Cu–Mn–Ce ternary mixed-oxide catalysts for catalytic combustion of toluene

Cu–Mn, Cu–Mn–Ce, and Cu–Ce mixed-oxide catalysts were prepared by a citric acid sol–gel method and then characterized by XRD, BET, H₂-TPR and XPS analyses. Their catalytic properties were investigated in the toluene combustion reaction. Results showed that the Cu–Mn–Ce ternary mixed-oxide catalyst with 1:2:4 mole ratios had the highest catalytic activity, and 99% toluene conversion was achieved at temperatures below 220°C. In the Cu–Mn–Ce catalyst, a portion of Cu and Mn species entered into the CeO₂ fluorite lattice, which led to the formation of a ceria-based solid solution. Excess Cu and Mn oxides existed on the surface of the ceria-based solid solution. The coexistence of Cu–Mn mixed oxides and the ceria-based solid solution resulted in a better synergetic interaction than the Cu–Mn and Cu–Ce catalysts, which promoted catalyst reducibility, increased oxygen mobility, and enhanced the formation of abundant active oxygen species.     

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process

Characteristics of toluene decomposition and formation of nitrogen oxide (NOx) by-products were investigated in a dielectric barrier discharge (DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide (MnOx), iron oxide (FeOx), cobalt oxide (CoOx) and copper oxide (CuO), supported on Al₂O₃/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO₂ selectivity. In addition, NOx was suppressed with the decrease of specific energy density (SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the CuO catalyst showed the best performance in NOx suppression. The MnOx catalyst exhibited the lowest concentration of O₃ and highest CO₂ selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.     

Wall losses of oxygenated volatile organic compounds from oxidation of toluene: Effects of chamber volume and relative humidity

Vapor wall losses can affect the yields of secondary organic aerosol. The effects of surface-to-volume (S/V) ratio and relative humidity (RH) on the vapor-wall interactions were investigated in this study. The oxygenated volatile organic compounds (OVOCs) were generated from toluene-H₂O₂ irradiations. The average gas to wall loss rate constant (k_gw) of OVOCs in a 400 L reactor (S/V = 7.5 m⁻¹) is 2.47 (2.41 under humid conditions) times higher than that in a 5000 L reactor (S/V = 3.6 m⁻¹) under dry conditions. In contrast, the average desorption rate constant (k_wg) of OVOCs in 400 L reactor is only 1.37 (1.20 under humid conditions) times higher than that in 5000 L reactor under dry conditions. It shows that increasing the S/V ratio can promote the wall losses of OVOCs. By contrast, the RH effect on k_gw is not prominent. The average k_gw value under humid conditions is almost the same as under dry conditions in the 400 L (5000 L) reactor. However, increasing RH can decrease the desorption rates. The average k_wg value under dry conditions is 1.45 (1.27) times higher than that under humid conditions in the 400 L (5000 L) reactor. The high RH can increase the partitioning equilibrium timescales and enhance the wall losses of OVOCs.     

Behaviors and kinetics of toluene adsorption‐desorption on activated carbons with varying pore structure

This work was undertaken to investigate the behaviors and kinetics of toluene adsorption and desorption on activated carbons with varying pore structure. Five kinds of activated carbon from different raw materials were selected. Adsorption isotherms and breakthrough curves for toluene were measured. Langmuir and Freundlich equations were fitted to the equilibrium data, and the Freundlich equation was more suitable for simulating toluene adsorption. The process consisted of monolayer, multilayer and partial active site adsorption types. The effect of the pore structure of the activated carbons on toluene adsorption capacity was investigated. The quasi-first-order model was more suitable for describing the process than the quasi-second-order model. The adsorption data was also modeled by the internal particle diffusion model and it was found that the adsorption process could be divided into three stages. In the external surface adsorption process, the rate depended on the specific surface area. During the particle diffusion stage, pore structure and volume were the main factors affecting adsorption rate. In the final equilibrium stage, the rate was determined by the ratio of meso-and macro-pores to total pore volume. The rate over the whole adsorption process was dominated by the toluene concentration. The desorption behavior of toluene on activated carbons was investigated,and the process was divided into heat and mass transfer parts corresponding to emission and diffusion mechanisms, respectively. Physical adsorption played the main role during the adsorption process.     

