二茂铁催化光助非均相类Fenton氧化法处理含罗丹明B废水

采用二茂铁(Fc)替代UV/Fenton体系中的催化剂Fe2+,构建了一个新的UV/H2O2/Fc非均相Fenton反应体系,研究了该反应体系对含罗丹明B模拟废水的脱色性能.结果表明,Fc对水中UV/Fenton反应具有良好的催化活性,对罗丹明B起氧化作用的主要物质是·OH和其他活性物质.对水中罗丹明B的氧化脱色反应的催化性稳定,对Fc重复回收利用3次后对模拟废水仍有99%以上的脱色率;UV/H2O2/Fc体系处理罗丹明B的最佳工艺条件是H2O2的浓度为1.5′10-2mol/L,Fc的投加量为0.13g/L,初始pH值在2~6之间.证实了Fc作为光助非均相Fenton体系催化剂的可能性.     

光助Fenton反应催化剂Fe/Al2O3的制备及其对六氯苯的催化活性研究

采用超声促进浸渍法制备了光助Fenton催化剂Fe/Al2O3,利用该催化剂对六氯苯（HCB）进行光助Fenton氧化降解,考察了浸渍液浓度、浸渍温度、灼烧温度和灼烧时间等制备条件对其催化降解六氯苯的活性的影响,确定了制备Fe/Al2O3的工艺条件,并对制得的催化剂进行表征。结果表明,超声促进浸渍法制备非均相光助Fenton反应催化剂Fe/Al2O3的最佳工艺条件为：浸渍液浓度25mmol/L,浸渍温度40℃,焙烧温度500℃,焙烧时间3h。在此条件下制备的催化剂对六氯苯的降解具有较高的催化活性。     

黄铁矿催化类Fenton反应处理阳离子红X-GRL废水

基于对天然矿物黄铁矿进行SEM、EDS表征的基础上,以黄铁矿为非均相类Fenton催化剂,以偶氮染料阳离子红X-GRL为目标污染物,考察了催化剂双氧水用量、溶液初始pH值、阳离子红X-GRL初始浓度、反应时间等因素对染料脱色效果的影响.结果表明,在H2O2浓度为26.6mg/L、矿用量1g/L、溶液初始pH值6.4左右的条件下,反应2min后,染料脱色率达95%左右.进行了黄铁矿在水溶液中的酸性氧化实验并且考察了Fe2+、SO42-浓度及溶液pH随矿重复利用次数的变化规律.初次使用的黄铁矿具有很强的酸性氧化特性,反应过程中伴随着大量Fe2+、SO42-及H+的溶出.染料的快速脱色主要是均相Fenton反应作用的结果.黄铁矿作为一种新的催化剂大大提高了类Fenton反应的催化活性,而且该新型类Fenton反应能克服传统Fenton反应适用pH范围小的局限性,拓展了Fenton反应在废水处理中的应用.     

超声强化非均相Fenton法处理甲基橙的研究

采用硅藻土负载Fe3+制备了非均相催化剂,并通过TiO2来提高催化剂的稳定性.研究了采用该催化剂的US/Fenton体系对甲基橙的降解效果.通过正交试验考察了pH值、H2O2浓度、催化剂投加量对处理效果影响的大小,分别为pH值＞H2O2＞催化剂.并通过单因素实验确定在最佳条件下:pH值=3,H2O2浓度为2 mmol/L催化剂投加量为2g/L,反应120min后,脱色率可以达到98%以上,COD的去除率也能够达到87.18%.此外Fe3+溶出实验表明TiO2可以提高催化剂的稳定性.     

天然矿物负载Fe/Co催化H2O2氧化降解阳离子红3R

类Fenton反应关键是催化剂的活性,利用浸渍法负载铁、钴双金属对天然矿物材料进行改性,提高其催化活性,并运用扫描式电子显微镜(SEM)、X射线能谱仪(EDS)、X射线衍射(XRD)等表征手段对负载前后的材料进行表征分析.结果表明负载后材料中生成Fe2O3和Co Fe2O4两种新物质.将合成的催化剂用于催化H2O2氧化阳离子红3R染料废水,在催化剂投加量3 g·L-1,H2O2投加量0.3 m L·L-1,反应时间1 h条件下,100 mg·L-1阳离子红3R废水脱色率可达99.8%,TOC去除率可达58.4%,催化剂中活性组分主要为表面负载的Fe2O3和Co Fe2O4,电子自旋共振(ESR)分析表明催化氧化过程中产生羟基自由基,阳离子红3R发色基团在1 min已被完全破坏,光谱分析表明反应过程中有小分子物质生成.催化氧化效果受染料废水初始p H值影响小,适应p H范围广,解决了传统Fenton反应p H条件苛刻的问题.研究结果为印染废水处理提供了具有工程应用潜力的技术方法.     

