湿式氧化-催化湿式氧化联用处理定影废水

采用湿式氧化(WAO)-催化湿式氧化(CWAO)两段工艺处理定影废水,重点考察了反应时间、温度、压力、pH等因素对WAO处理效果的影响,并进行了CWAO处理WAO出水氨氮的尝试,取得了较好的效果.实验确定WAO适宜的反应条件:温度为160℃、氧分压为1 MPa、反应时间为2 h、进水pH为4.8.该条件下的CODCr去除率达79%,出水pH为1.4.CWAO处理WAO出水时所选定的反应条件:pH为12.9、温度为250℃、氧分压为3 MPa、反应时间为2 h.采用CWAO和WAO联用的方法处理定影废水,CODCr去除率达99.8%,氨氮去除率达97.8%,pH为5.6.     

催化湿式氧化处理农药废水的研究

利用担载型双金属活性组分催化剂，考察了反应温度、压力、进料空速和V（空气）：V（H2O）（体积比）等反应条件对催化湿式氧化处理某农药废水效果的影响。对于该种废水，在4．2MPa，245℃，空速为2．0h^-1，V（空气）：V（H2O）＝300的反应条件下，废水的COD去除率可达到91．3％。经处理后废水的BOD5／COD＞0．5，说明其可生化性能良好。     

湿式氧化工艺处理高浓度苯酚废水试验研究

以高浓度苯酚废水为研究对象,采用湿式氧化（WAO）工艺对其进行CODCr降解试验。考察了反应温度、反应压力、废水pH值、苯酚初始质量浓度及反应时间等对WAO处理效果的影响。在此基础上,采用正交试验方法获得了相应的工艺参数,在废水初始pH值为12,初始CODCr的质量浓度为20 000 mg/L,反应温度为240℃,反应压力为4 MPa,反应时间不少于80 min的条件下,CODCr去除率可达89%。研究结果可为含酚废水WAO处理工艺的工程设计提供依据。     

催化湿式氧化法处理噻螨酮生产废水的试验

采用CuO-MnO2-La2O3为催化剂,以催化湿式氧化技术处理噻螨酮生产过程中产生的的高浓度有机废水.试验结果表明,用该复合催化剂在处理此种有机废水时表现出较好的催化活性.在230℃,氧气分压为2.5MPa和pH值为7.3的条件下,当废水CODCr的质量浓度为15 730 mg/L,在120 min内,CODCr去除率达到96.1%,而在相同条件下未加催化剂的湿式氧化CODCr去除率只有50.3%.     

催化湿式氧化法处理焦化废水的分析

概述了焦化废水水量大、成分复杂、污染物浓度高等水质特点和传统焦化废水处理方法及其缺陷，提出应用催化湿式氧化技术处理焦化废水这一新途径。并就技术和经济方面对催化湿式氧化技术处理焦化废水进行了分析，说明利用该技术处理焦化废水不仅技术上可行而且具有较好的综合效益。指出了催化湿式氧化技术在工业化过程中面临催化剂溶出和反应设备材质要求高等问题。     

湿式催化氧化/膜过滤组合工艺膜过滤机理

采用湿式催化氧化/膜过滤组合工艺,以Mo-Zn-Al-O粉末作为催化剂降解阳离子红GTL模拟染料废水,探讨在膜过滤过程中平均孔径为0.1 μm的微滤和0.022 μm的超滤聚偏氟乙烯(PVDF)中空纤维膜的过滤机理。实验结果表明,两种膜过滤组合工艺对染料的降解效果均优于单独湿式催化氧化,0.01 MPa恒压条件下运行120 min后微滤和超滤的膜通量分别衰减了26.63%和16.48%,其原因是粉末催化剂可在微滤膜孔内部沉积形成中间阻塞过滤,后在表面形成滤饼层;而在超滤膜表面仅形成滤饼层。通过实验结果对膜阻力进行计算,可知在相同反应过程后微滤膜产生的不可逆阻力大于超滤膜。在不同反应条件下,催化剂的沉积量与膜阻力呈现线性相关。     

