CuO impregnated activated carbon for catalytic wet peroxide oxidation of phenol

This paper presents an original approach to the removal of phenol in synthetic wastewater by catalytic wet peroxide oxidation with copper binding activated carbon (CuAC) catalysts. The characteristics and oxidation performance of CuAC in the wet hydrogen peroxide catalytic oxidation of phenol were studied in a batch reactor at 80 °C. Complete conversion of the oxidant, hydrogen peroxide, was observed with CuAC catalyst in 20 min oxidation, and a highly efficient phenol removal and chemical oxygen demand (COD) abatement were achieved in the first 30 min. The good oxidation performance of CuAC catalyst was contributed to the activity enhancement of copper oxide, which was binding in the carbon matrix. It can be concluded that the efficiency of oxidation dominated by the residual H₂O₂ in this study. An over 90% COD removal was achieved by using the multiple-step addition in this catalytic oxidation.     

Catalytic wet air oxidation of phenol over CeO2-TiO2 catalyst in the batch reactor and the packed-bed reactor

CeO2-TiO2 catalysts are prepared by coprecipitation method, and the activity and stability in the catalytic wet air oxidation (CWAO) of phenol are investigated in a batch reactor and packed-bed reactor. CeO2-TiO2 mixed oxides show the higher activity than pure CeO2 and TiO2, and CeO2-TiO2 1/1 catalyst displays the highest activity in the CWAO of phenol. In a batch reactor, COD and TOC removals are about 100% and 77% after 120 min in the CWAO of phenol over CeO2-TiO2 1/1 catalyst at reaction temperature of 150 degrees C, the total pressure of 3 MPa, phenol concentration of 1000 mg/L, and catalyst dosage of 4 g/L. In a packed-bed reactor using CeO2-TiO2 1/1 particle catalyst, over 91% COD and 80% TOC removals are obtained at the reaction temperature of 140 degrees C, the air total pressure of 3.5 MPa, the phenol concentration of 1000 mg/L for 100 h continue reaction. Leaching of metal ions of CeO2-TiO2 1/1 particle catalyst is very low during the continuous reaction. CeO2-TiO2 1/1 catalyst exhibits the excellent activity and stability in the CWAO of phenol.     

花球状CuO/CeO2材料上HCN的催化消除

利用水热法和沉积沉淀法分别合成了微米级花球状CeO2载体和含有不同质量分数CuO纳米颗粒的负载型CuO/CeO2材料.考察CuO/CeO2材料对HCN的防护时间和消除率,并与KZ09-1防毒活性炭样品对HCN的防护性能进行比较,进而评价CuO/CeO2催化材料对HCN的防护性能.催化材料在25℃、体积空速为120000 h-1、水汽体积分数为5％的反应条件下,对130 mg/m3 HCN的防护性能为:10％CuO/CeO2>15％CuO/CeO2>5％CuO/CeO2>KZ091>3％CuO/CeO2>1％CuO/CeO2.考察反应温度对HCN消除率的影响发现,当反应温度为100℃、反应时间为2 h时,催化材料对HCN的消除率可达98％.考察不同反应温度条件下反应产物的选择性,对HCN在催化材料上的反应机理进行推测,当反应温度为25～50℃时,催化材料对HCN的消除以化学吸附为主,伴随有催化水解和催化氧化反应;当反应温度为50～100℃时,HCN在催化材料表面通过化学吸附、催化水解及催化氧化反应消除,其中催化水解和催化氧化占主导作用;当反应温度为100～200℃时,HCN在催化材料表面通过化学吸附、催化水解、催化氧化以及NH3-SCR反应协同消除.     

Investigation of the catalytic wet peroxide oxidation of phenol over different types of Cu/ZSM-5 catalyst

In this work oxidation of phenol with hydrogen peroxide on Cu/ZSM-5 catalysts was studied. The catalysts samples were prepared by two different methods: by ionic exchange from the protonic form of commercial ZSM-5 zeolite, and by direct hydrothermal synthesis. Characterization of the catalysts extends to X-ray diffraction (XRD), while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and the temperature range from 50 to 80 degrees C. The mass ratio of the active metal component on the zeolite was in the range of 1.62-3.24 wt.%. for catalyst prepared by direct hydrothermal synthesis and 2.23-3.52 wt.% for catalyst prepared by ion exchange method. The initial concentration of phenol and hydrogen peroxide was 0.01 and 0.1 mol dm(-3), respectively. The influence of different methods of Cu/ZSM-5 preparation on their catalytic performance was monitored in terms of phenol conversion and degree of metal leached into aqueous solution.     

