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.     

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.      

中国部分城市铂族元素环境地球化学特征研究

自上世纪90年代起,汽车工业中大量引入铂族元素催化剂,将有害气体转变为二氧化碳和氮气,以降低这些温室气体的排放。但铂族元素催化剂释放的Pt,Pd和Rh等元素在城市道路尘土和路边土壤中聚积,其含量大大的超过正常背景值。本次研究在深圳,广州,北京和贵阳等城市的主要交通路段采集了尘土、土壤及新鲜土壤样品,采用改进的卡洛斯管法和蒸馏法对样品中的全部铂族元素进行了分析。结果表明,所有样品的铂族元素含量均高于背景值,尘土样品中铂族元素含量明显高于土壤样品,其中Pt,Pd,Rh含量明显高于其它铂族元素,并呈正相关,表明汽车尾气催化剂的主要组成为Pt,Pd,和Rh。所有样品Ru,Ir和Os的含量都明显高于背景值,具有高含量的Os、低的187 Os/188 Os比值特征,表明Ru,Ir和Os也来源于汽车尾气催化剂,并且可能以杂质的形式存在于汽车尾气催化剂中。     

Preparation of rare-earth metal complex oxide catalysts for catalytic wet air oxidation

Catalytic wet air oxidation (CWAO) is one of the most promising technologies for pollution abatement. Developing catalysts with high activity and stability is crucial for the application of the CWAO process. The Mn/Ce complex oxide catalysts for CWAO of high concentration phenol-containing wastewater were prepared by coprecipitation. The catalyst preparation conditions were optimized by using an orthogonal layout method and single-factor experimental analysis. The Mn/Ce serial catalysts were characterized by Brunauer-Emmett-Teller (BET) analysis and the metal cation leaching was measured by inductively coupled plasma torch-atomic emission spectrometry (ICP-AES). The results show that the catalysts have high catalytic activities even at a low temperature (80°C) and low oxygen partial pressure (0.5 MPa) in a batch reactor. The metallic ion leaching is comparatively low (Mn<6.577 mg/L and Ce<0.6910 mg/L, respectively) in the CWAO process. The phenol, COD_Cr, and TOC removal efficiencies in the solution exceed 98.5% using the optimal catalyst (named CSP). The new catalyst would have a promising application in CWAO treatment of high concentration organic wastewater. Translated from Techniques and Equipment for Environmental Pollution Control, 2005, 6(2): 40–44 [译自: 环境污染治理技术与设备]     

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.     

Pretreatment of apramycin wastewater by catalytic wet air oxidation

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

贵阳公路周边尘土和土壤铂族元素特征分析

为降低温室效应气体一氧化碳、氮氧化物及碳氢化合物的排放,全球自上世纪80年代末期开始在汽车中引入铂族元素(PGE)催化剂,其释放的Pt、Pd和Rh等元素在城市道路尘土和路边土壤中聚积,对自然环境及人体健康产生危害。本文在贵州省贵阳市的主要交通路段采集了尘土和土壤样品,对样品中的铂族元素进行了同位素稀释-等离子体质谱法测定。结果表明,所有样品的铂族元素均高于未被污染土壤的背景值,而尘土样品中铂族元素含量明显高于土壤样品。其中Pt、Pd和Rh含量明显高于其它铂族元素(Ru和Ir等),并与Ru和Ir呈一定的正相关关系,表明汽车尾气催化剂的主要组成为Pt、Pd和Rh;高含量的Os具有低的~(187)Os/~(188)Os比值,表明Ru、Ir和Os也源于汽车尾气催化剂,可能是以杂质的形式存在于汽车尾气催化剂中。     

Ru/AC催化臭氧氧化难生物降解有机物

研究了臭氧单独氧化和Ru/AC催化臭氧氧化DMP、酚类物质和消毒副产物前体物.结果表明,Ru/AC能显著提高臭氧氧化中有机物的矿化效果.在DMP降解中,反应100 min后TOC的去除率由单独臭氧氧化的28.84%提高到66.13%.在23种酚类物质降解中,反应60min后TOC的去除率由单独臭氧的9.57%~56.08%提高到41.81%~82.32%.相对于单独臭氧,Ru/AC催化臭氧氧化更能有效地降低水源水中消毒副产物的生成势,以卤乙酸生成势的降低最为明显,100 min后卤乙酸生成势由144.02μg/L降到58.50μg/L,低于美国环保局规定的限制浓度60μg/L.而使用单独臭氧处理并不能使卤乙酸生成势降到符合美国EPA的规定.比较了BAC、O3+BAC、O3/AC+BAC以及Ru/AC+O3+BAC工艺处理水源水的效果,TOC平均去除率分别为3.80%、20.14%、27.45%和48.30%;COD平均去除率分别为4.37%、27.22%、39.91%和50.00%;UV254去除率分别为8.16%、62.24%、67.03%和84.95%.Ru/AC+O3+BAC工艺相比其他工艺,更能有效地...     

