Production of copper-based rare earth composite metal materials by coprecipitation and applications for gaseous ammonia removal

This study addresses the oxidation of ammonia (NH3) at temperatures between 423 and 673 K by selective catalytic oxidation (SCO) over a copper-based, rare earth composite metal material that was prepared by coprecipitating copper nitrate, lanthanum nitrate, and cerium nitrate at various molar ratios. The catalysts were characterized using Brunner, Emmett, and Teller spectroscopy, Fourier-transform infrared spectroscopy, Xray diffraction, ultraviolet-visible spectroscopy, cyclic voltammetric spectroscopy, and scanning electron microscopy. At a temperature of 673 K and an oxygen content of 4%, approximately 99.5% of the NH3 was reduced by catalytic oxidation over the 6:1:3 copper-lanthanum-cerium (molar ratio) catalyst. Nitrogen (N2) was the main product of this NH3-SCO process. Results from the activity and selectivity tests revealed that the optimal catalyst for catalytic performance had the highest possible cerium content and specific surface area (43 m2/g).     

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%.     

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.     

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.     

Characterization and reactivity of natural manganese ore catalysts in the selective catalytic oxidation of ammonia to nitrogen

Natural manganese ore (NMO) catalysts were characterized and tested in the selective catalytic oxidation of ammonia to nitrogen oxides under dilute conditions. Also, the oxidation of ammonia (NH(3)) was carried out using pure MnO(2), Mn(2)O(3) for comparing with the activity. It is found that the activity of NMO was similar to that of MnO(2) at low temperature below 150 degrees C but above this temperature, the activity of these catalysts showed the difference. In the course of NH(3) oxidation, N(2), NO, N(2)O and H(2)O were produced. But the quantity of NO(2) produced in this experiment was negligible. At temperature below 250 degrees C, selectivity into N(2) from NH(3) oxidation was in the order, NMO > MnO(2) > Mn(2)O(3). This is the reverse of activity of these manganese oxides. Also the characterization of NH(3) oxidation was proposed and supported by the effect of space velocity, inlet O(2) and NH(3) concentration. The increase of space velocity remarkably influenced not only the conversion but also selectivity into N(2). The higher the reaction temperature was, the higher the effect of inlet O(2) and NH(3) concentration on the reaction rate was. By introducing NO during NH(3) oxidation reaction, the possibility of NMO as selective catalytic reduction catalyst at low temperature was studied and showed positive results.     

An assessment of the suitable operating conditions for the CeO2/gamma-Al2O3 catalyzed wet air oxidation of phenol

It has been shown that the CeO2/gamma-Al2O3 catalyst is a feasible alternative to CeO2 for the catalytic wet air oxidation (CWAO) of phenol because it remains an effective catalyst and yet is cheaper to prepare. In this study, we found that the optimal cerium content in the CeO2/gamma-Al2O3 catalyst was 20 wt.%, regardless of catalyst loading. Furthermore, at 180 degrees C, with a phenol concentration of 1000 mg l(-1), and an O2 partial pressure of 1.0M Pa or 1.5M Pa, the optimal catalyst loading was 3.0 gl (-1). The efficacy of CWAO of phenol improved with O2 partial pressure, although the effects of O2 pressure were more significant between 0.5 MPa and 1.5 MPa than between 1.5 MPa and 2.0 MPa. After 2 h of reaction, approximately 100% phenol conversion and 80% total organic carbon (TOC) removal was recorded at 180 degrees C, 1000 mg l(-1) of phenol and 3.0 g l(-1) of catalyst. Because these percentages subsequently leveled off, it is suggested that 2 h is a suitable time over which to run the reaction. The efficacy of CWAO of phenol decreased as initial phenol concentration was raised (from 400 to 2500 mg l(-1)), with the exception of phenol conversion after about 2 h, for which 400 mg l(-1) produced the lowest phenol conversion figure. Higher phenol concentrations require both catalyst loading and O2 partial pressure to be increased to maintain high performance. For example, for 2000 mg l(-1) and 2500 mg l(-1) phenol, nearly 100% phenol conversion and 90% TOC removal after 4 h of reaction at 180 degrees C required 4.0 g l(-1) of catalyst and 2.0 MPa.     

Catalytic Destruction of Dichloromethane Using Perovskite-Type Oxide Catalysts

Abstract

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 (C_o = 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 CH₂Cl_2.

