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.      

催化湿式氧化法处理有机废水的催化剂研究

催化湿式氧化法是处理高浓度、有毒有害、难降解有机废水的一种有效手段.本文分析总结了过渡金属、贵金属和稀土金属等作为均相催化剂与非均相催化剂,采用催化湿式氧化法处理有机废水的性能,特别是比较了它们处理多种有机废水时对COD的去除效率和载体的使用情况.从分析中可以看出,氧化铝是非常好的载体,多组分复合催化剂比单组分催化剂具有更好的催化性能,以Cu、Mn、Ce为主要活性组分的复合催化剂具有很高的催化活性,并且应用范围广.最后探讨了催化剂的反应机理和发展前景.     

垃圾渗滤液主要组分的催化湿式氧化降解

利用Mn/Ce复合氧化物催化剂对“年老”垃圾渗滤液主要组分正己酸、正丁酸、乙酸及氨氮进行催化湿式氧化(CWAO)降解,分析了CWAO降解过程中有机酸之间及氨氮与有机酸之间的关系.结果表明,CWAO可降解垃圾渗滤液中正己酸、正丁酸、乙酸,反应进行120min时TOC去除率均达90%以上.降解乙酸、正丁酸和正己酸混合溶液时,升温过程出现有机酸相互抑制降解现象.氨氮的存在导致正丁酸的降解率下降,而有机酸的存在也抑制了氨氮的降解.Ni2+可使催化剂中毒,使催化剂活性降低.     

羧酸类有机物催化湿式氧化过程中ZnFe0.25Al1.75O4催化剂的稳定性研究

草酸、甲酸和乙酸是催化湿式氧化过程3种最主要的小分子羧酸类中间产物．比较了ZnFe_0.25Al_1.75O₄催化剂降解这3种物质时的催化活性和铁离子溶出量的大小．160℃下草酸是唯一可被完全降解的物质,降解过程中铁溶出量高达9.5 mg·L^-1;而甲酸和乙酸对铁离子稳定性影响很小．由于草酸具有很强的酸性和还原性,铁溶出量在氮气气氛中比在氧气气氛中大．ZnFe_0.25Al_1.75O₄催化剂对水杨酸也具有很高的降解活性和稳定性．     

丙烯腈生产废水的催化湿式氧化

在高压反应釜中采用Mn-Ce和Co-Bi复合催化剂通过催化湿式氧化法处理丙烯腈废水。试验结果表明Mn-Ce和Co-Bi复合氧化物催化剂的活性强烈的依赖于Mn-Ce和Co-Bi的组成。Co-Bi复合催化剂对丙烯腈废水的氧化活性最高,且在酸性溶液中无金属离子溶出问题。在反应温度190～200℃,氧气的分压1.5～1.8MPa,反应时间为90min,丙烯腈废水的COD去除率超过90%。     

Change in genotoxicity of wastewater during chlorine dioxide and chlorine disinfections and the influence of ammonia nitrogen

The effects of chlorine dioxide and chlorine disinfections on the genotoxicity of different biologically treated sewage wastewater samples were studied by umu-test. The experiment results showed that when chlorine dioxide dosage was increased from 0 to 30 mg/L, the genotoxicity of wastewater first decreased rapidly and then tended to be stable, while when the chlorine dosage was increased from 0 to 30 mg/L, the genotoxicity of wastewater changed diversely for different samples. It was then found that ammonia nitrogen did not affect the change of genotoxicity during chlorine dioxide disinfection of wastewater, while it greatly affected the change of genotoxicity during chlorine disinfection of wastewater. When the concentration of ammonia nitrogen was low (< 10–20 mg/L), the genotoxicity of wastewater decreased after chlorine disinfection, and when the concentration of ammonia nitrogen was high (> 10–20 mg/L), the genotoxicity of wastewater increased after chlorine disinfection.     

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.     

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, H₂-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 CeO₂ 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.     

