CWAO催化剂及其在废水处理中的应用

催化湿式氧化技术是在高温高压条件下处理高浓度、有毒有害且难生物降解污染物的一种高级氧化技术。本文在检索了国内外大量参考文献的基础上,概述了催化湿式氧化技术的最新进展、机理及动力学,总结了催化湿式氧化技术中催化剂的分类、组成、特点及其在废水处理中的应用,以期对有关研究者提供一定的借鉴作用。本文最后肯定并展望了催化湿式氧化技术是有广阔应用前景的水处理技术。     

神经网络预测催化超临界水氧化废水效果的研究

在间歇式反应器中进行催化超临界水氧化DDNP废水试验,考察催化剂浓度、反应温度、压力、停留时间对氧化效果的影响。在实验基础上采用BP神经网络算法,建立以催化剂浓度、反应温度、压力、停留时间作为网络模型的输入层,COD去除率作为输出层的双隐层BP神经网络预测模型,预测催化超临界水氧化废水的效果,仿真结果表明模型预测效果较好。     

The influence of temperature on the deactivation of commercial Pd/Rh automotive catalysts

Automotive catalyst deactivation can be promoted by thermal and poisoning mechanisms. Catalyst efficiency is reduced by thermal degradation resulting in the agglomeration of precious metals and the reduction of the washcoat surface area. In this paper, the temperature influence on the commercial Pd/Rh-based automotive catalyst performance was studied. Textural and physicochemical characterisation techniques were employed, such as X-ray fluorescence (XRF), atomic absorption spectrometry (AAS), N₂ physisorption, X-ray diffraction (XRD), temperature programmed reduction (TPR) and scanning electron microscopy coupled with energy-dispersive X-ray analysis (SEM–EDX). The catalysts were evaluated for CO and propane oxidation with a stoichiometric gas mixture similar to engine exhaust gas. The results indicated the transformation of alumina into high temperature phases and the formation of new mixed oxide phases. Evidence of sintered particles and several spots of palladium agglomerates was seen by SEM–EDX analysis. The activity results showed the effects of thermal deactivation on the conversion of the pollutants. In spite of exposure to extreme temperature conditions (72 h at 1200 °C), significant activity was still observed for carbon monoxide and propane oxidation reactions.     

Effect of ultrasound irradiation and Ni-loading on properties and performance of CeO2-doped Ni/clinoptilolite nanocatalyst used in polluted air treatment

In this research nanocatalysts containing 5, 10 and 15 wt.% of Ni, dispersed by sonication over CeO₂–clinoptilolite composite support were compared toward total oxidation of toluene. Their catalytic performance at different temperatures between 150 and 350 °C was studied based on the oxidative destruction of toluene. The results indicated that the activity of Ni/CeO₂–clinoptilolite nanocatalyst for toluene oxidation increased from 33 to 44% at 250 °C by employing sonochemical method in synthesis of catalyst. Meanwhile, the catalytic activity was also improved when Ni content was increased from 5 to 10 and 15 wt.%. With the aid of several characterization techniques like XRD, FESEM, PSD, EDX, BET and FTIR, the correlation between nanocatalyst structure and its activity was addressed. It is indicated that sonochemical method can lift the catalytic activity due to the better dispersion of catalyst active components and also higher surface area. Among sonicated samples, 15 wt.% Ni nanocatalyst showed the highest toluene oxidation due to the better dispersion of catalyst active components and hence to more effective catalytic sites.     

Experimental investigation on oxidation of sulfurized rust in oil tank

Oxidation of sulfurized rust in oil tank is complicated, and it is influenced by numerous factors such as water content, air humidity, operating temperature etc. The paper focuses on the oxidation process of sulfurized rust in the wild. Firstly, samples collected from a petrochemical company were put into the sulfurization & oxidation experimental apparatus to gain wet and dry sulfurized rusts. Their chemical compositions and phase were analyzed by Energy Dispersive X-ray Spectrometer (EDS) -scanning electron microscope (SEM) technique. The results showed that both wet and dry sulfurized rusts had S, Fe₂O₃, Fe₃S₄ and FeS₂, whereas FeS only existed in wet sulfurized rust. The two kinds of rusts gave a short length of side, diamond appearance and a large pore size in structure. Then oxidation of wet sulfurized rust was investigated, which included electrochemical reaction stage, electrochemical & chemical reaction coexisting stage and chemical reaction stage. The final oxidation product of wet sulfurized was determined to be Fe₂O₃. On the basis of this study, an indicator for monitoring and early-warning was proposed to prevent plants in vicinity of the accidental vessel or tank from fire and explosion.     

