Fenton催化氧化降解藻毒素MCLR的效能研究

研究了Fenton试剂对饮用水中藻毒素MCLR的降解效能,考察了H2O2用量、Fe2+H2O2最佳摩尔比、pH值和反应时间对Fenton降解藻毒素的影响,得到Fenton降解藻毒素的最佳反应条件:H2O2浓度为0.24mol·L-1、Fe2+H2O2摩尔比1∶9、初始pH值为2～3.5、反应时间为45min.同时采用邻二氮菲Fe(Ⅱ)光度法检测Fenton反应中生成的羟基自由基,从而很好地阐明了Fenton催化氧化降解藻毒素的强氧化作用机制.高效液相色谱分析发现,作用机制可能是Fenton催化氧化藻毒素,生成某种相对稳定的中间产物,然后异构化Adda基团的共轭双键,使Adda基团的结构发生变化,从而降低其毒性.     

催化臭氧化降解磺基水杨酸的机理

通过对不同工艺参数的考察及催化剂活性组分变化的分析,探讨了VO₂/硅胶催化臭氧化降解磺基水杨酸的机理.结果表明,催化体系的本质是催化剂中的四价钒催化臭氧分解生成了活性更高的羟基自由基,所生成的五价钒对体系化学耗氧量(COD)的去除也有很大的贡献(近10%).循环使用试验表明,20min时,VO₂/硅胶催化剂在第1次和第10次的COD去除率分别为76%和70%,显示了较好的应用前景.     

Recent advances in catalytic decomposition of ozone

Ozone (O₃), as a harmful air pollutant, has been of wide concern. Safe, efficient, and economical O₃ removal methods urgently need to be developed. Catalytic decomposition is the most promising method for O₃ removal, especially at room temperature or even subzero temperatures. Great efforts have been made to develop high-efficiency catalysts for O₃ decomposition that can operate at low temperatures, high space velocity and high humidity. First, this review describes the general reaction mechanism of O₃ decomposition on noble metal and transition metal oxide catalysts. Then, progress on the O₃ decomposition performance of various catalysts in the past 30 years is summarized in detail. The main focus is the O₃ decomposition performance of manganese oxides, which are divided into supported manganese oxides and non-supported manganese oxides. Methods to improve the activity, stability, and humidity resistance of manganese oxide catalysts for O₃ decomposition are also summarized. The deactivation mechanisms of manganese oxides under dry and humid conditions are discussed. The O₃ decomposition performance of monolithic catalysts is also summarized from the perspective of industrial applications. Finally, the future development directions and prospects of O₃ catalytic decomposition technology are put forward.     

催化臭氧化降解磺基水杨酸

选用3种固体催化剂催化臭氧化降解磺基水杨酸.结果表明,MnO₂和V₂O₅催化活性并不明显,而自制的钒氧化物(VO)催化剂具有较好的催化臭氧化性能.在本实验条件下与单独臭氧化相比,30min后VO/O₃体系的COD和TOC去除率由原来的58%和25%提高到86%和61%.VO催化剂的作用机理是催化臭氧分解产生了高活性氧化剂(如羟基自由基等).     

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios (25, 50, 100 and 200) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350°C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5 (25) exhibited the highest selectivity to N₂, exceeding 90% at 350°C. These samples were investigated in detail by several characterizations to illuminate the dependence of the catalytic performance on redox properties, Cu species, and acidity. The characterization results proved that the redox properties and chemisorption oxygen primarily affect n-butylamine conversion. N₂ selectivity was impacted by the Brønsted acidity and the isolated Cu²⁺ species. Meanwhile, the surface acid sites over Cu-ZSM-5 catalysts could influence the formation of Cu species. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra was adopted to explore the reaction mechanism. The Cu-ZSM-5 catalysts are the most prospective catalysts for nitrogen-containing volatile organic compounds removal, and the results in this study could provide new insights into catalysts design for VOC catalytic oxidation.     