Catalytic wet air oxidation for the treatment of emulsifying wastewater

The wet air oxidation (WAO) and catalytic WAO(CWAO) of the high strength emulsifying wastewater containing nonionic surfactants have been investigated in terms of COD and TOC removal. The WAO and homogeneous CWAO processes were carried out at the temperature from 433 K to 513 K, with initial oxygen pressure 1.2 MPa. It was found that homogeneous catalyst copper(Cu(NO3)2) had an fairly good catalytic activity for the WAO process, and the oxidation was catalyzed when the temperature was higher than 473K. Moreover, several heterogeneous catalysts were proved to be effective for the WAO process. At the temperature 473 K, after 2h reaction, WAO process could achieve about 75% COD removal and 66% TOC removal, while catalysts Cu/Al2O3 and Mn-Ce/Al2O3 elevated the COD removal up to 86%-89% and that of TOC up to 82%. However, complete elimination of COD and TOC was proved to be difficult even the best non-noble catalyst was used. Therefore, the effluent from WAO or CWAO process need to be further disposed. The bioassay proved that the effluent from WAO process was amenable to the biochemical method.     

催化剂及其制备对催化湿式氧化反应的影响

催化湿式氧化法是一种有效的处理有毒、有害、高浓度有机废水的水处理技术,文章专门针对催化剂本身的制备对催化湿式氧化的影响,以及催化剂的失活、再生、重复利用等研究做出总结,以期对有关研究者提供一定的参考。     

温度对WAO/CWAO处理垃圾渗滤液的影响

催化湿法氧化 (CWAO)是用于处理有机废水十分有效的物理化学方法 ,本实验将该方法用于垃圾渗滤液的处理 .使用CWAO处理垃圾渗滤液 ,温度是一个重要的影响因素 ,因此本研究着重研究温度对污染物去除效率、降解速率的影响 ,建立了温度与速率常数之间的定量关系 ,并初步考察了催化剂 (Co/Bi)在降解垃圾渗滤液过程中的作用 .实验中利用高压反应釜并使用催化剂 ,在封闭条件下对垃圾渗滤液进行处理 ,研究温度对降解反应的影响 .结果表明 :有、无催化剂存在的条件下 ,随着温度的升高 ,总有机碳 (TOC)和COD的去除率均显著增大 ;用Elovich方程可以描述垃圾渗滤液降解反应的动力学过程 ,速率常数k值随着温度的升高而逐渐增大 ,并建立了速率常数k与温度的定量关系式 ;反应液 pH值在反应过程中先迅速降低 ,之后缓慢上升 ,主要由于反应初期生成了大量的有机酸 ,而随着有机酸逐渐被降解 ,反应液 pH值缓慢上升 .通过本研究可知 ,以Co/Bi作催化剂 ,利用CWAO降解稀释后的垃圾渗滤液 ,可以在较为温和的条件下达到较好的处理效果 ,但本研究仅探讨了温度对催化湿法氧化降解垃圾渗滤液有较大的影响 ,其它反应条件如氧化剂、催化剂用量以及垃圾渗滤液浓度等对CWAO法降解效率的影响还有待于进一步研究     

催化湿式氧化乐果农药废水及催化剂的研究

通过共沉淀法制备了用于湿式氧化乐果农药废水的Cu/Mn复合氧化物催化剂,研究了沉淀剂种类、沉淀温度、焙烧温度和活性组分配比等因素对Cu/Mn复合氧化物催化剂的活性及稳定性的影响,确定了最佳制备条件,利用BET比表面积测定和XRD对催化剂进行了表征。结果表明:优化条件制备的Cu/Mn复合氧化物催化剂催化湿式过氧化氢氧化处理乐果农药废水时,具有较高的催化活性和稳定性。催化剂用量以6 g/L,反应温度80℃,过氧化氢加入量为12.0 g/L,反应时间60 min,COD去除率为89.5%,活性组分溶出量较小。     

