催化氧化降解木质素的研究进展

本文从所用催化剂、反应条件、反应机理等几个方面综述了木质素催化氧化降解方面的研究,着重介绍了以O_2和H_2O_2为氧化剂的金属为催化中心的氧化降解,例如,金属有机催化氧化、金属/溴化物催化氧化、金属配合物催化氧化、金属复合氧化体系和钛矿型复合氧化物催化氧化、金属/分子筛催化氧化和以自身为氧化剂的催化氧化等,以及无金属催化氧化降解、微波辅助氧化降解、光催化氧化降解和电化学氧化降解。     

新型二氧化铅阳极电催化降解有机污染物的特性研究

通过XRD、SEM等表征,以酚类化合物为目标污染物,研究了经改性的新型含氟β-PbO2阳极电催化氧化污染物的特性.结果表明,该电极对酚类有机污染物的降解显示了良好的电催化活性、稳定性和抗腐蚀性,有较好的环保应用前景.进一步通过羟基自由基清除剂异丙醇加入前后降解效果的比较证实了本系统中有机污染物的降解主要基于羟基自由基的作用机理,是一种电化学高级氧化工艺.     

木质素氧化降解研究进展

木质素是当今世界上含量第二丰富的可再生高聚物.氧化降解是木质素价值增值过程中一种非常有前景的方法,它能提供高度官能化的单体和低聚物产品作为其他价值增值过程的起始原料,为代替化石燃料在化工和制药行业中的应用提供了一种可能.主要对木质素及其模型化合物的氧化改性方法进行了综述,包括生物催化、仿生催化、有机金属催化、电化学催化氧化及其他几种催化氧化法,并简单讨论了氧化降解过程的反应机理,为今后木质素的氧化价值增值研究提供一定的参考.     

二氧化钛纳米管阵列的构建及其光电催化性能

利用阳极氧化法制备了TiO2纳米管阵列, 研究了其光电化学性能, 并且应用该电极对偶氮染料催化降解进行了初步研究.     

负载型贵金属纳米粒子作为光/超声催化剂在化学合成和降解污染物方面的应用

综述了Au/TiO2、Au/ZrO2、Ag/AgCl等负载型贵金属纳米粒子作为有效的光/超声催化剂在化学合成和降解污染物方面的应用.负载型贵金属纳米粒子能够有效地将太阳能转化为化学能.在紫外光或可见光的辐照下,负载型贵金属纳米粒子能够催化一系列的选择性化学转化,如醇类化合物氧化为醛/酮类化合物、硫醇氧化为二硫化合物、苯氧化为苯酚、硝基苯类化合物还原为偶氮化合物等.在超声波辐射下,负载型贵金属纳米粒子能够有效地催化分解水产氢.此外,在紫外光或可见光的辐照下,负载型贵金属纳米粒子能够有效地催化降解多种污染物,如醛类、醇类、酸类、酚类化合物和染料等.在超声波辐射下,负载型贵金属纳米粒子也能够有效地催化降解包括染料在内的有机污染物.     

木质素氧化降解制备单酚类化合物

采用H2O2、CuO/Fe2(SO4)3复合氧化体系,在碱性条件、微波辅助作用下,对麦草碱木质素氧化降解制备单酚类化合物的工艺条件进行了研究。结果表明,在180℃相对温和的条件下,单酚类化合物的总收率可达11.86%,降解率为90.88%。单独H2O2作为氧化剂降解木质素导致了苯环的开裂,使得木质素的降解率虽高但单酚类收率偏低;Cu2+的参与促进了木质素侧链和醚键的断裂,有利于提高单酚类化合物的收率,而Fe3+的存在则提升了H2O2的氧化性能。适当提高氧化温度和延长降解反应时间有利于提高单酚类化合物收率。由于木质素的降解和聚合同时存在,防止降解产物的聚合成为提高单酚类化合物收率的关键。     

还原-氧化协同降解全/多卤代有机污染物

全/多卤代有机污染物大多具有生态毒性、生物蓄积性、环境持久性及长距离迁移性,不仅危害环境与生态安全,而且可经食物链传递威胁人类健康。由于卤原子是吸电子基团且取代数目多,这类物质的最高占据分子轨道能较低,难于被氧化降解,相反较易被还原法脱卤降解。随卤原子取代数减少,脱卤产物难被进一步还原,而其毒性甚至高于母体污染物。注意到低卤代有机物更容易发生氧化降解,一些研究构建了还原-氧化接力降解体系,即先利用还原法将全/多卤代有机污染物还原为低卤代产物,再利用氧化法降解这些中间产物,从而实现深度/完全脱卤和矿化。本文根据催化反应类型对还原-氧化联用法进行了归纳,分类介绍了基于传统化学催化、光催化、电化学、光电化学及机械化学等构建还原-氧化协同降解体系的原理及应用,以期为开发高效的处置技术提供思路和建议。     