催化燃烧技术处理VOCs的研究进展

催化燃烧是实现挥发性有机物(VOCs)高效燃烧的一种处理技术,文章总结介绍了国内外催化燃烧工艺的研究进展,比如固定床催化燃烧技术、整体式催化燃烧工艺、流化床催化燃烧反应工艺和流向变换催化燃烧与吸-放热耦合反应工艺,并在最后指出了今后催化燃烧的研究方向。     

催化臭氧化降解技术中的两个问题

探讨了有机物特性及中间产物H2O2在催化臭氧化中的作用。结果表明,有机物在自由基链反应过程中的特性直接影响催化臭氧化的降解效率。当目标有机物是对链反应具有促进作用的甲酸时,自由基引发反应可以明显提高甲酸的臭氧化效率。当目标有机物是对自由基链反应具有抑制剂作用的乙酸时,O3和Fe^2＋/O3对乙酸有着相似的降解效率。以上结果表明,自由基引发反应并不是臭氧化降解效率提高的充分条件。另外,当臭氧化过程有H2O2产生时,必须考虑类Fenton反应对臭氧化效率的影响。     

Studies on catalytic reduction of nitrate in groundwater

Catalytic reduction of nitrate in groundwater by sodium formate over the catalyst was investigated. Pd-Cu/γ-Al₂O₃ catalyst was prepared by impregnation and characterized by brunauer-emmett-teller (BET), inductive coupled plasma (ICP), X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy dispersive X-ray (EDX). It was found that total nitrogen was effectively removed from the nitrate solution (100 mg/L) and the removal efficiency was 87%. The catalytic activity was affected by pH, catalyst amount used, concentration of sodium formate, and initial concentration of nitrate. As sodium formate was used as reductant, precise control in the initial pH was needed. Excessively high or low initial pH (7.0 or 3.0) reduced catalytic activity. At initial pH of 4.5, catalytic activity was enhanced by reducing the amount of catalyst, while concentrations of sodium formate increased with a considerable decrease in N₂ selectivity. In which case, catalytic reduction followed the first order kinetics. Translated from Acta Scientiae Circumstantiae, 2006, 26(4): 567–571 [译自: 环境科学学报]     

铜前驱体对Cu/SSZ-13催化剂选择性催化氧化NH3性能的影响

采用浸渍法制备了一系列Cu/SSZ-13(X)催化剂,考察不同铜前驱体对催化剂选择性催化氧化氨(NH_3-SCO)性能的影响,并通过ICP、N_2吸附-脱附、XRD、XPS、EPR、UV-Vis、NH_3-TPD和H_2-TPR等手段对催化剂进行物化性质表征.活性测试结果表明,不同铜前驱体制备的Cu/SSZ-13催化剂活性顺序为Cu/SSZ-13(N) Cu/SSZ-13(AC) Cu/SSZ-13(Cl) Cu/SSZ-13(O).其中Cu/SSZ-13(N)具有最佳的低温活性,在200℃反应温度下NH_3转化率达85.5%,且N_2选择性达到80%以上.XRD、EPR和UV-Vis分析表明,CuO和孤立Cu~(2+)是Cu/SSZ-13催化剂的主要铜物种.NH_3-TPD分析表明,以硝酸铜为前驱体制备的Cu/SSZ-13(N)具有更多的酸性位点,有利于提高催化剂的NH_3吸附能力.H_2-TPR结果表明,Cu/SSZ-13(N)的氧化还原性最强,具有最优异的NH_3活化能力,从而使催化剂呈现最好的低温NH_3-SCO活性.     

非均相催化臭氧处理高浓度制药废水的研究

非均相催化臭氧是一种对高浓度制药废水进行预处理的有效方法.本研究采用单一活性炭吸附、单一臭氧氧化和臭氧/活性炭联用3种体系对实际制药废水进行预处理,并对处理过程中的工艺参数进行优化.结果表明,相比单一活性炭吸附和单一臭氧降解体系,臭氧/活性炭联用体系能显著提高COD、TOC的去除率及BOD5/COD值,并显示出良好的协...     