Catalytic wet air oxidation of chlorophenols over supported ruthenium catalysts

A series of noble metal (Pt, Pd, Ru) loaded zirconia catalysts were evaluated in the catalytic wet air oxidation (CWAO) of mono-chlorophenols (2-CP, 3-CP, 4-CP) under relatively mild reaction conditions. Among the investigated noble metals, Ru appeared to be the best to promote the CWAO of CPs as far as incipient-wetness impregnation was used to prepare all the catalysts. The position of the chlorine substitution on the aromatic ring was also shown to have a significant effect on the CP reactivity in the CWAO over 3wt.% Ru/ZrO(2). 2-CP was relatively easier to degradate compared to 3-CP and 4-CP. One reason could be the higher adsorption of 2-CP on the catalyst surface. Further investigations suggested that 3wt.% Ru/ZrO(2) is a very efficient catalyst in the CWAO of 2-CP as far as high 2-CP conversion and TOC abatement could still be reached at even lower temperature (393K) and lower total pressure (3MPa). Additionally, the conversion of 2-CP was demonstrated to increase with the initial pH of the 2-CP solution. The dechlorination reaction is promoted at higher pH. In all cases, the adsorption of the reactants and the reaction intermediates was shown to play a major role. All parameters that would control the molecule speciation in solution or the catalyst surface properties would have a key effect.     

CuO/CeO2催化剂的制备及低温催化CO性能测试

采用化学共沉淀法制备了CuO/CeO2催化剂,并用XRD,HRTEM和FT-IR等对样品进行了表征,利用微反色谱装置测定了其CO低温氧化活性.主要考察了反应温度对催化剂结构和性能的影响.结果表明,共沉淀反应温度影响CuO/CeO2的物性(形貌、粒度大小及分布等)和催化活性.在共沉淀反应温度为40℃时,CuO/CeO2催...     

介孔Ag/CeO2材料结构及湿式催化氧化性能研究

以硝酸铈、硝酸银为原料,嵌段聚合物F127为模板剂,采用微波辅助软模板法制备了不同Ag负载量的介孔Ag/CeO2复合材料.对材料进行XRD、N2吸附-脱附、XPS、SEM以及EDS表征分析.结果表明,Ag/CeO2复合材料属于介孔结构,具有较大的比表面积,存在Ce3+、Ce4+,Ag离子均匀负载于CeO2表面.考察了影...     

Effect of CeO2 doping on catalytic activity of Fe2O3/gamma-Al2O(3) catalyst for catalytic wet peroxide oxidation of azo dyes

In order to find a catalyst with high activity and stability for catalytic wet peroxide oxidation (CWPO) process under normal condition, with Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) catalysts prepared by impregnation method, the effect of CeO(2) doping on the structure and catalytic activity of Fe(2)O(3)/gamma-Al(2)O(3) for catalytic wet peroxide oxidation of azo dyes at 25 degrees C and atmospheric pressure is evaluated using BET, SEM, XRF, XRD, XPS and chemical analysis techniques, and test results show that, better dispersion and smaller size of Fe(2)O(3) crystal can be achieved by adding CeO(2), and the content of chemisorbed oxygen can also be increased on the surface of catalyst. CWPO experimental results indicate that azo dyes in simulated wastewater can be efficiently mineralized and the catalytic activity of Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) can be increased by about 10% compared with that of Fe(2)O(3)/gamma-Al(2)O(3) because of the promotion of the structural and redox properties of the ferric oxide by ceria doped. Leaching tests indicate that Fe(2)O(3)/gamma-Al(2)O(3) and Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) are stable with a negligible amount of irons found in the aqueous solution after reaction for 2h. It can therefore be concluded from results and discussion that in comparison with Fe(2)O(3)/gamma-Al(2)O(3), Fe(2)O(3)-CeO(2)/gamma-Al(2)O(3) is a suitable catalyst, which can effectively degrade contaminants at normal temperature and atmospheric pressure.     

Visible light induced degradation of methylene blue using CeO2/V2O5 and CeO2/CuO catalysts

In the present study, the nanocatalysts CeO₂, V₂O₅, CuO, CeO₂/V₂O₅ and CeO₂/CuO were synthesized by thermal decomposition method. This method is simple, fast and cost effective compared with other preparation methods. The synthesized catalysts were characterized by different techniques. The XRD and XPS results confirmed the structure and the oxidization states of the nanocomposite materials. DRS results suggested that the prepared CeO₂/V₂O₅ and CeO₂/CuO nanocomposites can generate more electrons and holes under visible light irradiation. The photocatalytic activities of prepared catalysts were evaluated using the degradation of aqueous methylene blue solution as a model compound under visible light irradiation. In addition, the nanocomposite (CeO₂/V₂O₅ and CeO₂/CuO) materials were employed to degrade the textile effluent under visible light condition.     