二氧化氯催化氧化难降解有机废水在我国的研究进展

难降解有机废水的处理对环境保护有十分重要的意义.在本文中,对用二氧化氯催化氧化技术在不同领域中难降解有机废水的处理和其催化氧化反应机理在我国的研究进展进行了介绍和评述,也指出了该技术未来的发展前景和进一步的研究方向.     

Ta/BDD薄膜电极电化学催化氧化硝基酚

研究了热丝化学气相沉积法(HFCVD)制备得到钽衬底掺硼金刚石膜电极(Ta/BDD)的物理性质和电势窗口, 并考察了其用于电化学催化氧化硝基酚过程中的性能及各种影响因素. 扫描电镜和拉曼光谱表明, Ta/BDD电极具有良好的物理性能, 通过测试Ta/BDD电势窗口发现, 该电极具有较高的析氧过电位. 在Ta/BDD电化学催化氧化硝基酚过程中, 化学需氧量(COD)和高效液相色谱测试表明, 硝基酚能够有效降解, 电流密度、支持电解液及浓度对降解过程影响较大, 温度影响不明显. 强化寿命实验表明, Ta/BDD电极具有较好的稳定性. 实验结果表明, Ta/BDD电极是一种适于硝基酚降解和COD去除的优良电极.     

TiO_2光电化学电池催化氧化甲基红

以钛基TiO2薄膜为光阳极,研究了光电化学电池中阳极光催化降解偶氮染料甲基红的动力学.结果表明,短接光电化学电池分隔了光催化过程的阴、阳极反应,有利于抑制光生载流子的复合,提高光催化氧化速率.相同实验条件下短路光电流越大,则甲基红降解速率越高.在基底和TiO2薄膜之间夹层SnO2得到组装电极Ti/SnO2/TiO2,进一步提高了光生载流子的分离效率;同时采用电化学阻抗谱(EIS)评价了电极的光催化性能.     

Several Rules for Treating Phenol Wastewater via Oxidation by O3/UV-formed Radicals

IntroductionA large amount of phenol wastewater comes fromdifferent sources with potential severe impact to life andenvironment.Phenol is a prototype poison,which istoxic to all living creatures.Phenol can coagulate pro-tein and devitalize cells,especiall…     

隔膜式电解槽生物膜阴极降解苯酚的过程及其条件的优化

以炼油废水中的主要污染物苯酚为目标污染物, 采用不同生物膜电极反应器对苯酚进行降解, 从而寻找出降解苯酚的最佳反应途径. 研究结果表明, 运用隔膜式电解槽生物膜阴极区域对苯酚废水进行处理, 其苯酚的去除效果虽然没有在生物膜阴极与阳极相混合的混合式反应器中处理效果好, 但在18 h内苯酚浓度降解到0, 并且其化学需氧量(COD)去除率最高, 在16 h内COD去除率达到80%. 对于隔膜式电解槽生物膜阴极区域的降解条件优化后发现, 电流设定为5 mA, 初始苯酚质量浓度低于200 mg/L, 温度为35 ℃时, 苯酚降解效果最佳.     