Low-temperature VOCs oxidation performance of Pt/zeolites catalysts with hierarchical pore structure

Different zeolites supported Pt catalysts with micro-mesoporous structure were prepared by organic base tetrapropylammonium hydroxide (TPAOH) treatment and their catalytic oxidation activity for various volatile organic compounds (VOCs) were evaluated. The results reveal that the synergistic effect between Pt nanoparticles and surface acid sites plays an important role in VOCs low-temperature removal. The small size and high dispersion of Pt nanoparticles on the surface of the zeolites would promote the catalytic oxidation of aromatics and alkanes over the Pt/zeolite catalysts, while strong acidity and abundant acid sites of catalysts are in favour of the oxidation of the VOCs containing N and O heteroatoms. In addition, it was found that Pt/ZSM-5 catalyst exhibits the highest oxidation activity for various VOCs low-temperature removal amongst all the catalysts due to the balance of both Pt dispersion and abundant acid sites in the catalyst. This comprehensive consideration should be very helpful when designing and preparing novel catalysts for the low-temperature removal of VOCs.     

高浓度难降解乳化废水湿式氧化影响因素研究

在2L高压间歇反应釜中,系统地研究了湿式氧化对乳化液废水的CODCr,TOC去除效果及影响因素。研究表明:温度是影响湿式氧化效果的关键因素,湿式氧化温度以220℃为宜,进水CODCr质量浓度为48000mg L时反应2h,CODCr和TOC去除率分别达86 4%,79 5%;供氧不足氧化受到显著限制,供氧量以(1 0～1 25)p(O2) 为宜;该法在较宽浓度范围内仍具有良好的处理效果;进水pH值对有机物氧化影响较小。      

Pt/TiO2/ZSM-5在日光下氧化氨氮的研究

采用溶胶-凝胶法和光沉积法制备了Pt/TiO2/ZSM-5催化剂。研究了铂修饰对催化剂的吸附性能的影响。考察了催化剂在日光照射下对氨氮的氧化,并以紫外光作为对比。结果表明铂的修饰,对催化剂的吸附能力有较大影响,还可以提高催化剂在日光照射条件下对氨氮的氧化效率和总氮去除率。在太阳光照射、空气曝气条件下,反应2h氨氮去除率达50.1%,总氮去除率达31.8%。     

铈掺杂Ru/Al2O3催化臭氧氧化降解邻苯二甲酸二甲酯

考察了铈(Ce)的掺杂对Ru/Al2O3催化臭氧氧化邻苯二甲酸二甲酯(DMP)溶液过程的影响.结果表明,Ce的掺杂可以显著提高臭氧氧化的效果,反应100min后,TOC的去除率可以由原催化剂的61.3%提高到75.1%,而单独臭氧氧化仅有14.0%.在实验范围内,Ru和Ce同时浸渍催化效果较好,且活性组分的溶出最少,Ce的最佳掺杂量为1.0%.通过催化剂吸附试验、单独臭氧氧化试验、Ce的均相催化试验及Ru-Se/Al2O3催化剂的非均相催化实验,证明Ru-Ce/Al2O3催化剂对DMP溶液臭氧氧化体系TOC的去除率达到50%,这是基于Ru-Ce/A12O3催化剂的非均相催化作用.     

In situ adsorption-catalysis system for the removal of o-xylene over an activated carbon supported Pd catalyst

An activated carbon (AC) supported Pd catalyst was used to develop a highly efficient in situ adsorption-catalysis system for the removal of low concentrations of o-xylene. In this study, three kinds of Pd/AC catalysts were prepared and tested to investigate the synergistic efficiency between adsorption and catalysis for o-xylene removal. The Pd/AC catalyst was first used as an adsorbent to concentrate dilute o-xylene at low temperature. After saturated adsorption, the adsorbed o-xylene was oxidized to CO2 and H2O by raising the temperature of the catalyst bed. The results showed that more than 99% of the adsorbed o-xylene was completely oxidized to CO2 over a 5% Pd/AC catalyst at 140℃. Brunauer-Emmett-Teller (BET) analysis, scanning electron microscopy (SEM), temperature-programmed desorption (TPD), and temperature-programmed oxidation (TPO) were applied to investigate the physical properties of o-xylene adsorption-desorption and the in situ adsorption-catalysis activity of the AC support and Pd/AC catalyst. A synergistic relationship between the AC support and the active Pd species for the removal of low concentrations of o-xylene was established.     