Catalytic wet peroxide oxidation of azo dye (Congo red) using modified Y zeolite as catalyst

The present study explores the degradation of azo dye (Congo red) by catalytic wet peroxide oxidation using Fe exchanged commercial Y zeolite as a catalyst. The effects of various operating parameters like temperature, initial pH, hydrogen peroxide concentration and catalyst loading on the removal of dye, color and COD from an aqueous solution were studied at atmospheric pressure. The percent removals of dye, color and COD at optimum pH₀ 7, 90 °C using 0.6 ml H₂O₂/350 ml solution and 1 g/l catalyst was 97% (in 4 h), 100% (in 45 min) and 58% (in 4 h), respectively. The % dye removal has been found to be less in comparison to % color removal at all conditions, e.g. dye removal in 45 min and at above conditions was 82%, whereas the color removal was 100%. The results indicate that the Fe exchanged Y zeolite is a promising catalyst for dye removal. Fe exchanged catalyst is characterized using XRD, SEM/EDAX, surface area analyzer and FTIR. Though the dye, color and COD removals were maximum at pH₀ 2 but as the leaching of Fe from the catalyst was more in acidic pH range, pH₀ 7 was taken as operating pH due to almost comparable removals as of pH₀ 2 and no leaching of Fe ions.     

Preparation,characterization and catalytic properties of CuO/CeO2 system

CeO₂ nano-particles and CuO/CeO₂ system were prepared by sol-gel and impregnation methods and characterized using combined spectroscopic techniques of XRD, XPS, TPR, FT–Raman, BET and HRTEM. It was found the CeO₂ was cubic phase with fluorite structure and CuO was highly dispersed on the CeO₂ particles. Temperature-programmed reduction (TPR) showed a two-step reduction for CuO/CeO₂ catalysts. XPS analysis indicated the presence of redox couple Ce⁴⁺/Ce³⁺ and reduced copper species in the CuO/CeO₂ catalysts. The factors, such as calcination temperature, calcination time and CuO loading, influenced on the catalytic properties of CuO/CeO₂ catalysts.     

Fe/FSM-16催化苯酚与过氧化氢反应合成二酚

中孔分子筛的改性是近年来研究的一个热点.采用铁改性的FSM-16催化苯酚与过氧化氢反应合成二酚,研究了铁负载量、催化剂用量、反应时间和温度等对催化剂性能的影响.在优化反应条件下,以水为溶剂,苯酚的转化率达到25.4％,二酚的选择性为88.9％.实验结果表明该催化剂可以重复使用.Fe/FSM-16与在工业生产使用的TS-...     

Kinetic and wet oxidation of phenol catalyzed by non-promoted and potassium-promoted manganese/cerium oxide

The wet oxidation of organic compounds to CO2 and H2O has been shown to be a very efficient technique in the outflows treatment. This work focuses on the interaction of the chemical element potassium with the catalyst MnO2-CeO2 in the wet degradation of phenol. The reaction has been carried out in an autoclave with a controlled system of agitation, pressure, temperature and sampling of the liquid phase. The experiments were performed in the presence of the catalysts MnO2-CeO2 and K-MnO2-CeO2 in the following operational conditions: temperature of 130 degrees C, P = 20.4 atm, catalyst concentration in the range 1.5-5.0 g/L, initial phenol concentration of 0.5 g/L, initial pH varying between 6.8 and 8.5, and percentage of potassium in the catalyst MnO2-CeO2 ranging between 0% and 10%. Curves indicating the profile of conversion of total organic carbon show that the phenol degradation is favored when the potassium quantity is reduced. This behaviour is confirmed by BET analysis, whereby the catalyst presents larger specific area when compared to the percentages of other components. Regardless of the catalyst used in the phenol oxidation, the kinetic constant of reaction had the same order of magnitude for two parallel stages proposed by a first-order kinetic model.     

Bimetallic catalysts for continuous catalytic wet air oxidation of phenol.

Catalytic wet oxidation has proved to be effective at eliminating hazardous organic compounds, such as phenol, from waste waters. However, the lack of active long-life oxidation catalysts which can perform in aqueous phase is its main drawback. This study explores the ability of bimetallic supported catalysts to oxidize aqueous phenol solutions using air as oxidant. Combinations of 2% of CoO, Fe2O3, MnO or ZnO with 10% CuO were supported on gamma-alumina by pore filling, calcined and later tested. The oxidation was carried out in a packed bed reactor operating in trickle flow regime at 140 degrees C and 900 kPa of oxygen partial pressure. Lifetime tests were conducted for 8 days. The pH of the feed solution was also varied. The results show that all the catalysts tested undergo severe deactivation during the first 2 days of operation. Later, the catalysts present steady activity until the end of the test. The highest residual phenol conversion was obtained for the ZnO-CuO, which was significantly higher than that obtained with the 10% CuO catalyst used as reference. The catalyst deactivation is related to the dissolution of the metal oxides from the catalyst surface due to the acidic reaction conditions. Generally, the performance of the catalysts was better when the pH of the feed solution was increased.     