负载型铜钴氧化物协同催化 H2O2/HCO3-降解苯酚

近年来,环境污染特别是水的严重污染使其治理成为一个极具挑战性的课题.各种污染物复杂的化学成分和催化剂在处理过程中的浸出、寿命及成本等问题是导致众多氧化催化剂难以实际应用的主要原因.相对而言, H2O2是一种活性氧含量高、清洁并可在温和条件下使用的氧化剂,在各种高级氧化技术中受到广泛关注.而碳酸氢盐是一种弱碱性物质,在自然界及水体系中广泛存在,且无明显毒害.它可活化 H2O2,加快其氧化各种有机物,并在废水处理领域开始受到关注.该体系的明显优势在于处理体系始终处于微碱性环境,可以有效避免金属氧化物催化剂在处理过程中由于体系酸化而带来的催化剂流失,从而延长催化剂寿命,降低催化剂成本.
　　本文采用浸渍法制备了一种双金属铜、钴氧化物催化剂及相关的对照催化剂体系,利用碳酸氢盐活化 H2O2用于降解苯酚模拟废水.通过各种空白实验发现,负载于γ-Al2O3表面的钴、铜氧化物催化剂 CuO?Co3O4@γ-Al2O3具有最好的催化降解活性,而 CuO@γ-Al2O3, Co3O4@γ-Al2O3, CuO?Co3O4及 CuO和 Co3O4的物理混合物均表现出较差的催化性能.由此可见,在 CuO?Co3O4@γ-Al2O3催化剂中,铜、钴离子在苯酚降解过程中存在协同效应,这可能与催化剂中钴、铜金属离子的相互作用相关. X射线衍射和 X射线光电子能谱结果表明,反应前后 CuO?Co3O4@γ-Al2O3催化剂中金属的氧化状态并未发生改变,在使用过程中钴离子的浸出率可以忽略,铜离子的浸岀率也仅有0.6 ppm.荧光分析实验和自由基捕获实验表明,只有添加?O2-和?OH的捕获剂能明显抑制降解反应,因而推测该反应体系对有机物的降解是一个自由基氧化过程,起关键作用的可能是?O2-和?OH.     

Fabrication of electrospun polyethersulfone/titanium dioxide (PES/TiO2) composite nanofibers membrane and its application for photocatalytic degradation of phenol in aqueous solution

The main objective of this research is to use the photocatalytic properties of PES/TiO₂ nanofibers membranes to remove the phenol as a toxic pollutant in various effluents. The uniform fibers in terms of minimum bead formation and fibers diameter were fabricated. Therefore, more TiO₂ catalysts are on the surface of the fibers which increase the active surface area of nanoparticles and consequently improve the phenol degradation efficiency. The effects of TiO₂ concentration on hydrophilicity, mechanical properties, porosity, mean pore size, and water flux of membranes were studied. The PES/TiO₂ nanofibers were evaluated for phenol degradation under UVA irradiation through a transparent membrane module. The amount of removable phenol was analyzed with high‐performance liquid chromatography. Central composite design was used as a statistical experimental design. Finally, the effect of TiO₂ content in nanofibers and initial phenol concentrations were investigated as well as pH values in synthetic wastewater, on phenol degradation. The results from analysis of variance (ANOVA) analysis indicated that TiO₂ content in nanofibers was the most important and effective parameter on phenol degradation. It was also presented that there is no significant interaction between parameters so that the effect of each parameter was investigated separately. Maximum phenol degradation was 43.0 ± 0.3% and found under conditions of TiO₂ content, initial phenol concentration, and pH value of 8%, 120 ppm, and 7, respectively.     

苯酚在含氯体系中的电化学氧化

以Ru-Ir/Ti三元电极作阳极电解处理苯酚废水,研究废水中Cl-初始浓度对处理效果的影响.结果表明,在一定的电解时间内,苯酚的电化学氧化符合一级动力学方程;废水中Cl-的初始浓度越大,苯酚完全被氧化所需的时间也越短,即其表观速率常数越大.苯酚在Cl-体系中降解的中间产物主要有4-氯苯酚,1-氯苯酚,2,4-二氯苯酚,2,6二氯苯酚,2,4,6-三氯苯酚及各种短链脂肪酸和氯代醇等;最终产物是CO2、CHCl2和CHCl3.电解中间体的生成和降解速率随废水中Cl-初始浓度的增加而增大.据此,导出苯酚在含Cl-体系中电化学氧化的反应途径.     

Enhanced photocatalytic performance of magnetite/TS-1 thin film for phenol degradation

Photocatalytic degradation method is an emerging technique for complete removal of pollutants. Several semiconductor photocatalysts are reported as photocatalysts for industrial wastewater treatment in environmental applications. In this study Magnetite/TS-1 composite materials was used for photocatalytic degradation of phenol. Magnetite nanoparticles (MNP) (10 wt%) were dispersed with nanocrystalline Titanium Silicate-1 zeolite (TS-1). The Magnetite/TS-1 composite materials were characterized with various techniques. The structural analysis reveals the presence of MNP and zeolite-MFI phases in Magnetite/TS-1 composite materials. The average particles size of the magnetite nanoparticles is less than 5 nm and that of the composite nanoparticles are in the range of about 90 nm with micropore volume 0.110 cm³/g and the external surface area 120 m²/g. The photocatalytic experiments were carried out in a thin film flow photoreactor under UV radiation. The results showed that Magnetite/TS-1 composite materials exhibited improved activity for the degradation of phenol compared to TS-1. Preliminary studies proves that aeration is necessary for the photocatalytic reaction. The reaction parameters such as flow rate, pH and phenol concentration are optimized as 8 ml/min, pH 7.0 and 75 mg/L respectively. To understand the active species involved in the degradation of phenol radical scavengers such as NaI, benzoquinone and isopropyl alcohol are used to trap hole (h⁺), superoxide anion radical and hydroxyl radical (OH), respectively. From the obtained results it is envisaged that hydroxyl radicals are predominantly involved in complete oxidation of phenol. The extent of degradation of phenol was determined by measuring the amount of CO₂ formed in the reaction. The results confirms that 99.6 % carbon in phenol is converted to CO₂.     

