Effects of tungsten oxide on the activity and thermal stability of a sulfate-derived titania supported platinum catalyst for propane oxidation

A Pt/WO₃/TiO₂ catalyst for propane oxidation was prepared by a stepwise wet impregnation method, and was aged at 800℃ for 5 hr. Compared to the sulfate-derived titania supported catalyst, the introduction of tungsten oxide as stable Bronsted acid sites led to the formation of more metallic platinum active sites at the Pt/WO₃ interface. The dissociation of surface intermediates for propane oxidation was promoted on the WO₃-modified catalyst. This, as well as the inhibition effects of tungsten oxide on the sintering of anatase and the phase transformation to rutile, resulting in a high activity and thermal stability for the Pt/WO₃/TiO₂ catalyst.     

Photocatalytic degradation of 4-tert-octylphenol in a spiral photoreactor system

A spiral photoreactor system (SPS) was developed for the degradation of 4-tert-octylphenol (4-t-OP) in aqueous phase. 4-t-OP was previously considered as a endocrine disrupting compound frequently present in water. The direct photodegradation reaction caused by the SPS was found to accord with the characteristic of apparent first-order reaction with reaction rate constantk= 4.8 × 10^-2 min^-1. However, the direct photodegradation reaction could not make the 4-t-OP mineralized. The photodegradation efficiency increased from 88% to 91.2% in 45 min irradiation period after the internal surface of SPS was sintered with TiO₂ thin film as catalyst. Catalyst concentration, number of catalyst coating layers and initial concentration of 4-t-OP were proven to be the factors affecting the photocatalytic degradation performance of the SPS on aqueous 4-t-OP. The degradation mechanism was investigated and the byproducts were analyzed using total organic carbon analyzer (TOC) and LC-MS. The possible chemical structures of the products were suggested. SPS with single layer of TiO₂ prepared by sintering 13.6% of TiO₂ precursor was proven to be more efficient than most of previous systems for removal of 4-t-OP from aqueous phase. 28.3% of the 4-t-OP was mineralized in 45 min according to the decreased amount of TOC value.     

Photodegradation of Norfloxacin in aqueous solution containing algae

Photodegradation of Norfloxacin in aqueous solution containing algae under a medium pressure mercury lamp (15 W, λ_max = 365 nm) was investigated. Results indicated that the photodegradation of Norfloxacin could be induced by the algae in the heterogeneous algaewater systems. The photodegradation rate of Norfloxacin increased with increasing algae concentration, and was greatly influenced by the temperature and pH of solution. Meanwhile, the cooperation action of algae and Fe(III), and the ultrasound were beneficial to photodegradation of Norfloxacin. The degradation kinetics of Norfloxacin was found to follow the pseudo zero-order reaction in the suspension of algae. In addition, we discussed the photodegradation mechanism of Norfloxacin in the suspension of algae. This work will be helpful for understanding the photochemical degradation of antibiotics in aqueous environment in the presence of algae, for providing a new method to deal with antibiotics pollution.     

Self-catalytic degradation of ortho-chlorophenol with Fenton''s reagent studied by chemiluminescence

The degradation of ortho-chlorophenol using Fenton's reagent was studied by chemiluminescence (CL). Without a special CL reagent, a weak CL emission from the mixture of ferrous ion and hydrogen peroxide was observed at room temperature. The CL intensity was increased by the addition of ortho-chlorophenol into the mixed solution. When the temperature was raised to 65℃, the CL intensity was enhanced strongly. The CL mechanisms for the system H₂O₂-Fe²⁺ with and without ortho-chlorophenol were studied by examining the CL spectrum, gas chromatography-mass spectrometry and electron spin resonance spectrum. The effects of various free radical scavengers, surfactants and fluorescence compounds on the CL intensity were also investigated. A self-catalytic oxidation mechanism was proposed. The results showed that singlet oxygen was the main emitter for the system H₂O₂-Fe²⁺. The strong CL from the system H₂O₂-Fe²⁺-ortho-chlorophenol was due to singlet oxygen and electronically excited quinone. The benzenediol-like intermediate product formed during the phenol oxidation process greatly promoted the Fenton's reaction and led to higher CL intensity. Chemiluninescence is a novel approach for the investigation of the oxidation of some organic pollutants by Fenton's reagent.     

