Catalytic amination and dechlorination of para-nitrochlorobenzene (p-NCB) in water over palladium-iron bimetallic catalyst

Chemical treatment of para-nitrochlorobenzene (p-NCB) by palladium/iron (Pd/Fe) bimetallic particles represents one of the latest innovative technologies for the remediation of contaminated soil and groundwater. The amination and dechlorination reaction is believed to take place predominantly on the surface site of the Pd/Fe catalysts. The p-NCB was first transformed to p-chloroaniline (p-CAN) then quickly reduced to aniline. 100% of p-NCB was removed in 30 min when bimetallic Pd/Fe particles with 0.03% Pd at the Pd/Fe mass concentration of 3g 75 ml(-1) were used. The p-NCB removal efficiency and the subsequent dechlorination rate increased with the increase of bulk loading of palladium and Pd/Fe. As expected, p-NCB removal efficiency increased with temperature as well. In particular, the removal efficiency of p-NCB was measured to be 67%, 79%, 80%, 90% and 100% for reaction temperature 20, 25, 30, 35 and 40 degrees C, respectively. Our results show that no other intermediates were generated besides Cl(-), p-CAN and aniline during the catalytic amination and dechlorination of p-NCB.     

Analysis of chlorothalonil and degradation products in soil and water by GC/MS and LC/MS

We present a method using gas chromatography (GC) and liquid chromatography (LC) coupled to a mass selective detector to measure concentrations of the fungicide chlorothalonil and several of its metabolites in soil and water. The methods employed solid-phase extraction using a hydrophobic polymeric phase for the isolation of analytes. In lake water, average analyte recoveries ranged from 70% to 110%, with exception of pentachloronitrobenzene that gave low recoveries (23%). The method detection limits were determined to be in the range of 1 and 0.1microg l(-1) for the LC and GC methods, respectively. In soil samples, recoveries ranged from 80% to 95% for 4-hydroxy-2,5,6-trichloroisophthalonitrile (metabolite II) and 1,3-dicarbamoyl-2,4,5,6-tetrachlorobenzene (metabolite III). Limits of detection (LOD) were 0.05 and 0.02microg g(-1), respectively. Chlorothalonil and other metabolites were analyzed by GC giving recoveries ranging from 54% to 130% with LOD of 0.001-0.005microg g(-1).     

Catalytic degradation of Orange II by UV-Fenton with hydroxyl-Fe-pillared bentonite in water

Although homogeneous photo-Fenton system is a very efficient method for organic wastewater treatment, it suffers from costly pH adjustment as well as difficult separation of catalysts from aqueous in practical application. Through cation exchange reaction, hydroxyl-Fe-pillared bentonite (H-Fe-P-B) was successfully prepared as a solid catalyst for UV-Fenton to degrade non-biodegradable azo-dye Orange II. Compared with raw bentonite, the content of iron, interlamellar distance and external surface area of H-Fe-P-B increased remarkably. H-Fe-P-B had good photosensitivity and catalyst reactivity. And the catalytic activity of H-Fe-P-B for H(2)O(2) came from hydroxyl-Fe between sheets rather than Fe(3+) or Fe(2+) in tetrahedral or octahedral sheets of bentonite. In UVA-H(2)O(2) system, H(2)O(2) could destroy the azo bond of excited Orange II molecules but could not effectively mineralize it. After 120 min treatment, 83% discoloration was obtained while only 2% of TOC was removed. When H-Fe-P-B was used as catalyst, a significant degradation of Orange II was observed at the same condition as UVA-H(2)O(2) system. Almost 100% discoloration and more than 60% TOC removal of Orange II could be achieved after 120 min treatment. Because of the strong surface acidity and the electronegativity of H-Fe-P-B, the pH range of this catalyst in the Orange II discoloration could be extended up to 9.5. And this catalyst showed good stability during Orange II degradation in water in wide range of pH (3.0-9.5). These results indicated that the H-Fe-P-B was a promising catalyst for UV-Fenton system.     