La0.8Ce0.2CoO3/Al2O3对油烟的催化净化

将稀土金属La、Ce和过渡金属Co按照一定的比例采用浸渍法负载在γ-Al2O3载体上制备成La0.8Ce0.2CoO3/Al2O3催化剂,用X-射线衍射仪和扫描电镜对催化剂负载层的表面形态、晶相结构和粒径大小进行了表征,并用正交实验法考察了其对油烟的催化净化效果。结果表明,当负载量30%、焙烧温度800℃、催化温度300℃、烟气流量10L/min时催化剂对油烟的净化效果最佳,净化效果可达88%,催化剂对油烟的催化具有较好的低温高活性。     

Fenton-like degradation of Methylene Blue using paper mill sludge-derived magnetically separable heterogeneous catalyst: Characterization and mechanism

For the paper industry, the disposal and management of the yielded sludge are a considerable challenge. In our work, the paper mill sludge-derived magnetically separable heterogeneous catalyst (PMS-Fe-380) was prepared easily through a facile synthesis method. The morphology and structure of PMS-Fe-380 were fully characterized by means of X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and Brunauer–Emmet–Teller analysis. The catalytic activity of PMS-Fe-380 was evaluated by degradation of Methylene Blue (MB). The reusability and stability of PMS-Fe-380 were evaluated in five repeated runs, which suggested that PMS-Fe-380 manifested excellent stability of catalytic activity. Moreover, leaching tests indicated that the leached iron is negligible (< 0.5 mg/L). This study provides an alternative environmentally friendly reuse method for paper mill sludge and a novel catalyst PMS-Fe-380 that can be considered as a promising heterogeneous Fenton-like catalyst.     

Mn基金属氧化物催化剂常温催化氧化甲醛

以硝酸铈和高锰酸钾为原料,采用络合法制备了一系列Mn-Ce-O混合氧化物催化剂,并通过正交实验设计方案,考察了Mn/Ce摩尔比、水化热温度、焙烧温度及焙烧时间对Mn-Ce-O混合氧化物催化剂常温催化氧化甲醛性能的影响,并采用X射线衍射仪（XRD）、扫描电镜（SEM）、透射电镜（TEM）和红外光谱（IR）等技术对催化剂进行微观表征与分析.结果表明：当Mn/Ce摩尔比1：1,水化热温度为180℃,焙烧温度为350℃时,催化剂表现出最佳的常温氧化活性,36h甲醛降解率可达94.2%,且稳定性良好.催化剂氧化活性的高低与材料比表面积并非正相关,而与材料结构形态存在密切关联,而材料结构主要取决于水化热温度,其次是Mn/Ce摩尔比.     

铁锰双金属氧化物对过硫酸氢钾降解酸性橙7的催化效果

为了发挥均相体系中过渡金属元素对PMS(过硫酸氢钾)的催化效果,同时解决存在的金属离子污染的问题,以AO7(酸性橙7)为目标污染物,研究了采用溶胶-凝胶法(sol-gel method)制备Fe-MnO_x(铁锰双金属氧化物)催化剂催化PMS的效果及降解机理. 结果表明:ρ(Fe-MnO_x)由50 mg/L升至200 mg/L后,35 min时AO7降解率由53.74%升至96.65%;继续升高ρ(Fe-MnO_x),AO7降解率提升效果不明显. 随着ρ(PMS)₀(PMS初始质量浓度)的升高,AO7的降解率变化趋势与之相同;而随着ρ(AO7)₀(AO7初始质量浓度)的升高,AO7降解率有所下降. 分别投加EA(乙醇)、TBA(叔丁醇)这2种捕获剂来验证体系氧化物种时发现,55 min时AO7降解率分别为79.40%和91.33%,氧化体系的主要氧化物种为·SO₄-(硫酸根自由基)和少量·OH(羟基自由基). XRD(X射线衍射)和XPS(X射线光电子能谱)结果显示,Fe-MnO_x催化剂中的Fe、Mn主要以Fe3+、Mn2+、Mn4+ 3种形式存在,Fe、Mn、O 3种元素中,Fe3+、Mn2+、Mn4+、O2-和表面羟基氧的摩尔比分别为20.49%、26.46%、5.60%、32.51%和14.91%. 研究显示,Fe-MnO_x催化剂具有金属离子溶出量低、催化性能良好等优良性能,能够有效催化PMS生成自由基,对水中的污染物具有良好的降解效果.      