紫外催化过硫酸盐深度处理垃圾焚烧厂渗滤液

为研究垃圾焚烧厂渗滤液生化出水的处理特性,对比了单独紫外(UV)体系、单独过硫酸盐(PS)体系以及紫外/过硫酸盐(UV/PS)体系深度处理垃圾渗滤液效果,发现UV/PS体系对渗滤液中有机污染物的去除效果较另外两体系的效果优异,因此采用UV/PS体系处理典型难降解有机物腐殖酸并考察体系的处理效能.在初始腐殖酸浓度为200mg/L、PS投加量为25mmol/L、初始pH值为4的条件下,UV₂₅₄最大去除率为89.62%,TOC最大去除率为76.17%.研究温度、初始pH值、药剂投加比例等因素对UV/PS工艺处理渗滤液的影响,结果表明,工艺处理效果良好,最优条件为温度为35℃、pH值为4、加药比为2、运行24h,COD的去除率最大为82.64%,TOC的最大处理效能为66.69%,同时该体系对色度的去除能力符合拟二级动力学方程.本文可为垃圾焚烧厂渗滤液深度处理提供数据依据.     

催化臭氧化饮用水中甲草胺的研究

利用Fe2+、Mn2+和腐殖酸对水中甲草胺进行了催化臭氧化研究.实验表明,少量的催化剂就可促进甲草胺的降解,过量则会产生抑制作用.深入研究表明,甲草胺的降解与具有极强氧化能力的羟基自由基有关.     

Complete catalytic oxidation of o-xylene over Ce02 nanocubes

The activities of CeO2 nanocubes calcined at different temperatures were tested for catalytic oxidation of o-xylene. Using CeO2 nanocubes as catalysts, complete catalytic oxidation of o-xylene was achieved below 210℃. The CeO2 nanomaterials were characterized by means of BET, X-ray diffraction (XRD), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). From the TEM images, all Ce02 nanocubes displayed cubic morphology irrespective of calcination temperature. The HRTEM images revealed that these nanocubes were enclosed by reactive {001}planes, which may contribute to the intrinsically catalytic property of o-xylene oxidation. The higher activity of Ce02 nanocubes calcined at 550℃ than those calcined at above 550℃ was attributed to their smaller crystallite size and larger surface area. The influences of reaction conditions were also studied, which found that a higher reaction temperature was necessary for complete catalytic oxidation of o-xylene at higher weight hourly space velocity (WHSV) and o-xylene concentration.     

Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H_2-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the Ce O_2 fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

微波诱导NiO催化降解水中邻苯二甲酸二甲酯

采用超声辐射沉淀-氧化法制备了纳米催化剂NiO,用XRD、XPS、BET和SEM等方法对其进行了表征.构建了微波-NiO催化反应体系,考察了该体系对DMP的去除效率及影响因素,并利用GC/MS、LC/MS鉴定降解产物,提出了可能的降解机理.结果表明：微波诱导NiO催化氧化技术是降解DMP的有效方法,在微波（750W）诱导NiO（0.4mg/L）催化降解体系中,15min内10mg/L DMP的去除率达70%以上.降解效率受到反应体系中不同条件的影响：微波功率的增加可以提高降解效率;催化剂NiO浓度越高,降解速率越快;溶液初始pH值对DMP的降解效率影响非常大,随着pH值的增大,降解效率明显提高.通过GC/MS、LC/MS分析,反应过程中DMP的降解产物主要包括双链水解产物邻苯二甲酸以及异构化产物对苯二甲酸、单链水解产物邻甲酯苯甲酸、苯环三取代产物甲酯基-邻苯二甲酸、侧链缩合形成的双环产物和少量小分子有机酸,由此推断DMP在微波诱导NiO催化体系中的降解主要包括6个途径：水解、异构化、甲酯基反应、侧链缩合成环、羟基化和开环等.     

