生化法净化低浓度挥发性有机废气的动力学模式研究

针对目前国际上常用的吸收－生物膜理论，在描述生化法净化低浓度挥发性有机废气机理过程中的存在问题，提出了吸附－生物膜的新理论，并依据这一新理论建立了生物膜填料塔净化低浓度甲苯废气的动力学模式。实验结果表明，其模拟计算值与实验值之间有很好的相关性，相关系数Ｐ〉０．９３，利用这一新理论及模式，可由已知操作参数对生物膜填料塔的净化效果进行预测计算，也能为有关的理论研究和实际操作提供参考。     

气相色谱法分离测定工业废气中乙酸乙酯、异丙醇、甲苯的方法研究

研究了用气相色谱法分离测定工业废气中乙酸乙酯、异丙醇、甲苯含量，进行了各种色谱条件选择、精密度、样品回收率、方法检出限及样品稳定性实验．     

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, H_2-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 Ce O_2 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 (NO_x) 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,NO_xwas suppressedwith 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 NO_x 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.     

CuO/BiVO_4催化剂制备及其可见光降解甲苯效果研究

采用水热法和浸渍法制备复合催化剂CuO/BiVO4。利用紫外-可见漫反射光谱(UV-Vis-DRS)和电化学测试手段对样品进行表征。UV-Vis-DRS表征表明,CuO的负载几乎不改变BiVO4的可见光吸收范围;线性扫描伏安法(LSV)和塔菲尔(Tafel)电化学表征说明复合催化剂中异质结的形成促进了光生电子-空穴的分离,提高了催化剂的光催化活性。通过考察CuO负载对该样品在可见光下光催化矿化甲苯效果的影响,结果显示Cu含量为4.0 wt%时BiVO4矿化甲苯效果最佳,光催化降解308 mg/m3的甲苯6 h后,最高矿化率由纯BiVO4的4.1%提高到19.5%。     

Multi tracer test for the implementation of enhanced in-situ bioremediation at a BTEX-contaminated megasite

At the Centre for Environmental Research Leipzig-Halle (UFZ) research site in Zeitz, Germany, benzene contaminates the lower of two aquifers with concentrations of up to 20 mg/l. Since the benzene plume has a minimum length of approximately 1 km, enhanced natural attenuation measures are being considered as a remediation strategy. This study describes the performance and evaluation of a multi-species reactive tracer test using the tracers fluorescein and bromide as conservative tracers and toluene as reactive tracer. Sampling was performed over a period of six months using a detailed network of multilevel sampling wells. Toluene was only slightly retarded in comparison to bromide, whereas fluorescein was retarded considerably stronger. Therefore, it was not possible to use fluorescein as an in situ tracer for the determination of groundwater velocities. The ionic nature of fluorescein is assumed to be the major reason for its retardation. The results show that the infiltration conditions were suitable to produce a wide spreading of the tracer front along the full thickness of the aquifer. Thus, a large aquifer volume can be treated in future enhanced bioremediation measures. The total quantity of infiltrated toluene (24 l) was degraded under sulfate-reducing conditions over a flow path of 50 m. Benzylsuccinate was identified as a metabolite of toluene degradation under sulfate-reducing conditions at this site. The modelling results show that toluene degradation was described more accurately using Monod kinetics than first-order kinetics. Since toluene was only slightly retarded in comparison to bromide, sorption and desorption processes were considered to be negligible.     