CeO_2改性MnO_2/γ-Al_2O_3催化剂的制备及在有机废水处理中的应用

利用浸渍焙烧法制得CeO2改性MnO2/γ-Al2O3催化剂,在常温常压下采用微波诱导氧化技术,将废水中有机污染物氧化分解。初步探讨了催化剂的制备条件,结果显示,当Ce(NO3)3浸渍浓度0.01mol/L,Mn(NO3)2浸渍浓度0.05mol/L,焙烧温度350℃,焙烧时间3h时,催化剂性能达到最佳。研究了微波辐照时间、催化剂投加量、微波功率、pH值、初始浓度等因素对甲基橙处理效果的影响。在优化条件下对甲基橙的处理效果达95%以上。     

火山灰-活性炭的制备表征及其催化湿式氧化研究

采用自制的酚醛树脂基火山灰-活性炭负载Ce稀土催化剂在间歇式反应釜中催化湿式氧化(Catalytic wet air oxidation,CWAO)降解高浓度苯酚废水至可生化要求。发现经过浸渍、固化、炭化3个循环后可以获得9%的含炭量、1 020 m2/g的比表面积、0.57 cm3/g的总孔容并能满足后续反应所需的传质要求。同时研究了不同的炭化升温速率和炭化温度对火山灰-活性炭的性能的影响,发现升温速率为4℃/min、炭化温度为850℃时火山灰-活性炭获得最佳的结构特征。通过最佳工艺制备得到的催化剂,COD去除率达到92.4%,甲醛、苯酚去除率接近100%,BOD5/COD=0.42,满足可生化处理的要求。     

影响一体式好氧膜生物反应器膜清洗周期的几个因素

一体式好氧中空纤维膜生物反应器不同操作条件下处理生活污水的试验结果表明,在膜通量１０．４Ｌ／ｍ＾２．ｈ）污泥龄２０ｄ,污泥去除负荷（ＣＯＤ／ＶＳＳ）为０．２２ｋｇ（ｋｇ．ｄ）的正常稳定运行条件下,该系统可在整个膜寿命期限内（３－５ａ）不同洗燕得到优质出水;ＣＯＤ〈２０ｍｇ／Ｌ,ＮＨ３－Ｎ〈１．０ｍｇ／Ｌ,无色无味透明,未检出大肠杆菌,其中,污泥去除负荷,系统运行稳定状况和反应器流态是影响膜清洗周期     

Conversion of the refractory ammonia and acetic acid in catalytic wet air oxidation of animal byproducts

Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) of slaughtered animal byproducts (ABPs) were investigated. Two step experiment was carried out consisting of a non-catalysedWAO run followed by a CWAO run at 170–275°C , 20 MPa, and reaction time 180 min. TheWAO (1st step) of sample (5 g/L total organic carbon (TOC)) yielded (82.0 4)% TOC removal and (78.4 13.2)% conversion of the initial organic-N into NH4 +-N. Four metal catalysts (Pd, Pt, Rh, Ru) supported over alumina have been tested in catalytic WAO (2nd step) at elevated pH to enhance ammonia conversion and organic matter removal, particularly acetic acid. It was found that the catalysts Ru, Pt, and Rh had significant e ects on the TOC removal (95.1%, 99.5% and 96.7%, respectively) and on the abatement of ammonia (93.4%, 96.7% and 96.3%, respectively) with high nitrogen selectivity. The catalyst Pd was found to have the less activity while Pt had the best performance. The X-Ray di raction analysis showed that the support of catalyst was not stable under the experimental conditions since it reacted with phosphate present in solution. Nitrite and nitrate ions were monitored during the oxidation reaction and it was concluded that CWAO of ammonia in real waste treatment framework was in good agreement with the results obtained from the literature for ideal solutions of ammonia.