NH_3的低温复相选择性催化氧化

采用Cu-Ag/Al2O3复合催化剂在低温下选择性催化氧化 NH3.实验结果表明,Ag/Al2O3 和 Cu/Al2O3分别具有高氧化活性和高 N2选择性的优点;一定负载量范围内,Cu-Ag/Al2O3复合催化剂既具有高氧化活性(介于Ag/Al2O3和Cu/Al2O3之间),又具有Cu/Al2O3的高N2选择性,当反应温度为280℃时,Cu5%-Ag5%/Al2O3对NH3的氧化率大于96%,N2选择性大于95%.催化剂表面上形成的Ag2O 颗粒及其大小是影响催化剂选择性的一个重要因素.     

纤维类废弃物的热化学催化液化试验研究

对纤维类废弃物热化学催化液化反应各反应物的用量比例、反应条件进行优化,并初步测定了最优条件下液化产物的组分.结果表明,纤维类废弃物在浓硫酸/苯酚(浓硫酸的质量分数为6%)的混合催化体系中,当温度为160℃,时间为70min时的液化效果最好.气相色谱-质谱联用仪和红外光谱仪的分析结果表明,液化产物中甲基和亚甲基等基团的振动加强,以及存在麦草纤维素的单体葡萄糖的衍生物,液化反应破坏了纤维类废弃物的晶格结构,从而打破了生物利用的禁锢,使其易被微生物降解.利用液化产物进行混合菌株发酵培养,其真蛋白含量可达到30.74%;其酒精含量可达到19.0%(V/V).     

Pretreatment of apramycin wastewater by catalytic wet air oxidation

IntroductionPharmaceuticalindustrybecomesmoreandmoreimportantallovertheworld .InChina ,therearemorethan30 0plantsmanufacturingantibioticproduction .However,theplantsoftenproducealotofwastewatercontaininghighconcentrated,colortoxicorganiccompounds.Ifthepol…     

超声协同非均相类Fenton反应氧化去除苯酚

用CuO-Ce/Al₂O₃为催化剂超声协同非均相类Fenton催化氧化去除苯酚,考察了H₂O₂浓度,催化剂用量,pH值,超声功率,不同工艺条件对苯酚去除率的影响,及催化剂使用过程中铜的溶出情况.通过XPS（X射线光电子能谱）、SEM（扫描电镜）、BET（Brunauer-Emmett-Teller）表征了催化剂使用过程有无超声的表面状态变化.结果表明,在pH值6.0,H₂O₂浓度1650mg/L,催化剂用量3.5g/L,功率500W的条件下,苯酚模拟废水去除率为99.65%,不同工艺去除苯酚的能力顺序为US/H₂O₂/CuO-Ce/Al₂O₃,H₂O₂/CuO-Ce/Al₂O₃,US/CuO-Ce/Al₂O₃,US/H₂O₂,US.催化剂比表面积、孔径孔容、活性组分表面含量是影响催化剂活性性能的重要原因,超声作用能够加速活性组分的溶出,但同时延缓比表面积、碳沉积、孔体积的恶化过程.     

臭氧/钛酸铋系化合物催化氧化降解橙黄Ⅳ的初步研究

采用化学溶液分解法制备了钛酸铋系化合物,并研究了其催化臭氧化降解橙IV(C18H14KN3O35)溶液的性能.结果表明,在Bi/Ti摩尔比12:1、热处理温度550℃条件下制备的催化剂性能最优,其COD去除率达40.3%,比单独臭氧作用(20.3%)提高了1倍,并明显优于TiO2和Bi2O3的催化效果(分别为28.9%和21.4%).同时,考察了催化剂投量、橙IV初始浓度、臭氧投量、pH值、重复使用等反应条件对催化剂性能的影响.初步推断,此催化臭氧化反应为非羟基自由基的含氧自由基作用机理.