Catalytic combustion of methane over commercial catalysts in presence of ammonia and hydrogen sulphide

The performance of different commercially available catalysts (supported Pd, Pt, Rh, bimetallic Pd-Pt, and Cr-Cu-Ti oxide catalyst) for the oxidation of methane, alone and in presence of ammonia and hydrogen sulphide is studied in this work. Catalysts performance was evaluated both in terms of activity and resistance to poisoning. The main conclusions are that supported Pd and Rh, present the highest activities for methane oxidation, both alone and in presence of ammonia, whereas they are severely poisoned in presence of H2S. Pt and Cr-Cu-Ti are less active but more sulphur resistant, but their activity is lower than the residual activity of sulphur-deactivated Pd and Rh catalysts. The Pd-Pt catalyst exhibits low activity and it is quickly deactivated in presence of hydrogen sulphide.     

CuO(-CeO_2)/SBA-15对萘氧化的催化活性及CO_2选择性研究

通过浸渍法制备CuO/SBA-15和CuO-CeO2/SBA-15两种介孔材料催化剂,采用BET、XRD、TPR和XPS等对催化剂进行表征,重点考察催化剂对萘氧化反应的催化活性及对产物CO2的选择性。BET、XRD和XPS等实验结果表明CuO高度分散于介孔分子筛SBA-15中,CeO2可促进CuO在载体上的分散,同时能降低催化剂的TPR还原温度。活性测试结果表明CuO/SBA-15对萘氧化反应的催化活性较高,但是催化氧化的CO2选择性较低,温度在380℃时CO2的生成率仅为60%左右;CeO2的添加不仅提高了CO2的生成率,15%CuO-15%CeO2/SBA-15在325℃使CO2生成率达到99%,而且CeO2增强了催化剂的稳定性。     

Catalytic wet-air oxidation of a chemical plant wastewater over platinum-based catalysts.

Catalytic wet-air oxidation (CWAO) of wastewater (chemical oxygen demand [COD] = 1800 mg O2/dm3) from a fine chemicals plant was investigated in a fixed-bed reactor at T = 393-473 K under total pressure of 5.0 or 8.0 MPa. Catalysts containing 0.3% wt. of platinum deposited on two supports, mixed silica-titania (SM1) and carbon black composites (CBC) were used. The CBC-supported catalyst appeared to be more active than the SM1-supported one. A slow decrease of activity of the platinum on SM1 (Pt-SM1) during the long-term operation is attributed to recrystallization of titania and leaching of a support component, while the Pt-CBC catalyst is deteriorated, owing to combustion of the support component. The power-law-kinetic equations were used to describe the rate of COD removal at CWAO over the catalysts. The kinetic parameters of COD reduction for the wastewater were determined and compared with the kinetic parameters describing phenol oxidation over the same catalysts. Rates of COD removal for the wastewater were found higher than those for phenol oxidation over the same catalysts and under identical operating conditions.     

Ni-Co bimetallic catalysts on coconut shell activated carbon prepared using solid-phase method for highly efficient dry reforming of methane

Ni-Co bimetallic catalysts supported on coconut shell activated carbon are synthesized using solid-phase method and investigated for dry reforming of methane, to explore the impact of Ni:Co ratio on the catalyst activity and stability. The catalyst performances are evaluated under the temperature varying from 600 to 900 °C and gas hourly space velocity (GHSV) of 7200 mL/h·g-cat. The characterization results show that metal nanoparticles are produced on the support, and the bimetallic catalyst with an explicit Ni:Co ratio (2:1) is the most beneficial for metal particle dispersion and acquires the minimum particle size of 4.41 nm. The bimetallic catalysts with an explicit Ni:Co ratio of 1:2 and 1:1 exhibit a synergistic effect towards the conversions of CH₄ and CO₂, respectively. The experimental results reveal that the highest CH₄ and CO₂ conversions rise to 94.0% and 97.5% within 12 h at 900 °C on average, respectively, assisted with the two bimetallic catalysts. The intensity of disordered carbon and thermal stability are enhanced with the extension of reforming process, contributing to a long-term catalytic stability. Besides, no obvious carbon deposition is detected, leading to a highly catalytic stability for the bimetallic catalysts.