Formaldehyde oxidation on Pd/USY catalysts at room temperature: The effect of acid pretreatment on supports

The complete catalytic oxidation of formaldehyde (HCHO) to CO₂ and H₂O at room temperature is a green route for indoor HCHO removal. Zeolite is an excellent carrier material for HCHO oxidation due to its large surface area, intricate pores and high adsorption capacity. However, the zeolite-supported noble metal catalysts have currently shown relatively low activity especially at room temperature. In this work, we present a facile acid treatment strategy for zeolite catalysts to improve the hydroxyl concentration and further enhance their catalytic activity for HCHO oxidation. Activity tests illustrated that HCHO could be completely oxidized to CO₂ and H₂O at a nearly 100% conversion rate with a weight hourly space velocity (WHSV) of 150,000 mL/(g∙hr) at 25°C, when the support of Pd/USY catalysts was pretreated by hydrochloric acid with a concentration of 0.20 mol/L. The characterization results revealed that the active hydroxyl groups originated from the dealumination in the acid treatment play a key role in the HCHO oxidation reaction. The deduced reaction mechanism suggests that bridging hydroxyl groups may oxidize HCHO to dioxymethylene (DOM) species and terminal hydroxyl groups are responsible for the transformation of DOM groups to formate (HCOO) species.     

Decolorization and bio degradation metabolism of azo dyes by Pseudomonas S-42

A bacterial strain was isolated from activated sludge and has been identified as Pseudomonas sp. S-42 capable of decolorizing azo dyes such as Diamira Brilliant Orange RR (DBO-RR), Direct Brown M (DBM), Eriochrome Brown R (EBR) and so on. The growing cells, intact cells, cell-free extract and purified enzyme of strain S-42 could decolorize azo dyes under similar conditions at the optimum pH 7.0 and temperature of 37℃. The efficiencies of decolorization for DBO-RR, DBM, EBR with intact cells stood more than 90%. When the cell concentration was 15mg (wet)/ml and the reaction time was 5 hours, the decolorizing activities of intact cells for above three azo dyes were 1.75, 2.4, 0.95 μg dye/mg cell, respectively. Cell-free extract and purified enzyme belonged to azoreductase with molecular weight about 34000±2000 and Vmax and Km values for DBO-RR of 13μmol/mg protein/nun and 54μmol, respectively. The results from the detection of the biodegradation products of DBO-RR by spectrophotometric and NaNO₂ reaction methods showed that the biodegradation of azo dyes was initiated by the reducing cleavage of azo bonds. The biodegradation metabolism path for DBO-RR by Psued. S-42 was hypothesized.     

Rubber sheet strewn with TiO2 particles:Photocatalytic activity and recyclability

A new method for the preparation of rubber sheet strewn with titanium dioxide particles (TiO₂-strewn sheet) is presented. This simple and low cost method is based on the use of TiO₂ powder (Degussa P25) being strewn onto the sheet made from rubber latex (60% HA) through a steel sieve. The characteristic of the TiO₂-strewn sheet was studied by using scanning electron microscopy/energy dispersive X-ray spectrometer (SEM/EDS) and X-ray diffractometer (XRD) techniques. The photocatalytic activity of TiO₂-strewn rubber sheet was evaluated using Indigo Carmine (IC) dye as a model for organic dye pollutant in water. The results showed that the TiO₂-strewn sheet could degrade IC dye solution under UV light irradiation. The effects of pH, initial concentration, and the intensity of UV light on the photodegradation were also investigated. Kinetics of the photocatalytic degradation was of the first-order reaction. The used TiO₂-strewn sheet can be recovered and reused. The recycling uses did not require any cleaning between successive uses and no decline in the photodegradation efficiency was observed compared with freshly prepared TiO₂-strewn sheet.     

Clean and effective removal of Cl(-I) from strongly acidic wastewater by PbO2

Recycling strongly acidic wastewater as diluted H₂SO₄ after contaminants contained being removed was previously proposed, however, Cl(-I), a kind of contaminant contained in strongly acidic wastewater, is difficult to remove, which severely degrades the quality of recycled H₂SO₄. In this study, the removal of Cl(-I) using PbO₂ was investigated and the involved mechanisms were explored. The removal efficiency of Cl(-I) reached 93.38% at 50℃ when PbO₂/Cl(-I) mole ratio reached 2:1. The identification of reaction products shows that Cl(-I) was oxidized to Cl₂, and PbO₂ was reduced to PbSO₄. Cl₂ was absorbed by NaOH to form NaClO, which was used for the regeneration of PbO₂ from the generated PbSO₄. Cl(-I) was removed through two pathways, i.e., surface oxidation and •OH radical oxidation. •OH generated by the reaction of PbO₂ and OH⁻ plays an important role in Cl(-I) removal. The regenerated PbO₂ had excellent performance to remove Cl(-I) after six-time regeneration. This study provided an in-depth understanding on the effective removal of Cl(-I) by the oxidation method.     