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%。     

Study on catalysts for combustion of lean CH_4

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焙烧再生废旧臭氧催化剂处理石化废水生化出水

为了解决臭氧催化氧化技术中废旧催化剂处理困难的问题,对用于某石化废水生化出水处理长达5年的废旧臭氧催化剂进行了焙烧再生研究.通过焙烧能够有效燃烧去除催化剂表面及孔隙中的有机物质,增大催化剂孔径和孔隙率,从而恢复废旧催化剂的部分活性.单因素试验对催化剂焙烧温度和焙烧时间优化结果表明：(1)随着焙烧温度从200℃提高到500℃,再生催化剂用于臭氧催化对石化废水生化出水TOC(总有机碳)的去除效果逐渐提升,500℃时TOC去除率可达44.30%,进一步提高焙烧温度去除效果提升不明显.(2)焙烧时间为2、3、4和5 h时,再生催化剂处理石化废水效能随焙烧时间增加先升高再降低,4 h时TOC去除效果最好.(3)在相同运行条件下,优化焙烧条件(500℃、4 h)下得到的再生催化剂对石化废水生化出水的TOC去除率可达新催化剂的77.46%,相较于新催化剂,再生催化剂的颗粒尺寸和平均孔径减小,而比表面积有所增大.(4)通过皮尔逊相关性分析,探索了废水中有机物和三维荧光测试结果的相关性,认为荧光区域积分体积可以间接反映石化废水中的有机物含量,也可间接反映臭氧再生催化剂的催化性能.研究显示,直接焙烧可以作...     

钙钛矿LaMnO3负载贵金属在催化氧化碳烟中的作用

采用共沉淀法制备钙钛矿LaMnO₃,并用浸渍法在LaMnO₃上负载不同的贵金属得到系列催化剂.利用程序升温氧化反应对催化剂催化氧化碳烟的性能进行了测试.程序升温还原(H₂-TPR)、BET、XRD、SEM和FT-IR等表征手段对催化剂进行了表征.结果表明,当Pd的负载量在0.5%时,催化剂Pd/LaMnO₃的催化性能最好,和单独的LaMnO₃相比,最高燃烧速率温度降低了40℃.当负载量较小和较多时,碳烟起燃温度反而会比LaMnO₃高.在5种贵金属负载的催化剂中,其中Pd催化性能最好,依次为Au、Ru、Pt和 Rh.TPR测试表明贵金属的负载有助于钙钛矿中Mn⁴⁺的还原,对高温时Mn³⁺的还原作用不大.XRD衍射角向低角度出现了少许偏移,显示负载在表面的贵金属部分进入钙钛矿LaMnO₃的晶格结构中,使其晶粒增大;BET和SEM结果表明催化剂在反应后出现了轻微团聚现象.IR图谱显示反应前后,主要特征红外吸收带没有明显变化, 表明催化剂具有较好的结构稳定性.适量的贵金属在钙钛矿LaMnO₃上负载,能够有效地提高催化燃烧碳烟的活性.     

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     

催化湿式氧化法降解活性艳蓝的研究

以Fe2O3/γ-Al2O3为催化剂的非均相催化氧化体系处理活性艳蓝KN-R。考察了反应时间、反应温度、pH和Fe2O3/γ-Al2O3投加量等因素对降解效果的影响。结果表明,染料初始浓度为200mg/L时,在温度150℃、压力0.5MPa、H2O233mg/L、pH=6,反应时间1h,Fe2O3/γ-Al2O3投加量为8g/L的最佳条件下,活性艳蓝KN-R色度几乎完全去除,TOC和COD去除率分别为95.6%和82.5%。     

铂、钯蜂窝催化剂高温老化对甲醇深度氧化的影响

本研究对铂、钯蜂窝催化剂及分别添加助化剂CeO_2或WO_3,并于500℃、700℃、900℃或1100℃下经受热老化4h后,考察催化剂比表面、晶相结构及其对甲醇深度氧化活性、产物分布及反应动力学网络变化的情况。实验证明,添加CeO_2后,降低了铂催化剂的耐高温性能,但对钯催化剂无明显影响。添加WO_3,降低了钯催化剂对甲醇的氧化活性。经X-线衍射分析证明,在1100℃高温下,WO_3与堇青石载体中的氧化镁和氧化钙发生强相互作用,生成了相应的钨酸盐。甲醇氧化反应动力学研究表明,甲醇在新鲜和高温热老化的铂催化剂上,反应动力学网络表示式是有区别的。