湿式氧化法处理高盐度难降解农药废水

采用湿式氧化技术研究高盐度、难降解农药废水在湿式氧化反应中COD去除率的影响因素及色度的去除效果。结果表明,该生产废水的湿式氧化效率受反应温度、氧分压、反应时间、反应体系酸度的影响较大。当反应温度280℃、氧分压4.2 MPa、反应液初始pH值为2.0,反应150 min后,废水中的COD去除率高达98.0%,色度的去除率达99.0%以上。研究结果可为在高含盐环境下处理难降解农药废水提供依据。     

Stable and efficient Ru/TiO2-ZrO2 catalysts for catalytic wet air oxidation of phenolsulfonic acid wastewater treatment

Catalytic wet air oxidation (CWAO) technology can efficiently treat organic wastewater, but the performance of existing catalysts, especially its stability, is far from industrial applications. In this study, ZrO₂ was used to modify TiO₂ support to form the stable Ru/TiO₂-ZrO₂ catalysts. It was found that the Ru/TiO₂-ZrO₂ catalysts showed excellent performance for catalytic wet air oxidation of phenolsulfonic acid wastewater. They gave high total organic carbon (TOC) conversions (>90%) and remained stable in 5 consecutive running in the Ti/Zr ratio range from 9∶1 to 7∶3. On the other hand, TOC conversion decreased from 99.1% to 65.3% in 5 consecutive cycles for the conventional Ru/TiO₂ catalyst. The characterization results of XRD, BET, XPS, H₂-TPR and ICP-OES indicated that ZrO₂ can enter the lattice of TiO₂ to form TiO₂-ZrO₂ solid solution, which prevented the transformation of TiO₂ from anatase to rutile. In addition, the modification of ZrO₂ strengthened the interaction between Ru and the support, which effectively inhibited the leaching of Ru metal. The stable support structure and good anti-loss performance are the main reasons for the excellent reaction performance of Ru/TiO₂-ZrO₂ catalyst.     

稳定高效Ru/TiO2-ZrO2催化剂处理苯酚磺酸废水

催化湿式氧化（CWAO）技术可高效处理有机废水,但现有催化剂的性能,尤其是其稳定性距工业应用还有很大差距。利用ZrO₂对TiO₂载体进行掺杂调变,研制出了具有良好稳定性的Ru/TiO₂-ZrO₂催化湿式氧化催化剂。结果表明, Ru/TiO₂催化剂在进行连续5次催化湿式氧化降解苯酚磺酸（phenolsulfonic acid,PSA）废水的反应后,总有机碳（total organic carbon,TOC）转化率由99.1%降低至65.3%;而Ru/TiO₂-ZrO₂催化剂在Ti/Zr质量比为9∶1~7∶3范围内,能表现出优良的反应性能,在连续5次反应后, TOC转化率稳定保持在90%以上。X射线仪衍射（XRD）、N₂吸脱附（BET）、X射线扫描微探针电子能谱仪（XPS）、氢气程序升温还原（H₂-TPR）和电感耦合等离子体发射光谱（ICP-OES）表征结果表明：ZrO₂能够进入TiO₂的晶格,TiO₂-ZrO₂固溶体的生成阻止了TiO₂由锐钛矿相向金红石相的转变。另外,ZrO₂的调变加强了Ru与载体的相互作用,有效抑制了活性金属Ru的流失。稳定的载体结构和良好的抗流失性能是Ru/TiO₂-ZrO₂催化剂具有优良反应性能的主要原因。     

催化湿式氧化法在苯酚废水预处理中的应用研究

与湿式空气氧化相比，催化湿式氧化可以在温和条件下达到较好的废水处理效果。考察了CuO/η－Al2O3和活性炭两种催化剂处理苯酚废水的催化效果，结果表明在温和条件下可以达到较高COD去除率：在140℃下，催化湿式氧化1h，CODcr去除率分别达到93．2％和88．4％。在160℃下，催化湿式氧化1h，CODcr去除率分别达到93．4％和90．1％。在140℃下，苯酚废水经过湿式空气氧化1h后，BOD5／CODcr仅仅达到0．08，不适合后续生物法处理；使用活性炭催化剂，BOD5／CODcr达到了0．18，而使用CuO／η－Al2O3催化剂，BOD5／CODcr达到了0．30，因此，用CuO／η－Al2O3催化剂处理苯酚废水可以在较低温度下达到预处理效果。     