粉煤灰负载铁离子催化氧化活性黄染料废水

以粉煤灰为载体,制备铁/粉煤灰负载型催化剂,并利用该催化剂催化H2O2氧化降解活性黄染料废水,探讨了H2O2投加量、催化剂投加量、染料初始浓度和初始pH值等因素对染料废水COD去除率和脱色率的影响。结果表明,当染料废水COD初始浓度为200 mg/L,初始pH值为1.7,投加0.5 g/100 mL催化剂及加入1.0 mL浓度为1.13 mol/L的H2O2溶液时,处理效果最好,此时染料废水的COD去除率和脱色率分别达到63%和99%,并且废水的可生化性得到很大的提高。利用该负载催化剂能够有效地减少活性黄染料废水中Fe3+的残留量。     

Monitoring the sonochemical degradation of phthalate esters in water using solid-phase microextraction

The sonochemical degradation of aqueous solutions containing low concentrations of six phthalate esters at an ultrasonic frequency of 80 kHz has been investigated. Ultrasonic treatment was found capable of removing the four higher molecular mass phthalates (di-n-butyl phthalate, butylbenzyl phthalate, di-(2-ethylhexyl) phthalate and di-n-octyl phthalate) within 30-60 min of irradiation. The rest (dimethyl phthalate and diethyl phthalate) were more recalcitrant and nearly complete removal could be achieved only after prolonged irradiation times. The relative reactivity of phthalates was explained in terms of their hydrophobicity. Experiments were carried out at an overall initial phthalate concentration of 240 microg l(-1), values of electric power of 75 and 150 W, temperatures of 21 and 50 degrees C and in the presence of NaCl to study the effect of various operating conditions on degradation. Solid-phase microextraction (SPME) coupled with GC-MS proved to be a powerful analytical tool to monitor the sonochemical degradation of phthalate esters at low microg l(-1) concentration levels, minimising the risk of secondary contamination during sample preparation, a major parameter to consider during phthalates analysis. The advantages as well as disadvantages of using SPME are also highlighted.     

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。     

高频超声辐照降解水中4-氯酚的研究

本文着重探讨了高频超声波 (1.7MHz)降解 4 氯酚的反应过程和反应机理 ,研究了高频超声波降解 4 氯酚的效果 ,并讨论了 4 氯酚初始浓度等因素对降解效果的影响。高频超声波降解 4 氯酚为一级反应 ,超声波空化效应在降解过程中起主导作用     

Cu2O光催化降解水中对硝基苯酚的研究

用CuCl水解法制备Cu2O粉末,用透射电镜(TEM)和X衍射(XRD)对Cu2O粒子进行了表征.在仿太阳光源的照射下,研究了Cu2O对水中难降解有机污染物对硝基苯酚的光催化降解效果.结果表明,在8 h内,对硝基苯酚几乎完全降解.在催化剂用量为0.2 g时,对浓度为22.4 mg/L的200mL对硝基苯酚溶液有良好的降解效果.降解反应符合一级反应动力学.     

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。     

催化超临界水氧化对氨基苯酚

采用CuO／γ-Al2O3和MnO2/γ-Al2O3为催化剂、H2O2为氧化剂，在一连续流固定床反应器中进行了超临界水氧化对氨基苯酚实验。实验结果表明，CuO和MnO2催化剂对于对氨基苯酚的氧化降解具有显著的促进作用。对氨基苯酚的去除率随反应温度和压力的升高、停留时间的延长而提高，在24～26MPa和400～450℃条件下，数秒钟内COD去除率可达到99％以上，催化剂CuO／γ-Al2O3的催化效果优于MnO2／γ-Al2O3。证明了催化超临界水氧化技术的高效性。     

Characterizing pesticide sorption and degradation in microscale biopurification systems using column displacement experiments

Biopurification systems treating pesticide contaminated water are very efficient, however they operate as a black box. Processes inside the system are not yet characterized. To optimize the performance, knowledge of degradation and retention processes needs to be generated. Therefore, displacement experiments were carried out for four pesticides (isoproturon, bentazone, metalaxyl, linuron) in columns containing different organic mixtures. Bromide, isoproturon and bentazone breakthrough curves (BTCs) were well described using the convection-dispersion equation (CDE) and a first-order degradation kinetic approach. Metalaxyl and linuron BTCs were well described using the CDE model expanded with Monod-type kinetics. Freundlich sorption, first-order degradation and Monod kinetics coefficients were fitted to the BTCs. Fitted values of the distribution coefficient K_f,column were much lower than those determined from batch experiments. Based on mobility, pesticides were ranked as: bentazone > metalaxyl - isoproturon > linuron. Based on degradability, pesticides were ranked as: linuron > metalaxyl - isoproturon > bentazone.     

