催化湿式过氧化（CWPO）偶氮染料反应机理及降解历程研究

采用浸渍法制备出具有较高催化活性的催化剂CuO/γ-Al2O3,通过XRD、电镜等手段对催化剂进行了表征。降解了几种不同结构的偶氮染料,并通过改变CWPO的反应条件推断了其催化反应机理。采用紫外/可见分光光度计（UV-Vis）和傅里叶红外光谱仪（IR）等手段对染料降解过程进行跟踪和分析,对比染料处理前后紫外可见光谱与红...     

催化湿式氧化法处理垃圾渗滤液

以北京某垃圾转运站的垃圾渗滤液原液为研究对象,采用催化湿式氧化技术进行实验研究。实验以Fe2+为催化剂,H2O2为氧化剂,在反应釜中高温高压处理转运站的渗滤液。同时,实验分别研究了反应温度、反应时间、催化剂种类和添加量等几种因素对渗滤液处理效果的影响。结果表明,当反应温度达到120℃,反应60 min时,在Fe2+催化条件下,按初始COD和Fe2+质量比为6投加催化剂,初始COD和H2O2当量比为1投加氧化剂,反应出水的COD去除率达到91%。     

H-酸的催化湿式氧化反应过程研究

湿式氧化（ＷＡＯ）和催化湿式氧化（ＣＷＡＯ）都能有效地处理染料中间体－－Ｈ－酸。所有的Ｈ－酸在５ｍｉｎ内均被支除和形成一些中间产物。在不同反应时间段测定了ｐＨ值及阴、阳离子和小分子有机酸等中间产物。分析表明,ｐＨ值与ＣＯＤ的去除及有机酸的产生有密切的联系,Ｈ－酸被氧化成ＮＨ４＾＋、ＳＯ４＾２－、ＨＣＯＯＨ和ＣＨ２ＣＯＯＨ。ＷＡＯ法的瓜速率慢而且氧化乙酸困难。而ＣＷＡＯ法的反应速率不但快而且能有效地     

乳化液废水的均相催化湿式氧化

在2L的高温高压反应釜中,以非贵的过渡金属盐作均相催化剂,研究了高浓度难降解的乳化液废水的催化湿式氧化.试验发现,单一金属盐催化活性为Cu2 ＞Mn2 ＞Co2 ,其中Cu2 在200℃时催化效果良好,可使TOC去除率提高13.3%;Cu2 受投量影响较明显,以200mg/L为宜;混合盐催化活性为Cu2 Mn2 ≈Mn2 Co2 (＞Cu2 )＞Cu2 Co2 .     

陶瓷-活性炭球为载体的CWAO催化剂

以陶瓷-活性炭球为载体制备载Ru催化剂,用于催化湿式氧化(CWAO)法处理酚醛树脂废水,考察了陶瓷-活性炭球载体、Ru负载量和陶瓷球宏孔孔径等对催化剂的催化活性和稳定性的影响。实验结果表明,催化剂催化活性的顺序为:Ru/KC-120>Ru/KC-80>Ru/KC-60>KC-120>无催化剂。在200℃,氧气分压为1.5 MPa等条件下,催化湿式氧化酚醛树脂废水,3% Ru/KC-120催化剂表现良好的催化活性与稳定性,在120 min内,COD和苯酚去除率分别达到91%和96%。     

废水催化湿式氧化稀土金属氧化物催化剂的研制

采用共沉淀法制得锰铈复合氧化物催化剂,催化湿式氧化处理高浓度苯酚废水。通过正交实验筛选催化剂制备条件,单因素实验优化制得催化剂。研究了CWAO处理废水条件下的金属离子溶出和催化剂的表征。结果表明,该催化剂在低温低压条件下具有优良的湿式氧化催化活性,且金属离子溶出量低,是一种CWAO处理高浓度有机废水中极具应用前景的新型高效催化剂。     

催化湿式氧化处理机械加工工业废水的研究

利用担载的双金属活性组分催化剂，考察了反应温度、压力、进料空速和污水pH等条件对催化湿式氧化处理某厂机械加工废水效果的影响。对于该厂的混合废水，在反应温度260℃，反应压力6．6MPa，空速为2．0h^-1，pH为3条件下处理后的废水CODCr去除率为90．2％。考察了助剂H2O2、絮凝剂对处理废水效果的影响和各种联用技术对废水的处理效果。     

催化湿式氧化技术处理山梨酸生产废水的研究

采用催化湿式氧化技术处理生产山梨酸过程中产生的高浓度有机废水,对催化剂组分进行优选.对反应温度、O2分压(Po2)和废水pH等工艺条件进行考察.实验结果表明:采用自制CuO-Cr2O3-La2O3/TiO2为复合催化剂处理该有机废水时表现出较好的催化活性;在190℃、Po2=2.1 MPa、pH=6.1、COD=10 030.0 mg/L时,反应90 min的COD去除率达到98.3%,而在相同条件下未加催化剂的湿式氧化的COD去除率只有60.1%.     