制备工艺对La改性湿式氧化催化剂活性和稳定性的影响

采用CWAO(催化湿式空气氧化)法处理甲基橙模拟印染废水,以过量浸渍法制备催化剂,以水样COD_Cr去除率和脱色率表征催化剂的活性,以催化剂使用后处理出水中溶出的金属离子质量浓度表征催化剂的稳定性. 结果表明,多组分催化剂的金属组分构成为Cu、Fe、La,m(Cu)∶m(Fe)∶m(La)为1∶1∶2, 35℃下动态共浸渍8h,450℃下焙烧3h,由此制备得到Cu-Fe-La/FSC催化剂. 应用该催化剂,以CWAO法处理模拟印染废水,废水COD_Cr去除率和脱色率可分别达到79.1%和98.9%,催化剂的活性较高;使用该催化剂处理后的废水中Cu、Fe、La、Al的溶出量(以ρ计)分别为6.1、2.4、2.2、3.2mg/L,说明金属元素的溶出量较低,催化剂的稳定性较高.      

树脂负载Fe3+/Cu2+多相类芬顿降解染料橙黄

制备了新型多相类Fenton催化剂(Fe3+cu2+)/R(Fe3+和cu2+同时负载于离子交换树脂),以橙黄Ⅳ为研究对象,探讨了初始过氧化氢浓度、橙黄Ⅳ浓度、催化剂量、初始pH值及温度等因素对催化反应速率的影响,并对该催化剂重复使用性能进行测试.研究结果表明,该催化剂(Fe3++Cu2+)/R与Fe3+/R相比表现出更好的催化过氧化氢分解的活性,使橙黄Ⅳ的降解率提高10%;催化过氧化氢氧化橙黄Ⅳ的反应遵循假一级反应动力学,反应活化能为10.71 kJ·mol-1;催化剂表现出良好的重复使用性能,Fe3+和cu2+在树脂表面负载比较牢固,具有较好的稳定性和耐用性.同时,电子顺磁共振(EPR)测试结果表明,cu2+的掺杂能有效地促进OH·的产生;X射线光电子能谱(XPS)测试结果表明,反应过程中存在高价态铁物种.因此,在该体系反应过程中产生的活性物种是OH·和高价态铁同时共存.     

赤铁矿光助类Fenton降解有毒有机污染物

可见光照射下(λ>420 nm)采用天然赤铁矿为催化剂降解罗丹明B(rhodamine B,RhB)和无色小分子2,4-二氯苯酚(2,4-dichlorophenol,DCP),探讨了溶液pH、催化剂用量、溶液中溶铁量对降解反应的影响,通过紫外-可见分光光度计、红外光谱仪、苯甲酸荧光光度法以及COD等跟踪降解过程,并对反应机制做了初步探讨.结果表明,Cata/RhB/H2O2/vis体系能有效地降解RhB,降解最佳条件为:催化剂用量0.6 g.L-1、pH为3.0、H2O2浓度1.5×10-3mol.L-1,反应180 min可完全脱色,且溶铁对催化体系的贡献较小;对2,4-DCP的降解,24 h后,降解率达56%.且该催化剂具有良好的稳定性,循环使用6次,催化剂活性无明显变化.苯甲酸荧光光度法检测到反应体系中产生了高活性氧化物种.OH,反应机制主要是.OH的异相类Fenton过程.     

响应面法优化印染废水的脱色研究

以肼黄染料废水为模拟对象,在单因素试验的基础上通过响应面法优化Fenton氧化的脱色效果,研究了初始pH值、Fe2+投加量和H2O2投加量3个因素在该废水脱色过程中的显著性和交互性.结果表明,这3个因素对肼黄染料废水的脱色率的影响均具有显著性,且初始pH值与Fe2+投加量的交互影响、Fe2+投加量与H2O2投加量的交互影响也具有显著性.响应面法优化得到的最佳脱色工艺:初始pH值为3.19,Fe2+质量浓度为23.2 mg/L,H2O2质量浓度为345.4 mg/L,反应温度45℃,反应时间5 min;在此条件下的理论脱色率为90.85％,与3次实际平行试验的脱色率均值仅相差2.30％.     