     

CuO（-CeO2）/SBA-15对萘氧化的催化活性及CO2选择性研究

通过浸渍法制备CuO/SBA-15和CuO-CeO2/SBA-15两种介孔材料催化剂,采用BET、XRD、TPR和XPS等对催化剂进行表征,重点考察催化剂对萘氧化反应的催化活性及对产物CO2的选择性。BET、XRD和XPS等实验结果表明CuO高度分散于介孔分子筛SBA-15中,CeO2可促进CuO在载体上的分散,同时能降低催化剂的TPR还原温度。活性测试结果表明CuO/SBA-15对萘氧化反应的催化活性较高,但是催化氧化的CO2选择性较低,温度在380℃时CO2的生成率仅为60%左右;CeO2的添加不仅提高了CO2的生成率,15%CuO-15%CeO2/SBA-15在325℃使CO2生成率达到99%,而且CeO2增强了催化剂的稳定性。     

双氧水催化氧化中Cu/γ-Al_2O_3催化剂的稳定性研究

针对废水湿式双氧水催化氧化,采用浸渍法制备Cu催化剂,研究非均相Cu催化剂在常温常压湿式双氧水催化氧化中的稳定性与失活问题。研究表明,催化剂制备条件及催化氧化反应条件对催化剂中Cu2＋溶出均有影响。研究同时表明,催化剂失活与活性组分流失和活性组分被有机中间产物覆盖有关,高温焙烧可对催化剂再生。     

Ni/Fe-supported over hydrotalcites precursors as catalysts for clean and selective oxidation of Basic Yellow 11: Reaction intermediates determination

In this work, Basic Yellow 11 (BY 11) was employed as model compound to study catalytic wet air oxidation as a pre-treatment step to the conventional biological oxidation. Ni and Fe catalysts supported over hydrotalcite (HT) were prepared by incipient wetness and excess impregnation to obtain catalysts with different metal loadings (from 1 to 10 wt.%). HTs were synthesized by co-precipitation and characterized with XRD, X-ray fluorescence (XRF), BET, thermogravimetric analysis and SEM. Results showed that dye conversion increased with Ni and Fe content up to 7 wt.% and that the most effective catalyst were prepared by incipient wetness impregnation. The influence of metal loading in the catalyst, and the preparation method as well as the reaction conditions was investigated. A mechanism and reaction pathways for BY 11 during catalytic liquid phase oxidation have also been proposed.     

Effects of acid treatments of activated carbon on its physiochemical structure as a support for copper oxide in DeSO(2) reaction catalysts

To enhance the dispersion of active sites, modification of the AC supports with different acid solution might result in various surface oxygen groups which act as anchoring sites for metallic precursor to stay and improve the reactivity between AC supports and copper precursor. In the present work, the AC support is tailored with HCl and HNO(3), respectively. The pore structure, surface oxygen groups of the AC support and catalysts as well as catalyst dispersion before and after acid treatments are systematically studied by BET, pH(slurry), TPD, and XRPD analyses. It is found that the order of activity in DeSO(2) reaction is as follows: Cu/AC-HCl>Cu/AC>Cu/AC-HNO(3). The same sequence is also observed for the pore structure of AC supports, the catalyst dispersion, but not for the amounts of CO(2) evolving during TPD experiments of supports. The key role of acid treatment on carbon surface chemistry and pore structure, which are closely related to catalyst dispersion and adsorption capacity, is examined to rationalize these findings. Furthermore, under the NO/NH(3)=1 the NO could be selective catalytic reduction with NH(3) in the presence of O(2), which catalyzed by fresh and spent AC-supported catalyst.     

Co3O4/介孔分子筛催化剂对苯催化完全氧化的研究

分别以介孔分子筛MCM-41、MCM-48、SBA-15为载体,采用等体积浸渍法制备了氧化钴/介孔分子筛催化剂,利用N₂吸附、X射线衍射、程序升温还原等技术对催化剂进行了表征,考察了Co₃O₄的负载量及载体的孔结构对催化剂完全催化氧化苯的性能的影响。结果表明,Co₃O₄的负载量为20%时,催化剂的催化活性最好;载体的孔径和催化剂的可还原性能是影响催化活性的主要因素,催化剂活性顺序为Co₃O₄ /SBA-15> Co₃O₄ /MCM41> Co₃O₄ /MCM-48。     

Activation of H2O2 by Amberlyst-15 resin supported with copper(II)-complexes towards oxidation of crystal violet

Copper(II) amine complexes supported on Amberlyst-15 cation resin were prepared and characterized by SEM, EDX and FTIR measurements. The kinetics of the heterogeneous oxidation of an organic dye, crystal violet, with H2O2 catalyzed by the supported catalysts was investigated in aqueous solution. The rate of reaction increases with increasing stability of the copper(II) amine complexes. The oxidation rate attained a first-order in the catalyst and the dye only at lower concentrations and second order in H2O2. A very fast formation of a peroxo-dye intermediate resulting from the interaction of H2O2 with the dye even in the presence of the catalyst was observed.     