催化湿式氧化处理助剂废水工程及过程模拟

助剂废水是一种高浓度难降解有机废水,以催化湿式氧化（CWAO）为主体的CWAO-UASB-AOA-接触氧化-混凝沉淀工艺能够对其进行有效降解。在CWAO工业化装置设计中,床层温升（Tg）和换热器总传热系数（K）是换热器设计的2个重要参数。采用Aspen Plus对CWAO过程进行稳态模拟,Aspen Plus对Tg模拟结果同分布式控制系统（DCS）实测结果相对误差在±2.0%以内。根据计算结果可知,K为800 W · (m2 · °C)-1。结合K和Tg可以用来估算换热面积,进而指导CWAO过程系统工程的工业化设计。     

催化湿式氧化中负载型催化剂的稳定性与应用

催化剂在应用过程中必须具有良好的催化活性和稳定性。优化制备的CuO／γ-Al2O3催化剂用于处理高浓度难降解的乳化液废水时具有良好的催化活性。在200℃时反应2h，TOC去除率为81．3％，比未加催化剂的湿式氧化提高了14．9％。该催化剂对分散兰废水具有更高的活性和稳定性：在220℃反应1．5h后，COD和TOC去除率分别为68．8％和56．5％，比非催化氧化分别提高了18．7％和18．9％。     

催化湿式氧化中负载型催化剂的稳定性与应用

催化剂在应用过程中必须具有良好的催化活性和稳定性.优化制备的CuO/γ-Al2O3催化剂用于处理高浓度难降解的乳化液废水时具有良好的催化活性,在200℃时反应2 h,TOC去除率为81.3%,比未加催化剂的湿式氧化提高了14.9%.该催化剂对分散兰废水具有更高的活性和稳定性:在220℃反应1.5 h后,COD和TOC去除率分别为68.8%和56.5%,比非催化氧化分别提高了18.7%和18.9%.     

Removal of nitrogenous compounds by catalytic wet air oxidation. Kinetic study

Aqueous wastes containing organic pollutants can be efficiently treated by wet air oxidation (WAO), i.e. oxidation by molecular oxygen in the liquid phase, under high temperature (200-325 degrees C) and pressure (up to 150 bar). However, organic nitrogen can be relatively resistant to oxidation and can be harmful to the environment. In the course of treatment, organic nitrogen (N-Org) is converted into ammonia (NH(3)), while organic carbon (C-Org) is converted mainly into carbon dioxide (CO(2)). This can be done without catalysts. In the presence of Mn/Ce composite oxides, it is possible to transform ammonia into molecular nitrogen at a temperature close to 260 degrees C. The direct conversion of organic nitrogen into molecular nitrogen also can be achieved using the same catalyst. This paper discusses the results obtained during the treatment of nitrogenous compounds like aniline, nitrophenol, beta-alanine and ammonia. Laboratory investigations were conducted in a stirred batch reactor with Mn/Ce composite oxides as catalysts. Very limited amounts of nitrites and nitrates were observed with amines, but more significant quantities were found with nitro-compounds. The kinetics of oxidation of ammonia, organic compounds, and more particularly aniline, were investigated. The treatment of a real waste (process wastewater) was also investigated. The dependence of the transformation rate on various parameters (amount of catalyst, temperature, etc.) was established. The rates of oxidation are described by first-order kinetic laws with respect to the various nitrogen species (aniline, NH(3)). Several parallel pathways are considered for the transformation of organic nitrogen, amongst which is an interaction with the catalyst surface. The orders with respect to oxygen and catalyst are established.     

催化湿式氧化吡虫啉农药废水催化剂的研究

通过共沉淀法制备了用于湿式氧化吡虫啉农药废水的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等对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氧化处理吡虫啉农药废水时,具有较高的催化活性和稳定性.催化剂用量4 g/L,反应温度190℃,氧分压1.6 MPa,反应120 min,COD去除率为92.3%,活性组分溶出量较小.     

Thermodynamic and kinetic study of phenol degradation by a non-catalytic wet air oxidation process

