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%.     

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.

     

Preparation of the Mn/Co mixed oxide catalysts for low-temperature CO oxidation reaction

The Mn/Co mixed powders with various Mn/Co molar ratios were prepared by the coprecipitation method and used in low-temperature CO oxidation. The physicochemical characteristics of these powders were characterized using the Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), temperature-programmed reduction (TPR), and scanning electron microscopy (SEM) analyses. The results demonstrated that the Mn/Co molar ratio significantly affected both the textural and catalytic properties and the sample with a Mn/Co = 1:1 possessed a BET area of 123.7 m²g⁻¹ with a small mean pore size of 6.44 nm. The catalytic results revealed that the pure cobalt and manganese catalysts possessed the low catalytic activity and the pure Co catalyst is not active at temperatures lower than 140 °C. The highest catalytic activity was observed for the catalyst with a Mn/Co = 1. The obtained results showed that the incorporation of Pd into the Mn/Co catalyst significantly enhanced the catalytic activity for oxidation of carbon monoxide and the highest CO conversion was observed for the catalyst with 1 wt.% Pd and this catalyst exhibited a CO conversion of 100% at 80 ^°C.

     

固体超强酸和金属氧化物类催化剂上CH4-SCR还原NOx研究进展

由于还原剂甲烷价廉易得,甲烷选择性催化还原NO_x（简称CH₄-SCR）被认为是最有潜力替代NH₃-SCR的催化还原技术。现有的CH₄-SCR催化剂中,分子筛类催化剂因催化活性高而被广泛研究,但由于其水热稳定性不好,使得非分子筛负载的催化剂成为近年来的研究热点,其中主要包括固体超强酸和氧化物两大类。综述了这两类催化体系在催化活性、反应机理及掺杂改性等方面的研究现状,比较了各种催化剂的优缺点,并对CH₄-SCR的发展前景进行了展望。     

高浓度钻井废水的混凝-催化氧化处理

以华北油田某深井的高浓度钻井废水(COD高达14 460.0 mg/L)为研究对象,提出了酸化-混凝-催化氧化-吸附的组合处理工艺。重点研制了钻井废水催化氧化处理催化剂(镍基催化剂),通过实验确定了最佳工艺参数条件。着重考察了催化氧化处理的工艺条件,在pH值为4,次氯酸钙投加量为4.4 g/L,催化剂投加量为1.6 g/L的条件下COD降至403.5 mg/L,进一步吸附处理后COD降至139.9 mg/L、色度为30倍、石油类含量为3.8 mg/L、pH为8.0和SS浓度为52mg/L,最终出水水质达到《污水综合排放标准》(GB 8978-1996)二级标准,处理成本为84.8元/m3。     

非均相催化湿式氧化亚甲蓝水溶液的研究

COD为2000 mg/L的亚甲蓝水溶液作为研究对象,用非均相催化湿式氧化技术进行处理,催化剂性能以COD去除率、脱色率以及稳定性来评价.对4种催化剂担体、15种可溶盐活性组分、4种优选铜催化剂的浸渍液浓度进行筛选,并对铜催化剂进行了改性.实验表明,最佳催化剂担体是FSC,活性组分是Cu(NO3)2,并按催化性能对活性组分进行了排序;浸渍液浓度6wt%Cu2 是最佳选择;改性的Cu-Ce/FSC催化剂与Cu/FSC催化剂相比,COD去除率分别为83.9%和84.5%,出水Cu溶出浓度分别为24.1 mg/L和36.1 mg/L,可见改性催化剂与原催化剂的活性相当,但是稳定性却有了大幅度的提高.     

氧化锰矿渣改性制备SCR脱硝催化剂

以锰酸钾生产过程中产生的氧化锰矿渣为原料,制备了一系列Mn基SCR脱硝催化剂。研究了活性炭、二氧化钛、以及含锰量的变化对催化剂的脱硝活性的影响。结果表明,直接由矿渣制备的催化剂和添加活性炭、二氧化钛制备的催化剂,其最大脱硝率分别为40%和78%。XPS表征发现催化剂中的锰元素存在多种氧化价态,活性炭的加入在一定程度上改变了不同价态之间的相对含量;在矿渣中加入硫酸锰后,发现总锰含量达到10%时,催化剂的最大脱硝率从78%降低至57%,XRD测试发现硫酸锰的加入导致S2O27-物种的生成,可能是引起催化剂活性下降的原因之一;而加入醋酸锰至总锰含量达到10%时,增大了催化剂的活性温度窗口,当总锰含量达到20%时,在空速10 000 h-1条件下,催化剂的最大脱硝率达到86.7%。     

Public Relations Handbook

A major difficulty encountered in laboratory research on the atmospheric interaction of an aerosol-gas system is the unstable nature of the aerosol phase. Previously reported aerosol stabilizing techniques often severely alter the aerosol so that laboratory results cannot be validly extrapolated to the atmospheric environment. A new technique which does not alter the nature of the aerosol is described in this paper.