Factors influencing the preparation of supported iron oxide in fluidized-bed crystallization

Our previous work applied a novel supported iron oxyhydroxide (FeOOH) catalyst to effectively treat benzoic acid by hydrogen peroxide. The FeOOH catalyst was prepared via the oxidation of Fe2+ by H2O2 in the acidic condition using a fluidized-bed crystallization reactor. The major components coated on the surface were identified as amorphous FeOOH and gamma-FeOOH. In terms of the crystallization conditions of FeOOH, some parameters including the operational pH, superficial velocity, specific iron loading, and influent H2O2 concentration were investigated to quantify their effects on the crystallization efficiency. All these parameters were found to significantly influence the crystallization efficiency. Two types of FeOOH catalysts were synthesized: FeOOH I was prepared at pH 3.5, and FeOOH II was formed by aging FeOOH I at pH 13. The percentages of surface amorphous FeOOH reduced from 70% to 30% after aging. The FeOOH II catalyst presented a higher reactivity toward H2O2 but lower stoichiometric efficiency in oxidizing benzoic acid than FeOOH I, similar to the result of the commercial goethite. Therefore, it is concluded that the crystalline property significantly affects the performance of catalytic oxidation.     

Photocatalytic degradation of AZO dyes by supported TiO2 + UV in aqueous solution

The photocatalytic degradation performance of photocatalysts TiO2 supported on 13-X, Na-Y, 4A zeolites with different loading content was evaluated using the photocatalytic oxidation of dyes direct fast scarlet 4BS and acid red 3B in aqueous medium. The results showed that the best reaction dosage of TiO2-zeolite catalysts is about 2 g/l and the photocatalytic kinetics follows first order for all supported catalysts. The photocatalytic activity order of the three series catalysts is 13X type >Y type >4A type. The physical state of titanium dioxide on the supports is evaluated by X-ray photoelectron spectra (XPS), powder X-ray diffraction (XRD), BET, and FTIR.     

A Study of Catalyst Support Systems for Fume-Abatement of Hydrocarbon Solvents

In a stainless steel pilot plant system, operating with combined thermal incineration and catalytic oxidation, studies have been made of the influence of catalyst-support geometry on abatement efficiency. Catalyst supports tested were ceramic spherical pellets, metal foils, and ceramic honeycomb structures, all with precious metal catalyst. Data obtained cover a range of space velocities from 30,000 to 175,000 scf/hr— cu ft bed and a range of catalytic reactor temperatures from 150 to 450°C. Results show that optimum fume-abatement performance is obtained by combining incineration and catalytic oxidation and that catalyst support geometry has a significant effect on performance.     

Catalytic destruction of dichloromethane using perovskite-type oxide catalysts

Dichloromethane (DCM, also known as methylene chloride [CH2Cl2]) is often present in industrial waste gas and is a valuable chemical product in the chemical industry. This study addresses the oxidation of airstreams that contain CH2Cl2 by catalytic oxidation in a tubular fixed-bed reactor over perovskite-type oxide catalysts. This work also considers how the concentration of influent CH2Cl2 (Co = 500-1000 ppm), the space velocity (GHSV = 5000-48,000 1/hr), the relative humidity (RH = 10-70%) and the concentration of oxygen (O2 = 5-21%) influence the operational stability and capacity for the removal of CH2Cl2. The surface area of lanthanum (La)-cobalt (Co) composite catalyst was the greatest of the five perovskite-type catalysts prepared in various composites of La, strontium, and Co metal oxides. Approximately 99.5% CH2Cl2 reduction was achieved by the catalytic oxidation over LaCoO3-based perovskite catalyst at 600 degrees C. Furthermore, the effect of the initial concentration and reaction temperature on the removal of CH2Cl2 in the gaseous phase was also monitored. This study also provides information that a higher humidity corresponds to a lower conversion. Carbon dioxide and hydrogen chloride were the two main products of the oxidation process at a relative humidity of 70%.     

Mn的氧化价态对Mn／γ-Al2O3催化剂催化臭氧氧化气相低浓度甲苯的影响

采用共沉淀法,以Al2O3为载体制备Mn／γ-Al2O3和Mn—Ce／Mn／γ-Al2O3催化剂,并分别在N2气氛和O2气氛下焙烧。采用固定床连续流动反应器,研究所制备催化剂在室温条件下催化臭氧氧化甲苯的性能。通过XRD、XPS和FTIR等手段对催化剂的结构和组成进行表征。结果表明,Mn／Mn／γ-Al2O3催化剂具有良好的催化臭氧氧化甲苯和催化臭氧自身分解的性能,共沉淀法制备催化剂的最佳Mn负载量为20％。O2气氛焙烧和Ce的加入,可以有效提高催化剂的活性和寿命。原因是O2气氛焙烧和Ce的加入可以提高Mn的氧化价态。催化剂失活的主要原因是有机副产物在催化剂表面吸附堆积,失活催化剂在550℃、空气气氛下焙烧可恢复催化性能。     

Evaluating the cytotoxicity of palladium/magnetite nano-catalysts intended for wastewater treatment