Catalytic liquid-phase oxidation of acetaldehyde to acetic acid over a Pt/CeO2–ZrO2–SnO2/γ-alumina catalyst

Pt/CeO₂–ZrO₂–SnO₂/γ-Al₂O₃ catalysts were prepared by co-precipitation and wet impregnation methods for catalytic oxidation of acetaldehyde to acetic acid in water. In the present catalysts, Pt and CeO₂–ZrO₂–SnO₂ were successfully dispersed on the γ-Al₂O₃ support. Dependences of platinum content and reaction time on the selective oxidation of acetaldehyde to acetic acid were investigated to optimize the reaction conditions for obtaining both high acetaldehyde conversion and highest selectivity to acetic acid. Among the catalysts, a Pt(6.4 wt.%)/Ce_0.68Zr_0.17Sn_0.15O_2.0(16 wt.%)/γ-Al₂O₃ catalyst showed the highest acetaldehyde oxidation activity. On this catalyst, acetaldehyde was completely oxidized after the reaction at 0°C for 8 hr, and the selectivity to acetic acid reached to 95% and higher after the reaction for 4 hr and longer.     

Removal of gaseous volatile organic compounds via vacuum ultraviolet photodegradation: Review and prospect

Volatile organic compounds (VOCs) have attracted much attention for decades as they are the precursors of photochemical smog and are harmful to the environment and human health. Vacuum ultraviolet (VUV) photodegradation is a simple and effective method to decompose VOCs (ranging from tens to hundreds of ppmV) without additional oxidants or catalysts in the air at atmospheric pressure. In this paper, we review the research progress of VOCs removal via VUV photodegradation. The fundamentals are outlined and the key operation factors for VOCs degradation, such as humidity, oxygen content, VOCs initial concentration, light intensity, and flow rate, are discussed. VUV photodegradation of VOCs mixture is elucidated. The application of VUV photodegradation in combination with ozone-assisted catalytic oxidation (OZCO) and photocatalytic oxidation (PCO) systems, and as the pre-treatment technique for biological purification are illustrated. Based on the summary, we propose the challenges of VUV photodegradation and perspectives for its future development.     

Pd/C气体扩散电极用于电生成H2O2降解苯酚的研究

采用自制的Pd/C气体扩散阴极和Ti/IrO2/RuO2阳极,在无隔膜电解槽中对苯酚模拟废水降解效果及机制进行了研究,采用电子自旋共振法(ESR)对电解体系中产生的羟自由基(·OH)进行了检测.结果表明,在Pd/C气体扩散体系中掺杂Pd催化剂可以促进H2 O2的生成(H2 O2的稳定浓度是7.5 mg/L),有利于·OH的产生.经电化学氧化处理120 min后,苯酚和COD的去除率分别达到97.2%和50%,表明在电催化氧化过程中苯酚被氧化生成了大量低分子量中间产物.废水的BOD5/COD值达到0.73是处理前的9.1倍,苯酚废水的可生化降解性通过电化学氧化处理后显著提高.在该电化学体系中苯酚的降解是在阳极直接、间接氧化及阴极产生的H2 O2、·OH的氧化共同作用下完成的.通过对紫外扫描光谱图的分析推断出苯酚在电解过程中有醌类物质生成;由GC-MS检测到了邻苯二酚、对苯二酚、苯醌等芳香族化合物和己二酸、顺丁烯二酸、反丁烯二酸、丁二酸、丙二酸、乙二酸等短链羧酸,据此提出了苯酚降解的可能历程.     