Aerosol particles are deposited on an inert substrate such as Teflon beads. The deposition is carried out in a fluidized-bed to ensure discrete aerosol deposition and to achieve a uniform distribution of aerosol concentration on the supporting beads. Aerosol-gas interactions can be investigated conveniently by exposing these stabilized aerosols to the reacting gases in dynamic or static systems. Laboratory results obtained by using stabilized aerosols may be extrapolated to the atmospheric environment.

This aerosol stabilizing technique was incorporated into an investigation of the particulate-catalyzed atmospheric oxidation of sulfur dioxide. Teflon beads with deposited aerosol particles of CuCl₂, MnCl₂, and NaCI were exposed to 4–42 ppm of sulfur dioxide in a plug flow reactor. The rate of oxidation of sulfur dioxide was found to be influenced by type of catalyst, concentration of catalyst, relative humidity and concentration of sulfur dioxide. The rate of oxidation by sodium chloride particulate was measurable at low to moderate relative humidities (45–60%), but the rate was several times higher when the sodium chloride catalyst particles change from solid form into droplet form at high relative humidities (>80%).     

Catalytic oxidation for air pollution control

Bench-scale experiments have been conducted to evaluate a series of titania-supported Pt-Pd (as oxides) catalysts in the presence and absence of MoO₃ and Fe₂O₃ additives for their effectiveness in the complete catalytic oxidation of volatile organic compounds (VOCs) in air likely to be found in waste gases. Under oxidizing conditions, all of the catalysts promoted the complete oxidation of VOCs to CO₂ and H₂O. 99 % Conversion was achieved with a C₂H₄-C₂H₆ gas mixture in air at temperatures between about 160–450 °C and at a space velocity of 20,000 h^?1. Oxidation activity for the titania supported catalysts were found to decrease in the order Pt-Pd-Mo-Fe > Pt-Pd-Mo > Pt-Pd-Fe > Pt-Pd. However, the addition of MoO₃ and Fe₂O₃ increase the catalyst activity and reduce the reaction temperature for the complete destruction. Ageing was also performed in order to study the stability of the most active catalyst. Pt-Pd-Mo-Fe (as oxides) on titania catalyst is effective in oxidizing a wide range of volatile organic compounds at relatively low temperatures (220–405 °C) and and at a space velocity of 40,000 h^?1 and is resistant to poisoning by halogenated and amine volatile organic compounds.     

Removal of ammonia solutions used in catalytic wet oxidation processes

Ammonia (NH(3)) is an important product used in the chemical industry, and is common place in industrial wastewater. Industrial wastewater containing ammonia is generally either toxic or has concentrations or temperatures such that direct biological treatment is unfeasible. This investigation used aqueous solutions containing more of ammonia for catalytic liquid-phase oxidation in a trickle-bed reactor (TBR) based on Cu/La/Ce composite catalysts, prepared by co-precipitation of Cu(NO(3))(2), La(NO(3))(2), and Ce(NO(3))(3) at 7:2:1 molar concentrations. The experimental results indicated that the ammonia conversion of the wet oxidation in the presence of the Cu/La/Ce composite catalysts was determined by the Cu/La/Ce catalyst. Minimal ammonia was removed from the solution by the wet oxidation in the absence of any catalyst, while approximately 91% ammonia removal was achieved by wet oxidation over the Cu/La/Ce catalyst at 230 degrees C with oxygen partial pressure of 2.0 MPa. Furthermore, the effluent streams were conducted at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes, and a reaction pathway was found linking the oxidizing ammonia to nitric oxide, nitrogen and water. The solution contained by-products, including nitrates and nitrites. Nitrite selectivity was minimized and ammonia removal maximized when the feed ammonia solution had a pH of around 12.0.     

氯甲烷与偶氮染料混合废水的超声脱色

使用40 kHz超声(US)脱色氯甲烷(包括CCl4、CHCl3和CH2Cl2)与偶氮染料(包括甲基橙与铬黑T)混合模拟废水,考察了氯甲烷初始浓度对偶氮染料超声脱色和TOC去除的影响.结果表明:偶氮染料的单独超声脱色速率很慢;而在CCl4与CHCl3存在时超声能使偶氮染料短时间内脱色至无色,但对其TOC的超声去除促进作...     