Palladium/magnetite nanoparticulate catalysts were developed for efficient elimination of halogenated organic pollutants from contaminated wastewater. Particle recovery from treated water can be ensured via magnetic separation. However, in worst-case scenarios, this catalyst removal step might fail, leading to particle release into the environment. Therefore, a toxicological study was conducted to investigate the impact of both pure magnetite and palladium/magnetite nanoparticle exposure upon human skin (HaCaT) and human colon (CaCo-2) cell lines and a cell line from rainbow trout gills (RTgill-W1). To quantify cell viability after particle exposure, three endpoints were examined for all tested cell lines. Additionally, the formation of reactive oxygen species was studied for the human cells. The results showed only minor effects of the particles on the tested cell systems and support the assumption that palladium/magnetite nano-catalysts can be implemented for a new wastewater treatment technology in which advantageous catalyst properties outweigh the risks.     

活性焦表面性质对CUO/AC脱硫性能的影响

分别以不同浓度的硝酸处理活性焦载体,采用硝酸铜溶液浸渍法制备CuO/AC催化剂,利用BET、FT-IR和XRD等方法对载体及催化剂进行表征.考察了不同浓度的硝酸处理对活性焦载体性质的影响,并对制得的催化剂的脱硫性能进行了比较.结果表明,活性焦经过硝酸处理后孔结构参数变化很小,而表面含氧酸性官能团的含量有了很大的提高,使...     

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans from catalytic and thermal oxidizers burning dilute chlorinated vapors

Emissions of polychlorinated dibenzo-p-dioxins and dibenzofurans (dioxins) have been found from 57 field tests on the oxidation of low (a few to a few hundred) parts per million levels of chlorinated and non-chlorinated volatile organic compounds (VOCs). The oxidation occurs in catalytic oxidizers with platinum, platinum/palladium or chromium(IV) oxide combustion catalysts, or in thermal oxidizers (without a catalyst). The catalyst inlet temperatures ranged from 293 to 573 degrees C. The thermal oxidizer operating temperatures (post-flame) were from 773 to 927 degrees C. Data of the toxic dioxin and furan isomers are reported and also weighted and expressed as international toxic equivalents (TEQ) of 2,3,7,8-tetrachlorodibenzo-p-dioxin. The maximum stack emissions, 1.07 ng/m3 TEQ, occurred at 293 degrees C. Salient results of this field study are: (1) TEQ levels in the stack exponentially increase with a decrease in operating temperature, an empirical equation is TEQ (ng/dscm)=8.4 exp(-0.0084T degrees C); (2) dioxin/furan production occurs at the combustion catalyst; (3) small variations in temperature cause large changes in the congener distribution of the dioxin and furan isomers; (4) molar TEQ yields from the parent compounds fed to the oxidizers are very small (10(-9)-10(-13)); (5) catalytic and thermal oxidizers may destroy dioxins fed from the ambient air; and (6) the oxidation of chlorinated VOCs with non-chlorinated VOCs reduces emissions of dioxins, likely due to the consumption of Cl in producing HCl. Laboratory investigations are needed to understand how dioxins are formed (and emitted) under conditions of this study.     

Heterogeneous water phase catalysis as an environmental application: a review

Catalytic water phase processes as an environmental application is a relatively novel subject with tremendous potential in the near future. This review of 120 references presents the wide scale of heterogeneous water phase applications studied mainly within past five years. Both oxidation and hydrogenation processes are included as well as TiO₂ assisted photocatalysis. According to the references, heterogeneous catalysis is developing rapidly. New bimetallic catalysts and supports with higher surface area have improved catalytic efficiency in both oxidation and hydrogenation processes. It also seems that study on use of some waste materials such as red mud as catalyst is a very progressive field. On the whole, the chemical aspects are pretty well known, but the catalyst durability, and in many cases activity as well, has to be improved.     

铁氧化物复合氧化铝催化臭氧化过程中溴酸盐的生成控制

以市售活性炭、硅藻土和氧化铝小球为载体,考察了负载铁基活性组分对催化臭氧化过程中溴酸盐的控制情况,其中,铁基复合氧化铝小球体现出更好的溴酸盐还原特性和催化剂稳定性,证实催化剂中铁氧化物是溴酸盐得到有效控制的主要活性组分。进一步考察了铁基复合氧化铝小球催化臭氧化处理实际原水过程中对溴酸盐的生成控制,以及反应过程中溶解性有机碳（DOC）的去除情况。结果表明,与单独臭氧化相比,该催化剂既能有效去除水中的溶解性有机物,又能明显抑制溴酸盐的生成,反应50h,其活性并没有明显下降。催化剂失活主要归因于吸附位点数量的下降,可以通过负载铁氧化物来实现催化剂的再生。