复合金属氧化物Sn-Sb-Mn/陶瓷粒子电极体系的电催化性能

通过热分解法制备了复合金属氧化物Sn-Sb-Mn/陶瓷粒子电极, 分别采用扫描电子显微镜(SEM)、能量色散X 射线能谱(EDS)、X射线衍射(XRD)和N2吸附-脱附等技术对电极的形貌、晶相组成、比表面积和孔径分布进行了表征. 考察了该三维粒子电极系统的析氧特性, 采用循环伏安法分析了三维系统的电催化性能, 并且进行了电化学催化降解苯酚的试验. 结果表明, 制备的陶瓷粒子电极涂层比表面较大、孔结构发达, 有利于电催化反应; 电催化降解主要发生在电化学析氧区; 粒子电极系统对苯酚降解作用显著, 明显高于二维电极系统, 苯酚的去除率为92.3%, 总有机碳(TOC)的去除率为66.7%. 研究结果表明, 该三维粒子电极系统具有优良的电催化性能.     

不同电催化工艺下苯酚的降解特性

比较了苯酚在电催化阳极氧化(AE)、阴阳两极协同降解(ACE)及亚铁离子存在下阴阳两极协同催化降解(FeACE)₃种工艺下的降解及产物变化.在电流0.25A下处理2h,废水中COD的去除率在AE下仅30％,在ACE下为60％,而在FeACE下高达90％.苯酚降解的中间产物主要为对苯二酚、邻苯二酚、间苯二酚、对苯醌、顺丁烯二酸、反丁烯二酸和草酸等.在FeACE工艺下,中间产物还有甲酸.最终产物为CO₂.FeACE不仅提高了COD的去除速率,而且还有助于有毒中间产物的迅速消除,并使有机物彻底氧化,因而在环境保护中更具有应用前景.采用水杨酸作捕获剂证实了3种电催化工艺降解有机物的羟基自由基作用机理,其进攻苯环的活性顺序为:对位>邻位>间位,根据产物变化提出了苯酚降解路径.     

Study of the effect of technological parameters of extractive wastewater purification in production of bisphenols

Effect of various technological parameters of the process in which wastewater formed in production of bisphenols is purified to remove phenol. The optimal parameters of the process were determined, with which a processed wastewater is obtained with phenol concentration that enables recycling of wastewater into the technological process and its partial delivery to treatment facilities.     

Assessment of the fate of some household micropollutants in urban wastewater treatment plant

Everyday domestic activity is a significant source of water pollution. The presence of six household micropollutants in an urban wastewater treatment plant (WWTP) was assessed in wastewater and sludge. A multi-target analytical method was developed for the quantification of ibuprofen, erythromycin, ofloxacin, 4-nonylphenol, 5-chloro-2-(2,4-dichlorophenoxy)phenol (triclosan), and sucralose. The micropollutants were extracted from the liquid and solid phases and their concentrations were determined by LC-MS/MS. The efficiency of micropollutants’ removal within a conventional activated sludge process was assessed. From 50 % to 90 % of ibuprofen and erythromycin was removed from the wastewater liquid phase. Their removal can be attributed to biological degradation as they were not found adsorbed on the outlet sludge. Ofloxacin and triclosan were removed from the liquid phase with similar efficiencies; however, they were adsorbed on the sludge, so it was not possible to determine their removal mechanism (whether biodegradation or displacement to solid phase/sequestration). Sucralose was not removed from wastewater (3 μg L^?1 in inlet and outlet liquid phase) and not adsorbed on the sludge. 4-Nonylphenol concentrations were sometimes higher in the WWTP outlet water; this may relate to the degradation of alkylphenol ethoxylates in the wastewater treatment process. 4-Nonylphenol was always present in the outlet sludge.