used to remove 2,2′,4,4′,5,5′-hexachlorobiphenyl from deionized water, and then applied to PCBs contaminated soil collected from an e-waste recycling area. The results indicated that the hydrodechlorination of 2,2′,4,4′,5,5′-hexachlorobiphenyl by nZVI and Pd/Fe bimetallic nanoparticles followed pseudo-first-order kinetics and Pd loading was beneficial to the hydrodechlorination process. It was also found that the removal efficiencies of PCBs from soil achieved using Pd/Fe bimetallic nanoparticles were higher than that achieved using nZVI and that PCBs degradation might be affected by the soil properties. Finally, the potential challenges of nZVI application to in situ remediation were explored.     

Treatment and reuse of wastewater in pesticide 2,4-D production

Waste-water from the production of pesticide 2,4-D often contains high concentrations of 2,4-DCP and 2,6-D as the primary pollutants. Treatment of waste-water collected from a 2,4-D manufacturer was carried out using a technology combining acidification with hyper-crosslinked resin NDA-150 adsorption process. The overall process recovered 5.4 kg of 2,4-DCP and 0.6 kg of 2,6-D per cubic metre of the wastewater. The treatment reduced the concentration of 2,4-DCP in the wastewater from >6000 mg/L to <0.5 mg/L. The optimal operation parameters of adsorption and desorption were determined. The hyper-crosslinked resin adsorbent can be re-used after regeneration by NaOH aqueous solution. The recovered 2,4-DCP with a sufficiently high purity may be re-used in the production of 2,4-D. The technology may thus be applied to the treatment of waste-water for reclamation of chemicals for 2,4-D production while minimising the environmental nuisances and hazards that may be caused by these chemicals.     

Acclimation of anaerobic sludge degrading chlorophenols and the biodegradation kinetics during acclimation period

The acclimation of sludge from Hangzhou citrate factory and Hangzhou municipal wastewater treatment plant for degradation dechlorination of chlorophenols (CPs) compounds, and its biodegradation kinetics were studied in batch process with or without addition of sucrose. Three monochlorophenols (2-CP; 3-CP; 4-CP) and pentachlorophenol (PCP) were concurrently fed to different bioreactors. The parameters that were monitored included biogas production, biogas composition and chemical oxygen demand (COD). The results showed that acclimation with chlorophenol can increase the degradation activity of anaerobic sludge and degradation rate of chlorophenolic compounds, and reduce the lag time. Degradation dechlorination activity of the acclimated sludge strongly depended on sludge source, microorganism population and chlorophenol congener. 2-CP was more easily acclimated than 3-CP and 4-CP. Among the four tested compounds, 4-CP was the most difficult to be acclimated. The observed degradation rate with presence of sucrose was higher than that with absence of sucrose, suggesting that addition of the external carbon source can stimulate the formation of acclimated sludge which could effectively degrade chlorophenols. Kinetic equations of biodegradation of chlorophenols were also presented in this paper.