CuO＋ZnO/CeO2/Al2O3水煤气变换活性及其表面形貌网络特征分析

以3 mm Al2O3作为主载体,采用浸渍与焙烧工艺,制备水煤气低温变换催化剂:CuO+ZnO/CeO2/Al2O3.利用X射线衍射(XRD)、扫描电子显微镜(SEM)、Raman散射光谱分别对催化剂的化学组成、表面形貌以及表面元素键合状态进行表征;对催化剂的水煤气变换反应(WGSR)活性进行测试.在对催化剂表面形貌进行数据挖掘的基础上,利用复杂网络方法对催化剂的表面形貌进行网络建模,并对其网络拓扑参数和同步性进行了计算.计算结果表明,CuO+ZnO/CeO2/Al2O3表面形貌网络度分布具有幂律分布特征;在催化WGSR以后,催化剂表面形貌网络同步性有所增强.     

Catalytic activity of CuOn-La2O3/gamma-Al2O3 for microwave assisted ClO2 catalytic oxidation of phenol wastewater

In order to develop a catalyst with high activity and stability for microwave assisted ClO2 catalytic oxidation, we prepared CuOn-La2O3/gamma-Al2O3 by impregnation-deposition method, and determined its properties using BET, XRF, XPS and chemical analysis techniques. The test results show that, better thermal ability of gamma-Al2O3 and high loading of Cu in the catalyst can be achieved by adding La2O3. The microwave assisted ClO2 catalytic oxidation process with CuOn-La2O3/gamma-Al2O3 used as catalyst was also investigated, and the results show that the catalyst has an excellent catalytic activity in treating synthetic wastewater containing 100 mg/L phenol, and 91.66% of phenol and 50.35% of total organic carbon (TOC) can be removed under the optimum process conditions. Compared with no catalyst process, CuOn-La2O3/gamma-Al2O3 can effectively degrade contaminants in short reaction time and with low oxidant dosage, extensive pH range. The comparison of phenol removal efficiency in the different process indicates that microwave irradiation and catalyst work together to oxidize phenol effectively. It can therefore be concluded from results and discussion that CuOn-La2O3/gamma-Al2O3 is a suitable catalyst in microwave assisted ClO2 catalytic oxidation process.     

Degradation of chemical substances using wet peroxide oxidation under mild conditions

The objectives of this study are to clarify the degradation mechanism of chemical substances using wet peroxide oxidation (WPO) under mild condition (150 degrees C) and to confirm the removal of polychlorinated biphenyls (PCBs) in soil using this oxidation process. Acetic and oxalic acids were mineralized using WPO. TOC removal rate of acetic acid was highest in the solution of pH 2.5. However, TOC removal rate was decreased with the increase in pH and TOC were hardly removed in the solution of pH 7 and 10. The decomposition rate of isobutyric acid by WPO decreased in the presence of radical scavenger (t-BuOH). The results suggested that the decomposition of chemical substances using WPO proceeded by hydroxyl radical (OH radical). PCBs in soil were also decomposed by performing WPO at 150 degrees C.     

Catalytic properties of carbon materials for wet oxidation of aniline

A mesoporous carbon xerogel with a significant amount of oxygen functional groups and a commercial activated carbon, were tested in the catalytic wet air oxidation of aniline at 200 degrees C and 6.9 bar of oxygen partial pressure. Both carbon materials showed high activity in aniline and total organic carbon removal, a clear increase in the removal efficiency relatively to non-catalytic wet air oxidation being observed. The best results in terms of aniline removal were obtained with carbon xerogel, an almost complete aniline conversion after 1h oxidation with high selectivity to non-organic compounds being achieved. The materials were characterized by thermogravimetric analysis, temperature programmed desorption, N(2) adsorption and scanning electron microscopy, in order to relate their performances to the chemical and textural characteristics. It was concluded that the removal efficiency, attributed to both adsorption and catalytic activity, is related to the mesoporous character of the materials and to the presence of specific oxygen containing functional groups at their surface. The effect of catalytic activity was found to be more important in the removal of aniline than the effect of adsorption at the materials surface. The results obtained indicate that mesoporous carbon xerogels are promising catalysts for CWAO processes.