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 La-CoO₃-based perovskite catalyst at 600 °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%.     

Simultaneous absorption of NO and SO2 into hexamminecobalt(II)/iodide solution

An innovative catalyst system has been developed to simultaneously remove NO and SO2 from combustion flue gas. Such catalyst system may be introduced to the scrubbing solution using ammonia solution to accomplish sequential absorption and catalytic oxidation of both NO and SO2 in the same reactor. When the catalyst system is utilized for removing NO and SO2 from the flue gas, Co(NH3)(6)2+ ions act as the catalyst and I- as the co-catalyst. Dissolved oxygen, in equilibrium with the residual oxygen in the flue gas, is the oxidant. The overall removal process is further enhanced by UV irradiation at 365 nm. More than 95% of NO is removed at a feed concentration of 250-900 ppm, and nearly 100% of SO2 is removed at a feed concentration of 800-2500 ppm. The sulfur dioxide co-existing in the flue gas is beneficial to NO absorption into hexamminecobalt(II)/iodide solution. NO and SO2 can be converted to ammonium sulfate and ammonium nitrate that can be used as fertilizer materials. The process described here demonstrates the feasibility of removing SO2 and NO simultaneously only by retrofitting the existing wet ammonia flue-gas-desulfurization (FGD) scrubbers.     

Catalytic wet oxidation of ammonia: why is N2 formed preferentially against NO3 -?

The role of catalyst and the reason for the preferential formation of N(2) in the catalytic oxidation reaction of ammonia in water over a Ru (3wt.%)/TiO(2) catalyst were elucidated. It was verified that the catalyst in the reaction had no direct relevance to the selective formation of N(2), but was responsible only for the oxidation of aqueous ammonia, NH(3)(aq), finally giving a molecule of nitrous acid. The preferential production of N(2) was experimentally demonstrated due to the homogeneous aqueous phase reaction of the nitrous acid-dissociated NO(2)(-) with NH(4)(+) ions. Even under the highly oxidizing condition, NO(2)(-) was much more likely to react with NH(4)(+) to form N(2) than being oxidized over the catalyst to NO(3)(-) as long as NH(4)(+) was available in solution.     

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

The Southeastern Aerosol Research and Characterization Study, part 3: continuous measurements of fine particulate matter mass and composition

Deployment of continuous analyzers in the Southeastern Aerosol Research and Characterization Study (SEARCH) network began in 1998 and continues today as new technologies are developed. Measurement of fine particulate matter (PM2.5) mass is performed using a dried, 30 degrees C tapered element oscillating microbalance (TEOM). TEOM measurements are complemented by observations of light scattering by nephelometry. Measurements of major constituents include: (1) SO4(2-) via reduction to SO2; (2) NH4+ and NO3- via respective catalytic oxidation and reduction to NO, (3) black carbon (BC) by optical absorption, (4) total carbon by combustion to CO2, and (5) organic carbon by difference between the latter two measurements. Several illustrative examples of continuous data from the SEARCH network are presented. A distinctive composite annual average diurnal pattern is observed for PM2.5 mass, nitrate, and BC, likely indicating the influence of traffic-related emissions, growth, and break up of the boundary layer and formation of ammonium nitrate. Examination of PM2.5 components indicates the need to better understand the continuous composition of the unmeasured "other" category, because it contributes a significant fraction to total mass during periods of high PM2.5 loading. Selected episodes are presented to illustrate applications of SEARCH data. An SO2 conversion rate of 0.2%/hr is derived from an observation of a plume from a coal-fired power plant during early spring, and the importance of local, rural sources of NH3 to the formation of ammonium nitrate in particulate matter (PM) is demonstrated.     

Effects of NO2 and SO2 on selective catalytic reduction of nitrogen oxides by ammonia

The selective catalytic reduction (SCR) characteristics of NO and NO(2) over V(2)O(5)-WO(3)-MnO(2)/TiO(2) catalyst using ammonia as a reducing agent have been determined in a fixed-bed reactor at 200-400 degrees C. The presence of NO(2) enhances the SCR activity at lower temperatures and the optimum ratio of NO(2)/NO(x) is found to be 0.5. During the SCR reactions, there are some side reactions occurred such as ammonia oxidation and N(2)O formation. At higher temperatures, the selective catalytic oxidation of ammonia and the nitrous oxide formation compete with the SCR reactions. The denitrification (DeNO(x)) conversion decreases at lower temperatures but it increases at higher temperatures with increasing SO(2) concentration. The presence of SO(2) in the feeds inhibits N(2)O formation.     