吸收协同高级氧化工艺处理低浓度含氰废气实验研究

以乙腈作为含氰废气的典型组分,考察吸收协同不同高级氧化体系下低浓度乙腈的去除效率以及产物分配情况.研究结果表明：UV/PS和VUV/PS体系均能有效吸收并降解乙腈,在60 min内其脱除效率近100%,且矿化率近80%或以上.主要原因是吸收液中的过硫酸盐（PS）可以在紫外光的激发下产生大量的HO^·和SO₄^·-,这些自由基可以促进乙腈和中间产物的氧化.同时实验还观察到乙腈中的氮元素主要被转化为NO₃^-和NH₄⁺,这说明乙腈的直接氧化和水解反应同时进行.NO₃^-的累积会竞争消耗反应体系中的自由基,这是其稳定性实验中乙腈矿化率下降的主要原因.此外,干扰离子Cl^-也会由于自由基的捕获作用抑制乙腈的降解.最后,根据产物的分析结果,提出了包含氧化与水解路径的乙腈总体降解反应途径.     

NOx和/或NH3气氛下SO2在高岭土表面非均相转化的实验研究

利用自制气溶胶反应器研究了NO_x和/或NH_3气氛下SO_2在高岭土表面的非均相转化过程,应用扫描电镜(SEM)对高岭土颗粒物形貌进行了表征.结果表明:高岭土颗粒表面的SO_2非均相转化致使其成分和形貌产生了较大变化.相同实验条件下,SO_2转化的协同作用程度由高到低依次为NH_3、NO_x/NH_3和NO_x气氛,相对湿度40%、有光照条件下,SO_2转化量增幅最高可分别达125%、75%和50%.所有气氛下,协同作用在无光照时在高相对湿度(40%~70%)区间更为突出,有光照时其显著性则体现在低相对湿度(20%~40%)区间.SO_2、NO_x、NH_3三者共存时,在高岭土颗粒表面发生的非均相反应过程既有协同作用又存在竞争反应.     

Influence of environmental temperature and relative humidity on photocatalytic oxidation of toluene on activated carbon fibers coated TiO2

TiO₂ supported on active carbon fiber (TiO₂/ACF), an absorbable photocatalyst, is a new kind of material applied in air purification. In this paper, the influence of environmental temperature (T) and relative humidity (RH) on the gas-solid adsorption of toluene and the photocatalytic oxidation (PCO) efficiency of adsorbed toluene on TiO₂/ACF were studied, and then, the purification capability of TiO₂/ACF was estimated. PCO results showed that although the PCO efficiency increased under high RH and T levels, the amount of adsorption of toluene decreased. Moreover, quantitative analysis results of intermediates indicated that more environmental risk emerged when PCO of toluene was carried out at higher environmental T and RH levels because more toxic intermediates would be accumulated on the TiO₂/ACF. So, it is significant to control the environmental T and RH conditions in the application of the PCO technique. T = 25°C and RH530% is the optimal condition for purifying toluene in our experimental system. __________ Translated from Urban Environment & Urban Ecology, 2007, 20(5): 10–13 [译自: 城市环境与城市生态]     

环境因素对气相甲苯光氧化反应机制的影响

以低压汞灯为光源,采用石英管连续流动态反应系统和特氟龙气袋静态反应系统,研究了环境因素〔RH(相对湿度)、温度、光照强度、有氧(空气)/无氧(氮气)气氛条件〕对低浓度(10~20 mg/L)气相甲苯光氧化过程的影响. 结果表明:①RH对甲苯光氧化反应影响显著. 干燥条件(RH为0%~5%)下甲苯光氧化去除率在8.3%~8.7%之间;当环境中有水蒸气存在(RH为20%)时,甲苯光氧化去除率降至6.5%~7.2%,其后光氧化去除率随着RH的进一步增加而逐渐增大,在RH为60%时达到最大值(9.4%~11.5%);但当RH继续增至80%时,去除率迅速降至4.4%~5.6%. ②甲苯光氧化去除率随着温度、光照强度的增加而提高. ③无论是干燥(RH为0%~5%)还是湿润(RH为60%)环境下,甲苯在有氧气氛下的去除率均高于无氧气氛;甲苯在有氧气氛下光氧化产物主要是苯和苯甲醛,在无氧气氛中的产物主要是苯. ④在干燥、有氧条件下,O(1D)应是甲苯光氧化的活性物种;在湿润、有氧条件下,甲苯的光氧化主要是通过·OH氧化降解;在无氧条件下,甲苯的光氧化主要是通过甲苯的直接光解完成.      