Optimization of mixture ratio of electrolyte for reducing activation resistance of proton exchange membrane fuel cell

The purpose of this study is to find an optimal mixture ratio of the platinum-loaded carbon catalyst and the electrolyte in a membrane electrode assembly (MEA) of a proton exchange membrane fuel cell for reducing the activation resistance, which influences the electrochemical surface area, activation polarization, and maximum power density of the MEA. First, mixture ratios of 10, 20, 40, and 60 wt% platinum-loaded carbon catalysts and electrolyte were examined. The results indicated that the fuel cell performance improved for mixing weight ratios of 1.0:2.0 in 10 wt% Pt/C, 1.0:1.8 in 20 wt% Pt/C, 1.0:1.1 in 40 wt% Pt/C, and 1.0:0.5 in 60 wt% Pt/C. Next, we evaluated the activation resistances of the MEA from the AC impedance characteristics using the optimal mixing weight ratio of the platinum-loaded carbon catalyst and the electrolyte. It was found that the activation resistances of the anode and cathode decrease with an increase in the weight ratio of platinum-loaded carbon in the catalyst layer.     

超临界水氧化技术及在废水处理中的应用

超临界水氧化法是一种很有前途的废水处理方法。介绍了超临界水的性质、超临界水氧化技术的原理及在废水处理中的应用,并对该技术存在的问题和发展前景进行了探讨。     

Kinetics characteristics of coal low-temperature oxidation in oxygen-depleted air

The longwall gob (mined-out) area is one of the main places that are prone to coal spontaneous combustion and most of the residual coal in it is in oxygen-depleted air as it is a semi-enclosed space. A DSC (Differential scanning calorimetry) test system was designed to accurately test the heat generation of coal oxidation in different oxygen concentration atmosphere, based on which the kinetics parameters (activation energy and pre-exponential factor) of coal low-temperature oxidation in oxygen-depleted air were solved out. The results show that the kinetics parameters present obvious stage features and the lower the oxygen concentration is, the smaller is the difference of the kinetics parameters that in different oxidation stages. When the oxygen concentration is lower than 5% and 3% for jet coal and meagre coal respectively, the kinetics parameters of slow oxidation start to be greater than that of rapid oxidation. Both in the slow oxidation and rapid oxidation stage, with the decrease of oxygen concentration, kinetics parameters present significant decline on the whole while in different oxygen concentration range, the decline rate is different. It's concluded that when assessing the residual coal's self-heating risk, we need to use the corresponding kinetics parameters of coal oxidation in the oxygen concentration of the location where the residual coal is and the safety factor will be greater to only use the kinetics parameters of coal oxidation in slow oxidation stage. This study is of great significance for the assessment and control of the self-heating risk of coal that in different oxygen concentration atmospheres of the longwall gob areas.     

Low temperature CO oxidation over Pd–Ce catalysts supported on ZSM-5 zeolites

A series of Pd–Ce supported ZSM-5 zeolite catalysts for CO oxidation at low temperature were prepared by co-impregnation method. The effect of Pd–Ce synergistic function, Ce loadings, and properties of ZSM-5 zeolite on low temperature CO catalytic oxidation was investigated in detailed. The results showed that the Pd and Ce loading on ZSM-5 zeolite support at the same time enhanced catalytic activity compared with only Pd or Ce loading on ZSM-5 zeolite support. The properties of ZSM-5 zeolite had a strong influence for CO oxidation. Through the research, the ZSM-5 zeolite with high silicon aluminum ratio and small size also was helpful for CO oxidation. Among these catalysts, the catalyst with 19 wt% Ce loading displayed the highest catalytic activity. Chemical and physical properties of catalysts were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). XRD and TEM showed that Pd species were highly dispersed on the surface of ZSM-5 zeolite, which was strongly dependent on the amounts of Ce loading and the interaction among Pd species, Ce promoter and ZSM-5 support. The addition of CeO₂ improved the dispersion of Pd species over ZSM-5, and synergistic function of Pd and CeO₂ enhanced the catalytic activity. XPS characterization indicated that as the addition of Ce increased, Pd species was easy to enrich on the surface of the catalyst.     

Detoxification of hexavalent chromium in wastewater containing organic substances using simonkolleite-TiO2 photocatalyst

Innovative simple method for the preparation of simonkolleite-TiO₂ photocatalyst with different Zn contents was achieved. The prepared photocatalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), FT-IR, Raman and diffuse reflectance spectroscopy techniques. The photocatalytic activities of the materials were evaluated for the simultaneous detoxification of hexavalent chromium (Cr(VI)) and oxidation of organic compounds commonly present in wastewater under simulated solar light. The best photoreduction efficiency of Cr(VI) has been achieved at 1000 ppm simonkolleite-TiO₂ photocatalyst of 5% Zn/TiO₂ weight ratio, and pH value of 2.5 to enhance the adsorption onto catalyst surface. Photoreduction was significantly improved by using formic acid as holes scavenger owing to its chemical adsorption on the catalyst surface. Finally, 100% photoreduction of Cr(VI) could be achieved using formic/simonkolleite-TiO₂ systems under sunlight.     