Surface properties and catalytic performance of La(1-x)Sr(x)FeO(3) perovskite-type oxides for methane combustion

La(1-x)Sr(x)FeO(3) (x=0.0-1.0) perovskites were prepared and tested for the combustion of methane. X-ray diffraction (XRD) patterns revealed the presence of a single perovskite structure for substitutions 0x0.3, however Fe(2)O(3), SrCO(3) and SrFeO(3) phases were observed for substitutions x>0.3. The results of activity test indicate that with La(1-x)Sr(x)FeO(3) as the catalyst, the combustion of methane can take place at low temperatures around 400 degrees C. Partial substitution of La with Sr increases the activity and an optimal substitution fraction (x=0.5) exists in the La(1-x)Sr(x)FeO(3) catalysts. Catalyst activity can be well correlated to the product of the specific surface area and atomic ratio of Fe to La+Sr on the catalyst surface. Experimental results of O(2)-TPD and CH(4)-TPD in the range of 350-500 degrees C indicate that the amount of oxygen desorbed from the La(1-x)Sr(x)FeO(3) catalysts is far larger than that of methane. Therefore, it can be proposed that the catalytic oxidation of CH(4) over these catalysts proceeds with the surface reaction between CH(4) in the gas phase and the adsorbed O(2). Addition of water vapor or CO(2) to the feed inhibited catalyst activity, but the inhibition was reversible and became negligible at high reaction temperature.     

Mathematical Model for Photocatalytic Destruction of Organic Contaminants in Air

Abstract

Photocatalytic oxidation (PCO) was investigated in a bench-scale reactor for the abatement of two airborne organic contaminants: toluene and ethanol. A mathematical model that includes the impacts of light intensity, initial contaminant concentration, catalyst thickness, and relative humidity (RH) on the degradation of organic contaminants in a photocatalytic reactor was developed to describe this process. The commercially available catalyst Degussa-PtTiO₂ was selected to compare with the MTU-PtTiO₂-350 catalyst, which was synthesized by the sol-gel process, platinized, and calcined at 350 °C. For toluene removal using the MTU-PtTiO₂-350 catalyst, the degradation rate increased with increases in light intensity from 0.2 to 2.2 mW/cm² and in catalyst thickness from 0.00037 to 0.00361 cm. However, further increases in light intensity and catalyst thickness had only slight effect on the toluene degradation rate. Increasing the initial concentration from 6.29 to 127.9 μg/L and the RH from 10 to 85% resulted in decreases in the toluene degradation rate. For ethanol removal using the MTU-PtTiO₂- 350 catalyst, the degradation rate increased more rapidly with an increase in RH from 17 to 56%; the RH had little effect on the ethanol degradation rate while it further increased from 56% to 82%. We discuss applicability of the model to estimate the influence of process variables and to evaluate photocatalyst performance.     

Selective catalytic oxidation of ammonia over copper-cerium composite catalyst

This work considers the oxidation of ammonia (NH3) by selective catalytic oxidation (SCO) over a copper (Cu)-cerium (Ce) composite catalyst at temperatures between 150 and 400 degrees C. A Cu-Ce composite catalyst was prepared by coprecipitation of copper nitrate and cerium nitrate at various molar concentrations. This study also considers how the concentration of influent NH3 (500-1000 ppm), the space velocity (72,000-110,000 hr(-1)), the relative humidity (12-18%) and the concentration of oxygen (4-20%) affect the operational stability and the capacity for removing NH3. The effects of the O2 and NH3 content of the carrier gas on the catalyst's reaction rate also are considered. The experimental results show that the extent of conversion of NH3 by SCO in the presence of the Cu-Ce composite catalyst was a function of the molar ratio. The NH3 was removed by oxidation in the absence of Cu-Ce composite catalyst, and approximately 99.2% NH3 reduction was achieved during catalytic oxidation over the Cu-Ce (6:4, molar/molar) catalyst at 400 degrees C with an O2 content of 4%. Moreover, the effect of the initial concentration and reaction temperature on the removal of NH3 in the gaseous phase was also monitored at a gas hourly space velocity of less than 92,000 hr(-1).     