VUV/US耦合深度处理印染废水尾水的研究

采用真空紫外(VUV)/高频超声(US)耦合深度处理印染废水尾水,以TOC和UV254为污染物指标,比较了不同功率下VUV、US和VUV/US降解印染废水尾水的效果,以确定VUV/US的最佳功率组合;通过批式实验,探讨了反应时间、反应温度、初始pH值对VUV/US降解印染废水尾水效能的影响规律,解释了VUV/US对TOC和UV254的降解动力学.通过分析降解产物,揭示了VUV/US对印染废水尾水中残余难降解有机物的去除机理.结果表明,VUV/US的最佳功率组合为VUV16W、US100W,VUV/US处理印染废水尾水的效果明显优于单独UV和US的情况,存在着协同增效作用,反应120 min后VUV/US对TOC及UV254的去除率分别达到27.68%和93.03%.反应温度、初值pH值对VUV/US处理效果的影响较小.VUV/US降解TOC和UV254的反应动力学分别符合表观二级动力学模型和表观一级动力学模型.VUV/US过程是VUV直接光解、超声空化气泡内的热裂解和羟基自由基的氧化等协同作用,印染废水尾水中以苯系物为代表的难降解物主要通过羟基自由基的氧化作用去除.     

Efficient degradation of chlorobenzene in a non-thermal plasma catalytic reactor supported on CeO2/HZSM-5 catalysts

Chlorobenzene removal was investigated in a non-thermal plasma reactor using CeO₂/HZSM-5 catalysts. The performance of catalysts was evaluated in terms of removal and energy efficiency. The decomposition products of chlorobenzene were analyzed. The results show that CeO₂/HZSM-5 exhibited a good catalytic activity, which resulted in enhancements of chlorobenzene removal, energy efficiency, and the formation of lower amounts of by-products. With regards to CO₂ selectivity, the presence of catalysts favors the oxidation of by-products, leading to a higher CO₂ selectivity. With respect to ozone, which is considered as an unavoidable by-product in air plasma reactors, a noticeable decrease in its concentration was observed in the presence of catalysts. Furthermore, the stability of the catalyst was investigated by analyzing the evolution of conversion in time. The experiment results indicated that CeO₂/HZSM-5 catalysts have excellent stability: chlorobenzene conversion only decreased from 78% to 60% after 75 hr, which means that the CeO₂/HZSM-5 suffered a slight deactivation. Some organic compounds and chlorinated intermediates were adsorbed or deposited on the catalysts surface as shown by the results of Fourier Transform Infrared (FT-IR) spectroscopy, scanning electron microscope (SEM) and energy dispersive X-ray spectroscopy (EDS) analyses of the catalyst before and after the reaction, revealing the cause of catalyst deactivation.     

用于滤膜称重的饱和氯化镁溶液恒湿系统搭建与评估

目前中国大气颗粒物污染严重,许多颗粒物测量工作使用基于滤膜采样的重量分析法,滤膜称重过程的质量保障至关重要.本文搭建了一套具有恒湿能力的滤膜平衡称重箱(1.2 m×0.6 m×0.8 m)并自制流量控制系统用于平衡和称量滤膜.通过测试空白滤膜和负载大气颗粒物的滤膜在不同相对湿度下的质量变化确定了30%~40%的平衡相对湿度并选用饱和氯化镁溶液控制称重箱内的相对湿度.用20 L·min~(-1)的干燥气通过装有饱和氯化镁溶液的恒湿箱,再将平衡后的气体通入平衡称重箱使其相对湿度达到稳定,随后用5 L·min~(-1)的流量维持.通过一个月的测试表明,系统在称重箱外相对湿度变化较大时,仍可维持称重箱内相对湿度在30.1%~34.0%之间.使用该恒湿系统称量60张滤膜,恒湿3次后称量的偏差均值不超过±0.02mg.相比于其他恒湿系统,这套系统具有简单、稳定、易于维护和成本低的特点.     

几种难降解有机废水的光化学处理研究

采用日光和中压汞灯为光源,分别在充空气、加入Ｈ２Ｏ２或ＴｉＯ２等半导体催化剂条件下,对几种难降解的有机废水进行了光化学处理研究。结果表明：石化和焦化废水中挥发酚,油和ＣＯＤ的去除率分别为８６．３％－１００％,３９．８％－９７．８％,２６．４％－６０％,几种偶氮染料水溶液的脱色率、ＣＯＤ去除率分别为８０．０％－１００％,４８．０％－７５．０％,还测定了苯酚的降解产物,讨论了影响光解的要素和苯酚的降解