元素硫高温腐蚀产物氧化自燃性影响因素的研究

用差热-热重分析仪考察元素硫与Fe(OH)3发生硫化腐蚀反应的初始温度,分析硫化温度、硫化时间、氧化温度和水对高温硫腐蚀产物氧化自燃性的影响。结果表明:元素硫与Fe(OH)3发生硫化反应的初始温度为287.67℃;硫化温度越高,硫化时间越长,元素硫高温硫化腐蚀产物中FeS2的含量越高,氧化自燃性越大;氧化温度对高温硫腐蚀产物的氧化自燃性有很大影响,室温时几乎不发生氧化反应,氧化温度超过95℃后,腐蚀产物的氧化反应速率大幅度提高,对炼油装置安全构成极大威胁;水对高温硫腐蚀产物的氧化自燃性起着重要作用,无水时,高温硫化产物基本不发生氧化反应,少量水存在即可极大影响高温硫腐蚀产物的氧化速率。     

Preparation of Co–MgO mixed oxide nanocatalysts for low temperature CO oxidation: Optimization of preparation conditions

In this study, a series of Co–MgO mixed oxides (30 wt.% Co) were prepared by co-precipitation method and employed as catalyst in low temperature CO oxidation reaction. The preparation conditions were optimized by the Taguchi method of experimental design to synthesize a sample with high catalytic performance toward CO oxidation reaction. The effects of four variables, pH of solution, aging temperature, aging time and molarity of precursor solution at three levels were investigated. The optimized sample was characterized by X-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed desorption of oxygen (O₂-TPD), N₂ adsorption/desorption, thermal gravimetric and differential thermal analysis (TGA/DTA), and transmission electron microscopy (TEM) techniques. The results revealed that the optimized sample showed a mesoporous structure with a narrow pore size distribution centered in the range of 7–17 nm and particle size about 5.5 nm. It was found that the molarity of solution and aging time had the most influence on the CO conversion, respectively. The catalytic results showed that the highest CO conversion obtained from samples synthesized by Taguchi orthogonal array was about 90% at 200 °C, while the CO conversion for optimized sample was 95%. In addition, the effect of operational conditions was studied over optimized sample.     

催化氧化法处理焦化污水生化出水的中试研究

采用ClO_2三相催化氧化工艺对焦化污水二沉池出水的处理进行了中试研究,考察了进水量、供气量、加药量等参数对焦化污水COD处理效果的影响,得出的最佳工艺条件为:进水量0.2 m~3/h,有效催化剂用量0.5 m~3,供气量10 m~3/h,盐酸投加量60 m L/h,氯酸钠投加量30 m L/h。最佳工艺条件下,平均出水COD为44 mg/L,平均去除率为80.3%,能达到国家一级排放标准。     

Removal of humic substances from landfill leachate by Fenton oxidation and coagulation

In this study, chemical oxygen demand (COD) was characterized as total organic constituents and the isolated humic substances (HS) were characterized as an individual organic contaminant in landfill leachate. It was found that the HS content of landfill leachate was 83.3%. The results of laboratory tests to determine the roles of HS in reducing the organic content of landfill leachate during Fenton process are presented. Furthermore, the performances of oxidation and coagulation of Fenton reaction on the removal of HS and COD from leachate were investigated. The change curves of HS removal were similar to those of COD. The HS removal was 30% higher than COD removal, which indicated that HS were mostly degraded into various intermediate organic compounds but not mineralized by Fenton reagent. The oxidation removal was greatly influenced by initial pH relative to the coagulation removal. The oxidation and coagulation removals were linear dependent with hydrogen peroxide and ferrous dosages, respectively. Ferrous dosage greatly influenced the coagulation removal of COD at low ratio ([H₂O₂]/[Fe²⁺] < 3.0), but not at extremely high ratio ([H₂O₂]/[Fe²⁺] > 6.0). The coagulation removal of HS was not affected obviously by oxidation due to both Fenton oxidation and coagulation remove high molecular weight organics preferentially. Higher temperature gave a positive effect on oxidation removal at low Fe²⁺ dosage, but this effect was not obvious at high Fe²⁺ dosage.     