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.     

A study on the reaction characteristics of vanadium-impregnated natural manganese oxide in ammonia selective catalytic reduction

This study investigated the effect of adding vanadium (V) to natural manganese oxide (NMO) in ammonia (NH3) selective catalytic reduction (SCR). The addition of V to NMO decreased the catalytic activity at low temperatures by blocking the active site. However, the enhancement of catalytic activity was achieved by controlling NH3 oxidation at high temperatures. From the NH3 temperature programmed desorption and oxygen on/off test, it was confirmed that the amount of Lewis acid site and active lattice oxygen of the catalyst affects the catalytic performance at low temperature.     

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.     

Incinerating volatile organic compounds with ferrospinel catalyst MnFe2O4: an example with isopropyl alcohol

This paper concerns the incineration of isopropyl alcohol (IPA) using the ferrospinel catalyst MnFe2O4. It covers the preparation of the ferrospinel catalyst, the screening of catalytic activity, catalytic incineration testing, and 72-hr decay testing of the catalyst. The experimental results of catalyst screening reveal that the Mn/Fe catalyst is the best of five prepared catalysts (chromium/iron [Cr/Fe], manganese/iron [Mn/Fe], zinc/iron [Zn/Fe], nickel/iron [Ni/Fe], and pure magnetite [Fe3O4]). In tests of the catalytic incineration system used to convert IPA, 98% conversion was obtained at a space velocity of 24,000 hr(-1), an oxygen (O2) content of 21%, 1700 ppm of IPA, and a reaction temperature of 200 degrees C.     

Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420 degrees C, with space velocities varying from 1900 to 5000 hr(-1). Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs.     

Photocatalytic oxidation of gaseous DMF using thin film TiO2 photocatalyst

The heterogeneous photocatalytic oxidation of gaseous N,N'-dimethylformamide (DMF) widely used in the manufacture of synthetic leather and synthetic textile was investigated. The experiments were carried out in a plug flow annular photoreactor coated with Degussa P-25 TiO2. The oxidation rate was dependent on DMF concentration, reaction temperature, water vapor, and oxygen content. Photocatalytic deactivation was observed in these reactions. The Levenspiel deactivation kinetic model was used to describe the decay of catalyst activity. Fourier transform infrared (FTIR) was used to characterize the surface and the deactivation mechanism of the photocatalyst. Results revealed that carbonylic acids, aldehydes, amines, carbonate and nitrate were adsorbed on the TiO2 surface during the photocatalytic reaction. The ions, NH4+ and NO3-, causing the deactivation of catalysts were detected on the TiO2 surface. Several treatment processes were applied to find a suitable procedure for the regeneration of catalytic activity. Among these procedures, the best one was found to be the H2O2/UV process.     

CeO2-CoO／ACF低温SCR烟气脱氮性能的研究

活性炭纤维（ACF）经硝酸处理后采用浸渍法制备了CeO2-CoO／ACF复合催化剂，测试了其在以氨气为还原剂的低温SCR过程中的催化活性，同时研究了金属氧化物浸渍顺序及负载量、催化剂煅烧温度、空速比（SV）、NH，／NO（摩尔比）、O2含量等因素对NO转化效率的影响。研究发现，负载量为10％的CeO2-CoO／ACF复合催化剂经煅烧后在120—240℃时具有很高的催化活性，并且在N0初始浓度为1000mg／m3、空速比（SV）为6000h～、NH3／NO为1．05、O：体积分数在3．0％时具有较高的NO转化效率。     

CeO_2-CoO/ACF低温SCR烟气脱氮性能的研究

活性炭纤维(ACF)经硝酸处理后采用浸渍法制备了CeO2-CoO/ACF复合催化剂,测试了其在以氨气为还原剂的低温SCR过程中的催化活性,同时研究了金属氧化物浸渍顺序及负载量、催化剂煅烧温度、空速比(SV)、NH3/NO(摩尔比)、O2含量等因素对NO转化效率的影响。研究发现,负载量为10%的CeO2-CoO/ACF复合催化剂经煅烧后在120~240℃时具有很高的催化活性,并且在NO初始浓度为1 000 mg/m3、空速比(SV)为6 000 h-1、NH3/NO为1.05、O2体积分数在3.0%时具有较高的NO转化效率。