This work is dedicated to an accurate evaluation of thermodynamic and kinetics aspects of phenol degradation using wet air oxidation process. Phenol is a well known polluting molecule and therefore it is important having data of its behaviour during this process. A view cell is used for the experimental study, with an internal volume of 150 mL, able to reach pressures up to 30 MPa and temperatures up to 350 °C. Concerning the thermodynamic phase equilibria, experimental and modelling results are obtained for different binary systems (water/nitrogen, water/air) and ternary system (water/nitrogen/phenol). The best model is the Predictive Soave Redlich Kwong one. This information is necessary to predict the composition of the gas phase during the process. It is also important for an implementation in a process simulation. The second part is dedicated to kinetics evaluation of the degradation of phenol. Different compounds have been detected using GC coupled with a MS. A kinetic scheme is deduced, taking into account the evolution of phenol, hydroquinones, catechol, resorcinol and acetic acid. The kinetic parameters are calculated for this scheme. These data are important to evaluate the evolution of the concentration of the different polluting molecules during the process. A simplified kinetic scheme, which can be easily implemented in a process simulation, is also determined for the direct degradation of phenol into H₂O and CO₂. The Arrhenius law data obtained for the phenol disappearance are the following: k = 1.8 × 10⁶ ± 3.9 × 10⁵ M⁻¹ s⁻¹ (pre-exponential factor) and E_a = 77 ± 8 kJ mol⁻¹ (activation energy).     

Decolorization of cationic red X-GRL by wet air oxidation: performance optimization and degradation mechanism

The decolorization of a strong colored azo dye solution of cationic red X-GRL was investigated by wet air oxidation under relatively mild conditions (60-180 degrees C, PO2 = 0-1.2 MPa). Mono-factor experiments were carried out to investigate the effect of the operation factors and the relatively important parameters were selected for optimization using response surface methodology to explore the interactions of these relatively important parameters. Model regeneration analysis and the check experiments showed that the data of the general linear model agreed with the experiment results well. With multistage Monte-Carlo optimization, the best region of these variables could be predicted to dye color removal. At typical operational conditions, the intermediates of dye degradation were detected and confirmed by GC/MS system. Considering the intermediates and the structure analysis with the help of Gaussian 03W (version 6.0) and the theory of dye color, a possible degradation mechanism for the wet air oxidation of cationic red X-GRL was discussed and the probable degradation pathway was deduced.     

非均相催化湿式氧化法活性炭再生

使用浸渍法制备的CuO Al2 O3催化剂对吸附苯酚饱和的活性炭进行非均相催化湿式氧化再生研究 ,考察了反应温度、反应时间、催化剂投加量、反应氧分压、投炭量、蒸馏水量对非均相催化湿式氧化再生活性炭的影响结果 ,同时在该实验中得到非均相CuO Al2 O3催化湿式氧化再生活性炭的最佳条件。对催化剂进行了X衍射分析 ,并通过对催化剂的稳定性进行实验 ,得出该催化剂在进行催化湿式氧化再生活性炭的过程中具有较好的稳定性     

微波辅助催化湿式氧化技术降解高浓度苯酚废水

以纳米CuO为催化荆,采用微波辅助催化湿式过氧化氢氧化方法对高浓度苯酚废水(1 000 mg/L)进行降解处理,并与传统的催化湿式过氧化氢氧化技术进行比较,研究了微波强化作用对该技术的处理工艺条件、降解效率及机制的影响.结果表明,在微波的辅助作用下,当温度仅为60℃、压力为0.3 MPa时,催化湿式氧化反应15.0 min,苯酚废水的TOC去除率即达到90.8%.这表明微波促使催化湿式氧化反应可以在温和的条件下实现,而且效率高、速率快.进一步的降解机制研究发现,在微波的作用下,苯酚于2.0min内完全氧化转化,主要发生直接开环反应,生成短链羧酸,所经历氧化过程更为简单.     

Treatment of organic aqueous wastes: Wet air oxidation and Wet Peroxide Oxidation

There is growing concern about the problems of waste elimination. We should consider our environment as being borrowed from future generations and refrain from leaving a legacy of problems we are not able to solve. Various oxidation techniques are suited for the elimination of organic aqueous wastes, but because of the environmental drawbacks of incineration, enclosed processes, like liquid phase oxidation should be preferred. Wet air oxidation (WAO) under high temperature (200-325 degrees C) and pressure (50-150 bar) is suited to such liquid wastes and various catalysts, including hydrogen peroxide, can be used in order to increase the efficiency without increasing temperature and pressure. Wet Peroxide Oxidation (WPO) is a similar process. A comparable oxidation efficiency is obtained when using hydrogen peroxide as the oxidising agent instead of oxygen, at a temperature of only 100-120 degrees C. As opposed to WAO, which is capital intensive, WPO needs limited capital but generates higher running costs. The paper reviews the major results obtained for both processes and assesses the field of possible application of each of them. TOC removal efficiencies typically obtained range from 65 to 90% or more for most of the pollutants.     

Wet air oxidation of nitrobenzene enhanced by phenol

Simultaneous nitrobenzene and phenol wet air oxidation was investigated in a stainless autoclave at temperature range of 180-220 degrees C and 1.0 MPa oxygen partial pressure. Compared with the single oxidation of nitrobenzene under the same conditions, the presence of phenol in the reaction media greatly improved the removal efficiency of nitrobenzene. The effect of temperature on the reaction was studied. Phenol was considered as a type of initiator in the nitrobenzene oxidation.