Sources of underground CO: Crushing and ambient temperature oxidation of coal

As a harmful gas in underground coal mine, CO seriously threatened the safety of miners. Currently, the spontaneous combustion of residual coal in goaf is generally considered as the main source of underground CO. CO gas is also widely used as an indicator gas in fire prediction in mines. However, high concentrations of CO are also detected in some mines without spontaneous combustion of coal. Therefore, in the paper, with four ranks of coal, we studied other two potential CO sources: crushing and oxidation at ambient temperature. The more completely crushed coal produces more CO. The concentration of generated CO is inversely proportional to moisture content in coal. Therefore, the addition of water can inhibit the generation process of CO during the crushing process of coal. Lignite with low metamorphic grade can be oxidized to produce CO at ambient temperature (25 °C), and anthracite with high coal rank can be only oxidized to produce CO at 60 °C. Infrared spectra indicated that the coal with rich aliphatic hydrocarbons and oxygen-containing functional groups are more susceptible to oxidation at room temperature. Moreover, the smaller particle size of coal is more beneficial to the oxidation at ambient temperature to generate CO. CO generation during coal oxidation is also closely related to the ventilation rate.     

水分影响下阴燃传播及气相反应发生的研究

为了解阴燃传播及其反应状态发生变化的特点,采用一半干燥一半加湿的聚氨酯泡沫材料进行实验。在自然对流条件下,阴燃由下到上从干材料传播到湿材料。各次实验中阴燃在干材料部分都保持稳定传播,而湿材料部分所设计的含水率则从8.4%到21.7%。水分的吸热作用使阴燃状态随含水率大小发生极大的变化。在含水率较小时,阴燃仍能继续传播但温度和速度都有所下降;含水率稍大时,阴燃反应受到抑制,在内部有氧气剩余的情况下则会发生气相反应;当含水率进一步增大,阴燃就会熄灭。如果阴燃能传播到材料末端,外界的大量氧气进入阴燃区将使其向明火发生转化。     

Recursive Operability Analysis as a decision support tool for Risk-Based Maintenance

This work was developed with the support of MEMC, one of the most important producers of ultra-pure silicon wafers for electronic applications throughout the world. The availability of ultra-pure water is of prime importance in the silicon production process. In order to maximize the availability of UP water, MEMC has developed a preventive maintenance program and a detailed record of each maintenance intervention is recorded. This has allowed a complete failure rate data bank to be developed. In order to optimize the maintenance intervention, a Recursive Operability Analysis (ROA) has been used as a decision support tool. The results of the ROA, coupled with the failure rates, have made it possible to calculate the expected number of events (ENE) of various top events (TEs). The magnitude of each TE has been estimated on the basis of the monetary losses provoked by each event. The risk then has been calculated and the events ranked on this basis. Maintenance policies have been optimized with the aim of reducing the risk of the top ranked events.     

The degradation of cyanide by anodic electrooxidation using different anode materials

Cyanides are very popular electrolytes used in metal electroplating, metal ore processing, chemical and electrochemical applications. Due to wide utility of these technologies cyanides become increasingly harmful effluent, which has to be treated. One of the best ways to degrade cyanides is an anodic electrooxidation. In this work the destruction of free cyanide on platinum, titanium and stainless steel (SS) electrodes has been investigated. It was determined that anode material greatly influences the process of cyanide electrooxidation. The best results were obtained by using the Pt electrode. This kind of anode allows us to reduce CN^? concentration from 0.1 M to 0.06 M during the first hour of electrolysis at a current density of 200 A m^?2, with a current efficiency up to 80%. To substitute expensive Pt anodes Ti electrodes covered with nanolayers of Pt were prepared and used for the anodic oxidation of cyanide ions. An effect of a thickness of Pt layer and temperature of an electrolyte solution were studied. It was established that using platinized Ti electrodes the current efficiencies of electrooxidation of cyanides of about 60% can be obtained. The usage of chloride ions to facilitate the destruction of cyanide was also studied.     

TiO2光催化氧化法处理草浆纸厂废水的研究

以TiO2做催化剂,用光催化氧化法处理碱法草浆纸厂废水.讨论了pH值、H2O2的用量、催化剂用量、光照时间等因素对CODCr去除率的影响,优选了反应条件.结果表明:在 pH=6.08,TiO2用量为0.03 g,光照时间3 h,H2O2量(体积分数)为0.60%的条件下,废水的CODCr去除率可达96%以上.处理后废水达到排放标准.     

冷轧乳化液废水处理试验研究

对武钢冷轧乳化液废水采用超滤和氧化破乳法进行对比试验,从试验运行效果、投资费用、运行成本等方面进行了比较分析,得出处理冷轧乳化液废水的最佳方法－超滤法。对冶金行业乳化液废水的处理具有一定的参考价值。