Effects of gas flow rate, inlet concentration and temperature on the biofiltration of toluene vapors

In this work the variation in the elimination capacity of a biofilter as a function of the gas flow and toluene concentration was studied. A bioreactor 0.75 m high x 14.5 cm diameter was used, divided into three equal stages, using compost to support the microorganisms, and sea shells to control the pH. The biofiltration of toluene was evaluated for flows between 0.12 and 0.73 m(3)h(-1) in a concentration range of 1-3.2 gm(-3). It was observed that on increasing the toluene inlet load by 90% (from 37 to 70 gm(3)h(-1)), the conversion by the biofilter varied by only 5% (from 98% to 93%). The biofiltration system used achieved elimination capacities of up to 82 gm(-3)h(-1) for a toluene load of 100 gm(-3)h(-1).     

掺杂改性纳米二氧化钛粒子光催化降解甲苯的研究

通过共沉淀法制备了掺铁纳米TiO2粒子，并用掺铁后的纳米TiO2粒子作为催化剂，对气相甲苯进行光催化降解实验。利用色谱、质谱、红外等测试方法研究了掺铁浓度对TiO2光催化性能的影响，同时探讨了光催化降解甲苯的机理。     

二氧化钛涂覆材料对甲苯的光催化降解作用

在自制的模拟小室中对二氧化钛涂覆材料的光催化性能进行了初步研究，在玻璃、瓷砖和日光灯这3种常见材料表面涂覆了二氧化钛，并以甲苯为模型化合物，测试了3种材料的净化性能。结果表明，3者对甲苯均有一定的降解效果，是有实用前景的光催化净化材料。     

Promotional effect of cobalt doping on catalytic performance of cryptomelane-type manganese oxide in toluene oxidation

The cryptomelane-type manganese oxide (OMS-2)-supported Co (xCo/OMS-2; x = 5, 10, and 15 wt.%) catalysts were prepared via a pre-incorporation route. The as-prepared materials were used as catalysts for catalytic oxidation of toluene (2000 ppmV). Physical and chemical properties of the catalysts were measured using the X-ray diffraction (XRD), Fourier transform infrared spectroscopic (FT-IR), scanning electron microscopic (SEM), X-ray photoelectron spectroscopy (XPS), and hydrogen temperature-programmed reduction (H₂-TPR) techniques. Among all of the catalysts, 10Co/OMS-2 performed the best, with the T_90%, specific reaction rate at 245°C, and turnover frequency at 245°C (TOF_Co) being 245°C, 1.23 × 10⁻³ mol_toluene/(g_cat·sec), and 11.58 × 10⁻³ sec⁻¹ for toluene oxidation at a space velocity of 60,000 mL/(g·hr), respectively. The excellent catalytic performance of 10Co/OMS-2 were due to more oxygen vacancies, enhanced redox ability and oxygen mobility, and strong synergistic effect between Co species and OMS-2 support. Moreover, in the presence of poisoning gases CO₂, SO₂ or NH₃, the activity of 10Co/OMS-2 decreased for the carbonate, sulfate and ammonia species covered the active sites and oxygen vacancies, respectively. After the activation treatment, the catalytic activity was partly recovered. The good low-temperature reducibility of 10Co/OMS-2 could also facilitate the redox process accompanied by the consecutive electron transfer between the adsorbed O₂ and the cobalt or manganese ions. In the oxidation process of toluene, the benzoic and aldehydic intermediates were first generated, which were further oxidized to the benzoate intermediate that were eventually converted into H₂O and CO₂.     

工业废气中甲苯的生物降解研究

采用生物膜填料塔进行净化低浓度甲苯废气的研究结果表明，构成生物膜的假单胞菌属中的短杆菌对废气中甲苯有很强的生化降解能力，每升体积的生物膜填料对甲苯的生化去除量最大可达１０４．４ｍｇ／ｈ，且当入口气体甲苯浓度约低于２．０ｍｇ／Ｌ时，单塔净化效率可保持在８０％以上。反应级数的转换约在其液相浓度为０．８—１．２ｍｇ／Ｌ（相当于气相浓度约１．７—２．１ｍｇ／Ｌ）时发生。     

生物法处理低浓度有机废气的填料选择研究

采用不锈钢环、瓷环、陶粒、塑料环、海藻石、轻质陶块、煤渣等作为填料的试验研究，结果表明七种填料的净化性能顺序为：海藻石＞轻质陶块＞陶粒＞瓷环＞不锈钢环＞煤渣＞塑料环。