微波辐射Bi2O3/沸石-H2O2体系降解废水中的硝基苯

研究了微波辐射下,以负载于沸石上的三氧化二铋为催化剂,以双氧水为氧化剂的催化氧化体系处理硝基苯工艺。通过单因素实验法,从反应催化剂负载量、pH、双氧水用量、微波功率、反应时间、催化剂用量等方面初步考察了硝基苯在该体系中的催化氧化效果。在氧化铋负载量3%（质量比）,pH=2,2 mL 30%双氧水,火力为中火,催化剂投加量为0.7 g,反应2 min,对降解过程所得的中间产物和终产物进行了分析。结果表明,该体系对硝基苯的去除率能够达到99.2%,COD去除率为73.91%。     

Superior Pillared Clay Catalysts for Selective Catalytic Reduction of Nitrogen Oxides for Power Plant Emission Control

ABSTRACT

Fe³+-, Cr³+-, Cu²+-, Mn²+-, Co²+-, and Ni²+-exchanged Al₂O₃-pillared interlayer clay (PILC) or TiO₂-PILC catalysts are investigated for the selective catalytic reduction (SCR) of nitric oxide by ammonia in the presence of excess oxygen. Fe³+-exchanged pillared clay is found to be the most active. The catalytic activity of Fe-TiO₂-PILC could be further improved by the addition of a small amount of cerium ions or cerium oxide. H₂O and SO₂ increase both the activity and the product selectivity to N₂. The maximum activity on the Ce-Fe-TiO₂-PILC is more than 3 times as active as that on a vanadium catalyst. Moreover, compared to the V₂O₅-WO₃/TiO₂ catalyst, the Fe-TiO₂-PILC catalysts show higher N₂/N₂O product selectivities and substantially lower activities (by ~85%) for SO₂ oxidation to SO₃ under the same reaction conditions. A 100-hr run in the presence of H₂O and SO₂ for the CeO₂/Fe-TiO₂-PILC catalyst showed no decrease in activity.     

用于气态零价汞转化的催化剂研究

零价汞的高效去除是燃煤烟气汞污染控制过程中的关键环节。为了促进烟气中的零价汞转化为易于去除的氧化态汞,分别考察了在有HCl存在时,几种过渡金属氧化物(Cu、Fe、Mn、Co和Zr)对零价汞氧化的催化作用,以筛选出性能较好的催化组分;为提高催化剂的抗SO2性能,分别尝试了利用几种金属元素(Sr、Ce、W和Mo)对催化剂进行掺杂改性的方法。结果表明,锰氧化物的催化作用最好,其最佳使用温度在573 K左右;SO2对零价汞的催化氧化有明显抑制作用,在无SO2及1 400 mg/m3SO2时锰催化剂对零价汞催化氧化效率分别为93%和78%。而Mo改性的锰氧化物催化剂的抗硫性能大幅提高,在1 400 mg/m3SO2存在的情况下其对零价汞的催化氧化效率可达到90%以上,较其他改性元素高。     

La1-x Cex Cuy Mn1-yO3／HZSM-5催化剂低温去除柴油机碳烟和NOx

为实现对柴油机碳烟和NOx的低温同步去除,采用柠檬酸络合法制备分子筛负载钙钛矿型金属复合氧化物催化剂,应用x衍射分析仪（XRD）和电镜扫描仪（SEM）对催化剂性能进行表征,并在微型固定床反应器中对催化剂低温去除碳烟和NOx进行活性评价。利用程序升温反应（TPR）技术,进行催化剂活性评价、柴油机负荷和排放等特性实验。结果表明,A位用适量Ce部分取代La,B位用适量cu部分取代Mn,可使碳颗粒燃烧温度降低,CO2选择性好,NOx转化率升高。La0.4 Ce0.6 Cu0.2 Mn0.8O3／HZSM-5催化剂的最大NOx转化率为81．0％,Ti、Tm和Tf分别为250、350和475℃,表明该催化剂具有较好的催化活性,能在低温条件下去除碳烟和NOx。     

铜铈掺杂六铝酸盐的脱硝性能

用共沉淀法制备用于脱除NO的六铝酸盐催化剂LaMxAl12-xO19(M =Cu,Ce,CuCe).用XRD、H2-TPR和BET对催化剂进行了结构和物性表征.用微型催化反应装置考察了催化剂在CO选择性催化还原NO中的活性.结果表明,Cu离子易于进入六铝酸盐晶格内,形成完整的六铝酸盐结构.Ce离子不易于进入六铝酸盐晶格内,主要以CeO2的形式存在.在CO+ NO条件下,3种催化剂都表现出较好的脱硝活性,LaCuCeAl10O19中由于Cu离子与Ce离子间产生协同作用,该催化剂的脱硝活性有所增加.加入SO2后,3种催化剂都有不同程度的失活现象发生,其中LaCuAl11O19催化剂受SO2中毒影响最严重,LaCuCeAl10O19催化剂的脱硝活性在三者中最好.