高浓度难降解有机废水湿式氧化可行性研究

选择四种高浓度难降解有机废水,在2L高压间歇反应釜中,研究了湿式氧化效果与技术可行性。结果表明:从氧化的容易程度来看,乳化液废水>丙硫咪唑废水>甲胺磷废水>分散蓝废水;各废水湿式氧化后可生化性得到显著改善;Cu2+有不同程度的催化作用;甲胺磷废水和丙硫咪唑废水对不锈钢反应釜腐蚀严重,乳化液废水最适宜湿式氧化。反应温度显著影响废水湿式氧化效果,温度越高氧化率越高。     

Process intensification in wastewater treatment: ferrous iron removal by a sustainable membrane bioreactor system

Biooxidation of ferrous iron (Fe²⁺) from strongly acidic industrial wastewater with a high Fe²⁺ content by Thiobacillus ferrooxidans in a packed bed reactor and subsequent removal of ferric iron (Fe³⁺) by a crossflow microfiltration (membrane) process have been investigated as functions of wastewater flowrate (54–672 cm³ h^?1), Fe²⁺ concentration (1.01–8.06 g dm^?3), and pH (1.5–5.0). A natural (vegetable) sponge, Luffa cylindrica, was used as support matrix material. The fastest kinetic performance achieved was about 40 g Fe²⁺ dm^?3 h^?1 at a true dilution rate of 19 h^?1 corresponding to a hydraulic retention time of 3.16 min. Steady state conversion was observed to be about 10% higher at pH 2.3 than that at pH 1.5. Increasing the flowrate of the inlet wastewater caused a reduction in conversion rate. The oxidation rate reduced along the reactor height as the wastewater moved towards the exit at the top but conversion showed the opposite trend. Increasing Fe²⁺ concentration up to a critical point resulted in an increased oxidation rate but beyond the critical point caused the oxidation rate to decrease. Luffa cylindrica displayed suitable characteristics for use as a support matrix for formation of a Thiobacillus ferrooxidans biofilm and showed promising potential as an ecological and sustainable alternative to existing synthetic support materials. Membrane separation was shown to be a very effective means of Fe³⁺ removal from the wastewater with removal changing from 92% at pH 2.3 to complete removal at pH 5.0. Copyright © 2003 Society of Chemical Industry     

高浓度有机废水的均相催化湿式氧化影响因素

乳化液废水的均相催化湿式氧化实验发现,单一金属盐催化活性:Cu(NO3)2＞MnSO4＞CoCl2.考察了不同反应条件(温度、氧分压、进水有机物浓度)对铜盐均相催化湿式氧化的影响,结果表明,该工艺在200℃活性最高,在进水COD 48 400 mg/L,反应2 h时,COD去除率为86.6%;供氧量以初始氧分压0.93～1.16 MPa(25℃)为宜;该工艺在较宽进水浓度范围内有较高的去除率.     

湿式催化氧化降解焦化废水

以Cu(NO₃)₂·3H₂O为原料,采用共沉淀法制备了CuMgLa/Al₂O₃催化剂,TEM和N₂吸附-脱附结果表明,该催化剂具有介孔结构,主活性组分CuO的粒径约为25nm。以喹啉为降解目标污染物,考察了温度、催化剂质量浓度等对湿式催化氧化降解喹啉效果的影响。结果表明,当喹啉模拟废水质量浓度为1000mg/L,催化剂质量浓度为0.2 g/L,反应温度为240℃,O₂分压为0.53 MPa,反应60 min时,喹啉去除率接近100.0%,化学需氧量(COD)去除率达到94.8%。通过UV光谱、LC-MS分析喹啉降解生成的中间体,结合叔丁醇淬灭实验,发现·OH氧化在湿式催化氧化降解喹啉体系中起主导作用,推测了喹啉可能的降解路径。在最优工艺条件下,COD质量浓度为7000mg/L的模拟焦化废水COD的去除率达94.6%;而COD质量浓度为4740.0 mg/L,NH₃-N质量浓度为884.2 mg/L的实际焦化废水C...     