气相色谱法测定环境空气中氯化苄和甲苯

用串联的乙醇吸收管收集环境空气中的氯化苄和甲苯,以毛细管柱分离,氢火焰检测器测定,保留时间定性,峰高定量。氯化苄平均浓度在４．２９ｍｇ／Ｌ～２１．４ｍｇ／Ｌ时,相对标准偏差在３．３％～４．６％之间;甲苯平均浓度为４．１８ｍｇ／Ｌ～２０．６ｍｇ／Ｌ时,相对标准差在４．４％～７．８％范围内。方法快速、灵敏度高,有较好的精密度与准确度。     

生物滴滤器中水分对憎水性气态污染物净化性能的影响

通过改变稳定工况下的液气比和测定风干过程中滴滤床净化和阻力性能变化,研究了水分对气体生物滴滤器(BTF)净化甲苯性能的影响,结果表明,生物滴滤器净化憎水性挥发性有机物的性能受滤床水分影响较大,与通常气液吸收过程不同,憎水性气体挥发性有机物的生物滴滤过程存在达到最佳净化效果的液气比,风干过程实验表明,滴滤器中水分含量太高,会影响憎水性污染物和氧气等在气相与生物相之间的传质过程;但水分太低又会影响滴滤器内生物相的活性,对生物滴滤器净化憎水性挥发性有机物而言,存在最适滤床水分,可通过监测设备压降来控制滴滤塔内水分。     

Competing pathways of cresol formation in toluene photooxidation: OH-toluene adducts react with NO2 or with O2?

Methyl-hydroxy-cyclohexadienyl radicals (OTAs) are the key products of the photooxidation of toluene, with implications for the fate of toluene. Hence, we investigated the photooxidation mechanisms and kinetics of three main OTAs (o-OTA, m-OTA, and p-OTA) with NO₂ using quantum chemical calculations as well as the fate of OTAs under the different concentration ratios of NO₂ and O₂. The mechanism results show that the pathway of H-abstraction by NO₂ to anti-HONO (anti-H-abstraction) is more favorable than the syn-H-abstraction pathway, because the strong interaction between OTAs and NO₂ is formed in the transition states of the anti-H-abstraction pathways. The branching ratios of the anti-H-abstraction pathways are more than 99% in the temperature range of 216−298 K. The total rate constant of the OTA-NO₂ reaction is 9.9 × 10⁻¹² cm³/(molecule∙sec) at 298 K, which is contributed about 90% by o-OTA + NO₂, and the main products are o-cresol and anti-HONO. The half-lives of the OTA-NO₂ reaction in some polluted areas of China are 35 times longer than those of the OTA-O₂ reaction. In the atmosphere, the NO₂- and O₂- initiated reactions of OTAs have the same ability to form cresols as [NO₂] is up to 142.1 ppmV, which is impossible to achieve. It implies that under the experimental condition, the [NO₂]/[O₂] should be controlled to be less than 7.8 × 10⁻⁵ to simulate real atmospheric oxidation of toluene. Our results reveal that for the photooxidation of toluene, the yield of cresol is not affected by the concentration of NO₂ under the atmospheric environment.     

Effect of NOx and RH on the secondary organic aerosol formation from toluene photooxidation

The secondary organic aerosol (SOA) formation mechanism and physicochemical properties can highly be influenced by relative humidity (RH) and NOx concentration. In this study, we performed a laboratory investigation of the SOA formation from toluene/OH photooxidation system in the presence or absence of NOx in dry and wet conditions. The chemical composition of toluene-derived SOA was measured using Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS). It was found that the mass concentration of toluene decreased with increasing RH and NOx concentration. However, the change of SOA chemistry composition (f₄₄, O/C) with increased RH was not consistent in the condition with or without NOx. The light absorption and mass absorption coefficient (MAC) of the toluene-derived SOA only increased with RH in the presence of NOx. In contrast, MAC is invariant with RH in the absence of NOx. HR-ToF-AMS results showed that, in the presence of NOx, the increased nitro-aromatic compounds and N/C ratio concurrently caused the increase of SOA light absorption and O/C in wet conditions, respectively. The relative intensity of CHON and CHO_xN family to the total nitrogen-containing organic compounds (NOCs) increased with the increasing RH, and be the major components of NOCs in wet condition. This work revealed a synergy effect of NOx and RH on SOA formation from toluene photooxidation.