超声波降解水中的氯苯

考察了用超声波降解水中氯苯的可行性、动力学、产物和TOC变化。在 2 0kHz和 4 0W的超声波作用下 ,氯苯的一级降解常数为 0 0 5 /min。随着所加超声功率的增高 ,氯苯降解常数呈线性增加。 30min内超声脱氯效率达到 6 6 % ,TOC去除达到 4 3%。     

Light-induced degradation of metsulfuron-methyl in water

Photodegradation of metsulfuron-methyl, a sulfonylurea herbicide, has been investigated in aqueous solution at different pH and excitation wavelengths. The efficiency of the process has been evaluated through quantum yield determinations. The identification of the photoproducts indicates that the major photochemical pathway is initiated by C-S bond dissociation followed by involvement of water to yield the main final products; the behaviour in water is shown to differ markedly from that in an organic environment.     

催化超临界水氧化对氨基苯酚

采用CuO/γ-Al2O3和MnO2/γ-Al2O3为催化剂、H2O2为氧化剂,在一连续流固定床反应器中进行了超临界水氧化对氨基苯酚实验.实验结果表明,CuO和MnO2催化剂对于对氨基苯酚的氧化降解具有显著的促进作用.对氨基苯酚的去除率随反应温度和压力的升高、停留时间的延长而提高,在24～26 MPa和400～450℃条件下,数秒钟内COD去除率可达到99%以上,催化剂CuO/γ-Al2O3的催化效果优于MnO2/γ-Al2O3.证明了催化超临界水氧化技术的高效性.     

Characterisation of the abiotic degradation pathways of oxytetracyclines in soil interstitial water using LC-MS-MS

The fate of oxytetracyclines (OTCs) in soil interstitial water was investigated and the structure of a number of degradation products elucidated in a time-related experiment. A previously developed separation method for LC–MS–MS able to base separate and quantify OTC and three of its epimers and degradation products was applied. Compounds detected were 4-epi-oxytetracycline (EOTC) (t_R=3.0 min), OTC (t_R=4.4 min), -apo-oxytetracycline (-apo-OTC) (t_R=11.4 min) and β-apo-oxytetracycline (β-apo-OTC) (t_R=18.4 min). Furthermore, we tentatively identified 4-epi-N-desmethyl-oxytetracycline (E-N-DM-OTC) (t_R=3.0 min), N-desmethyl-oxytetracycline (N-DM-OTC) (t_R=3.5), N-didesmethyl-oxytetracycline (N-DDM-OTC), 4-epi-N-didesmethyl-oxytetracycline (E-N-DDM-OTC) (t_R=3.7 and 4.7 min) and 2-acetyl-2-decarboxamido-oxytetracycline (t_R=8.7) in all samples. Most compounds were only present in trace concentrations (less than 2%) relative to the parent OTC. EOTC was on the other hand formed up to a ratio of 0.6 relative to parent OTC concentration. Only EOTC, E-N-DM-OTC, N-DM-OTC, N-DDM-OTC and E-N-DDM-OTC were formed during the time-related experiment. All other compounds were probably only present as impurities in the spiked OTC formulation as they declined in concentration from the start of the experiment. Half-lives (T_1/2, days) of the OTCs in soil interstitial water were in the order of 2 days (EOTC) to 270 days (β-apo-OTC).     