高级氧化技术处理染料废水的研究进展

由于染料废水中含有高浓度难降解有机污染物,对其有效处理一直是个难题.综述了近几年国内外采用湿式氧化法、Fenton法、光化学与光催化氧化法、电化学法、臭氧氧化法、微波辅助氧化法和超声氧化法等高级氧化技术处理染料废水的进展情况,并指出了高级氧化技术在染料废水处理中的发展趋势.     

Efficient mineralization of sugar industry wastewater by catalytic wet air oxidation as an eco-friendly method and its kinetic modelling

In this study, catalytic wet air oxidation using lanthanum cobalt oxide (LaCoO₃) as catalyst was employed for the efficient treatment of synthetic sugar industry wastewater in a single process. A parametric study was performed to determine the optimum conditions. The results showed that reaction temperature and theoretical air percentage were the most effective parameters. Sugar derivatives were almost completely destroyed at the optimum conditions and total organic carbon (TOC) and chemical oxygen demand (COD) removals were determined as 91% and 87%, respectively, indicating a high mineralization degree, which was the main goal of advanced oxidation. The reaction kinetics were investigated by pseudo-homogeneous and heterogeneous models based on two different parameters: sucrose and TOC concentration. The degree of fit showed that the reaction order was determined as two for the pseudo-homogeneous approach. According to the surface concentration calculations for heterogeneous models, the presence of mass transfer limitations was only observed for oxygen as gas reactant. All heterogeneous models also fitted the reaction rate data accurately, but the Mars–van Krevelen was the selected model for sucrose and TOC oxidation with the best fit.     

焦化废水膜法组合深度处理工艺设计与应用

针对煤化工企业焦化废水的二级生化出水可生化性差、含盐量与COD高,以及废水中包含多环芳香族化合物、脂肪族化合物等难生物降解污染物的特点,采用Fenton氧化+电渗析+超滤+反渗透膜法组合深度处理工艺对废水进行处理。运行结果表明,产水水质达到并优于《工业循环冷却水处理设计规范》(GB 50050—2007)中再生水水质要求,产水可作为厂区生产补充新水使用,废水回收率稳定达到75%。采用Fenton氧化与电渗析粗脱盐技术相结合的强化预处理设施,可以有效缓解反渗透装置的膜污染,延长反渗透膜的清洗周期至3个月。     

催化湿式氧化技术处理高浓度污染废水的研究进展及应用

催化湿式氧化技术是一种可有效处理高浓度、高毒性以及难生物降解有机废水的方法.作者介绍了催化湿式氧化技术的发展过程,重点分析和归纳了催化湿式氧化技术的工艺流程、催化剂的研究进展和应用领域,分析了该技术存在的技术和应用问题,总结了我国湿式催化氧化技术工业应用的现状,对该技术的研究方向提出了建议.     

Biodegradability of linear alkylbenzene sulfonates subjected to wet air oxidation

Shake flask experiments were conducted to determine the biodegradability of aqueous linear alkylbenzene sulfonate (LAS) and LAS (1600 mg dm^?3) subjected to wet air oxidation (WAO), to assess the suitability of WAO as a pre‐treatment for biological degradation. The effects of WAO temperature (180–240 °C) and the concentration of the orthophosphoric acid catalyst (0–1.0 mol dm^?3) were investigated. Results showed that a higher WAO temperature increased the biodegradability of the WAO effluent. This was due to a greater removal of both recalcitrant sulfonated organics and organic concentration (TOC and COD). Conversely, greater orthophosphoric acid concentrations decreased the biodegradability of the WAO effluents. This was because the higher acid concentration increased the ionic strength and changed the WAO intermediate and product distribution, inhibiting microbial action. Nevertheless, the effluents from both variations of WAO were still more biodegradable than LAS at equivalent concentrations. However, since higher WAO temperatures can substantially increase capital costs, future work should focus on developing a WAO catalyst that both desulfonates and mildly oxidises LAS at moderate temperatures (200 °C). © 2002 Society of Chemical Industry