制备工艺对La改性湿式氧化催化剂活性和稳定性的影响

采用CWAO(催化湿式空气氧化)法处理甲基橙模拟印染废水,以过量浸渍法制备催化剂,以水样COD Cr去除率和脱色率表征催化剂的活性,以催化剂使用后处理出水中溶出的金属离子质量浓度表征催化剂的稳定性.结果表明,多组分催化剂的金属组分构成为Cu、Fe、La,m(Cu)∶m(Fe)∶m(La)为1∶1∶2,35℃下动态共浸渍8 h,450℃下焙烧3 h,由此制备得到Cu-Fe-La/FSC催化剂.应用该催化剂,以CWAO法处理模拟印染废水,废水COD Cr去除率和脱色率可分别达到79.1%和98.9%,催化剂的活性较高;使用该催化剂处理后的废水中Cu、Fe、La、Al的溶出量(以ρ计)分别为6.1、2.4、2.2、3.2 mg/L,说明金属元素的溶出量较低,催化剂的稳定性较高.     

Photoassisted Fenton degradation of phthalocyanine dyes from wastewater of printing industry using Fe(Ⅱ)/γ-Al2O3 catalyst in up-flow fluidized-bed

Fe(II)/γ-Al2O3 powders synthesized using the dipping method were produced from a mixed aqueous solution containing aluminium oxide(γ-Al2O3) and iron(II)-precursor(FeSO4), and used for photoFenton degradation of phthalocyanine dyes(PCS) under ultraviolet(UV) irradiation in an up-flow fluidized bed. The catalysts were characterized by XRD, ESCA, BET, EDS and SEM. The results showed that Fe2+ion was compounded on the γ-Al2O3 carrier. The effects of different reaction parameters such as catalyst activity, dosage and solution pH on the decolorization of PCS were assessed. Results indicated that maximum decolorization(more than 95%) of PCS occurred with20 wt% Fe(II)/γ-Al2O3 catalyst(dosage of 60 g/L) using a combination of UV irradiation and heterogeneous Fenton system. The degradation efficiency of PCSincreases as pH decreases, exhibiting a maximum efficiency at pH 3.5. The recycled catalyst was capable of repeating three runs without a significant decrease in treatment efficiency, and this demonstrated the stability and reusability of catalyst.     

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process

Characteristics of toluene decomposition and formation of nitrogen oxide(NOx) by-products were investigated in a dielectric barrier discharge(DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide(Mn Ox), iron oxide(Fe Ox), cobalt oxide(Co Ox) and copper oxide(Cu O), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density(SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the Cu O catalyst showed the best performance in NOx suppression. The Mn Ox catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.     

Iron-doped Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO with NH3

The catalysts of iron-doped Mn-Ce/TiO 2(Fe-Mn-Ce/TiO 2) prepared by sol-gel method were investigated for low temperature selective catalytic reduction(SCR) of NO with NH 3.It was found that the NO conversion over Fe-Mn-Ce/TiO 2 was obviously improved after iron doping compared with that over Mn-Ce/TiO 2.Fe-Mn-Ce/TiO 2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity.The results showed that 96.8% NO conversion was obtained over Fe(0.1)-Mn-Ce/TiO 2 at 180°C at a space velocity of 50,000 hr 1.Fe-Mn-Ce/TiO 2 exhibited much higher resistance to H 2 O and SO 2 than that of Mn-Ce/TiO 2.The properties of the catalysts were characterized using X-ray diffraction(XRD),N 2 adsorption,temperature programmed desorption(NH 3-TPD and NOx-TPD),and Xray photoelectron spectroscopy(XPS) techniques.BET,NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping.It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe3+ state.The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts.The oxygen concentrations on the surface of the catalysts were found to increase after iron doping.Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H2 O and SO2.     