水体系中正癸烯的光催化降解

以中压汞灯为光源 ,研究了水体系中正癸烯 (n C10 H2 0 )在TiO2 光催化氧化作用下的降解。结果表明 ,降解反应符合一级动力学方程 ;n C10 H2 0 在不同粒径TiO2 下的反应速率常数k为 6 .80— 9.90× 10 -3 min-1(在 30 0W中压汞灯下 ) ,其值随粒径的增加而降低 ;在相同粒径下 ,k值随光强增加而增大。同时测定了在水体中掺杂 1wt% (即过渡金属质量占Ti原子质量的百分数 )的过渡金属离子时 ,n C10 H2 0 的光降解速率常数k为 11.4— 15 .9× 10 -3 min-1,因而其对光降解的影响顺序是 :Ag+ >Fe3 + >Pb2 + >Fe2 + >Zn2 + >Mn2 + 。产物经GC/MS分析表明 ,水体中n C10 H2 0 光催化降解生成辛醛、壬醛、癸醛和 2 癸酮。     

Preparation of a novel iron-based biochar composite for removal of hexavalent chromium in water

The chitosan-stabilized ferrous sulfide nanoparticles were loaded on biochar to prepare a composite material FeS-CS-BC for effective removal of hexavalent chromium in water. BC and FeS-CS-BC were characterized by Brunauer–Emmett–Teller (BET), scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. Batch experiments were employed to evaluate the Cr(VI) removal performance. The experimental results showed that the removal rate of Cr(VI) by FeS-CS-BC(FeS:CS:BC?=?2:2:1) reached 98.34%, which was significantly higher than that of BC (44.58%) and FeS (79.91%). In the pH range of 2–10, the removal of Cr(VI) by FeS-CS-BC was almost independent of pH. The limitation of coexisting anions (Cl^?、SO₄^2?、NO₃^?) on Cr(VI) removal was not too obvious. The removal of Cr(VI) by FeS-CS-BC was fitted with the pseudo-second-order dynamics, which was a hybrid chemical-adsorption reaction. The X-ray photoelectron spectroscopy (XPS) analysis result showed that Cr(VI) was reduced, and the reduced Cr(VI) was fixed on the surface of the material in the form of Cr(VI)–Fe(III).

Removal of hexavalent chromium from wastewater by FeS-CS-BC composite synthesized by impregnation.

     

Modeling and optimization of reductive degradation of chloramphenicol in aqueous solution by zero-valent bimetallic nanoparticles

Purpose

The present study aims to investigate the individual and combined effects of temperature, pH, zero-valent bimetallic nanoparticles (ZVBMNPs) dose, and chloramphenicol (CP) concentration on the reductive degradation of CP using ZVBMNPs in aqueous medium.

Method

Iron?Csilver ZVBMNPs were synthesized. Batch experimental data were generated using a four-factor statistical experimental design. CP reduction by ZVBMNPs was optimized using the response surface modeling (RSM) and artificial neural network-genetic algorithm (ANN-GA) approaches. The RSM and ANN methodologies were also compared for their predictive and generalization abilities using the same training and validation data set. Reductive by-products of CP were identified using liquid chromatography-mass spectrometry technique.

Results

The optimized process variables (RSM and ANN-GA approaches) yielded CP reduction capacity of 57.37 and 57.10?mg?g^?1, respectively, as compared to the experimental value of 54.0?mg?g^?1 with un-optimized variables. The ANN-GA and RSM methodologies yielded comparable results and helped to achieve a higher reduction (>6%) of CP by the ZVBMNPs as compared to the experimental value. The root mean squared error, relative standard error of prediction and correlation coefficient between the measured and model-predicted values of response variable were 1.34, 3.79, and 0.964 for RSM and 0.03, 0.07, and 0.999 for ANN models for the training and 1.39, 3.47, and 0.996 for RSM and 1.25, 3.11, and 0.990 for ANN models for the validation set.

Conclusion

Predictive and generalization abilities of both the RSM and ANN models were comparable. The synthesized ZVBMNPs may be used for an efficient reductive removal of CP from the water.     

双金属系统还原脱溴降解多溴联苯醚(PBDEs)研究进展

多溴联苯醚(PBDEs)是一类新型持久性有机污染物。双金属系统催化还原脱溴技术作为一种处理环境中PBDEs的方法,具有出较好的应用前景。综述了双金属系统催化还原PBDEs脱溴的研究进展,详细阐述了双金属系统催化PBDEs脱溴降解的机理、途径以及不同双金属系统的脱溴效能。提出了利用双金属系统降解PBDEs存在的问题和发展前景。