Treatment of phenol wastewater by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process

The catalyst of CuOx/Al2O3 was prepared by the dipping-sedimentation method using γ-Al2O3 as a carrier. CuO and Cu2O were loaded on the surface of γ-Al2O3, characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). In the presence of CuOx/Al2O3, the microwave-induced chlorine dioxide (ClO2) catalytic oxidation process was conducted for the treatment of synthetic wastewater containing 100 mg/L phenol. The relationships between removal percentage and initial ClO2 concentration, catalyst dosage, microwave power, contact time, initial phenol concentration and pH were investigated and the results showed that microwave-induced ClO2-CuOx/Al2O3 process could effectively degrade contaminants in a short reaction time with a low oxidant dosage, extensive pH range. Under a given condition (ClO2 concentration 80 mg/L, microwave power 50 W, contact time 5 min, catalyst dosage 50 g/L, pH 9), phenol removal percentage approached 92.24%, corresponding to 79.13% of CODCr removal. The removal of phenol by microwave-induced ClO2-CuOx/Al2O3 catalytic oxidation process was a complicated non-homogeneous solid/water reaction, which fitted pseudo-first-order by kinetics. Compared with traditional ClO2 oxidation, ClO2 catalytic oxidation and microwave-induced ClO2 oxidation, microwave-induced ClO2 catalytic oxidation system could significantly enhance the degradation efficiency. It provides an effective technology for the removal of phenol wastewater.     

TiO2及负载Fe(Ⅲ)可见光催化H2O2降解扑草净的协同效应

以TiO2P25(TIO-P25)及Fe(NO3)3为前驱物制备TiO2负载Fe3+多相催化剂Fe/TIO-P25,研究Fe/TIO-P25可见光催化H2O2降解扑草净的协同效应.XRD、XPS、EDS及SEM结果表明,Fe元素以Fe2O3形式高度分散于TiO2表面,负载量约1.5%(wt%),未对TIO-P25的粒径及形貌产生明显影响,Fe/TIO-P25的粒径约20~40nm;光催化结果表明,Fe/TIO-P25能可见光催化H2O2降解扑草净,反应30min降解率达100%,远大于TIO-P25的催化活性,负载Fe与TIO-P25之间存在明显的协同效应;通过对反应体系的荧光光谱分析显示,扑草净的降解涉及较单纯羟基自由基(·OH)过程更为复杂的反应机理.     

光助非均相芬顿体系中羟基自由基的荧光光谱法测定与影响因素研究

以TiO2/Al2O3为载体制备了Fe2O3/TiO2/Al2O3催化剂,建立了三相流化床光助非均相芬顿反应体系.选取香豆素为羟基自由基捕获剂,采用荧光法检测光助非均相芬顿反应体系中产生的活性中间体,发现在体系中有高活性的羟基自由基生成.实验讨论了溶液的pH值、H2O2投加量、催化剂投加量、光强对光助非均相芬顿反应体系中羟基自由基生成量的影响.结果表明,以香豆素为羟基自由基捕获剂的实验方法可以较好地检测不同实验条件下光助非均相芬顿反应体系中产生的羟基自由基,且该光助非均相芬顿反应体系中羟基自由基的生成在30 min内符合零级反应动力学.溶液的pH值、H2O2投加量、催化剂投加量、光强均对反应体系中羟基自由基的生成存在一定的影响.     

吸附树脂/铁酞菁对甲基橙的光催化降解

针对铁酞菁在水溶液中易于聚合而降低催化活性,同时在均相光催化体系中分离困难、难以重复利用的问题,将铁酞菁负载在吸附树脂上,制得多相催化剂。该催化剂在可见光的照射下能有效地催化H2O2降解偶氮染料甲基橙。考察了催化剂用量、H2O2投加量、pH值、温度等因素对甲基橙去除效果的影响。结果表明,甲基橙初始浓度为50 mg/L,卤灯功率为100 W,催化剂投加量为1.0 g/L,H2O2用量为0.2 mol/L,pH为3,温度为35℃时,反应10 h,甲基橙去除率达到91%,且催化剂所含铁离子无流失,具有很好的稳定性,可重复使用。     

不同纳米级锐钛型TiO2的V2O5基催化剂脱氮性能

以2种不同纳米级锐钛型TiO2为载体负载V2O5和WO3制备得到脱氮催化剂H和Z,在自制固定床反应器中测试其DeNOx活性,结果表明,催化剂H的活性比催化剂Z低得多.利用XRD、BET、FT-IR和SEM等手段对2种催化剂进行比较,BET表面积虽然会对DeNOx活性产生一定的影响,但催化剂H主要因为活性物质V2O5和载体TiO2发生反应,生成V3Ti6O17,导致其DeNOx活性大幅下降,而在催化剂Z中TiO2仍然保持锐钛型,未与V2O5发生反应.