低温等离子体催化氧化甲烷的实验研究

采用电容耦合等离子体和催化剂协同作用对干空气中的甲烷进行了氧化实验,并和没有放置催化剂时进行了对比,结果表明,放置催化剂后甲烷的分解效率明显提高,反应产物中CO2的选择性增加,副产物NO和NO2的浓度减少,反应所需的能耗降低.甲烷的最终氧化产物为CO、CO2和H2O.     

低温等离子体催化氧化甲烷的实验研究

采用电容耦合等离子体和催化剂协同作用对干空气中的甲烷进行了氧化实验，并和没有放置催化剂时进行了对比，结果表明，放置催化剂后甲烷的分解效率明显提高，反应产物中CO2的选择性增加，副产物NO和NO2的浓度减少．反应所需的能耗降低。甲烷的最终氧化产物为CO、CO2和H2O。     

Sn(Ⅳ)掺杂纳米TiO2/AC降解橙黄G的动力学与机理研究

采用溶胶凝胶法制备了掺杂Sn(Ⅳ)的TiO2/AC光催化剂,以生物染料橙黄G为目标降解物,研究了多相光催化降解橙黄G的动力学规律.研究表明,该反应符合Langmuir-Hinshelwood动力学方程,速控步为吸附反应.同时,利用GC/MS联用仪探讨了橙黄的中间产物及其降解机理:橙黄G在强氧化性自由基·OH、·OOH、·O2-的作用下逐渐分解氧化为小分子有机醛、酮、酸,最后转化为CO2、NH4 、NO3-、NO2-、SO42-和H2O等无机小分子.     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni（NO3）2和Fe（NO3）3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO＋NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni(NO3)2和Fe(NO3)3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO+NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

TG-FTIR研究生物质成型燃料热解与燃烧特性

利用热重-红外联用分析仪(TG-FTIR)研究了生物质成型燃料(玉米秸杆)的热解和燃烧特性。结果表明,热解和燃烧反应过程均可分为3个阶段:干燥脱气(100~200℃)、挥发分反应(200~400℃)与碳化反应(400~1 000℃)。热解和燃烧主要失重阶段(200~400℃),燃烧反应速率总体上大于热解反应速率。利用Coats-Redfern方法对玉米秸杆的主要失重阶段进行动力学分析发现,热解和燃烧的反应过程符合一级反应模型;在主要失重阶段(200~400℃),热解和燃烧所需的活化能相差不大。FTIR分析表明,热解的气相产物主要分为轻质类气体(H2O、CO2、CO、CH4、HCl、NH3和HCN)和焦油类(酸类和酚类)物质,而燃烧的气相产物主要以CO2和H2O析出为主。     

溶胶-凝胶法制备颗粒状催化剂低温SCR脱硝性能

采用溶胶凝胶法制备了Mn-Ce/Ti O2催化剂,并将其用于低温NH3选择催化还原NO的反应(NH3-SCR),考察了反应温度、空速、氧气浓度、氮氧化物浓度和氨氮比等反应条件对催化剂性能的影响。结果表明,NO入口浓度为800~1 600 mg/m3时,催化剂活性受NO初始浓度的影响较小。反应温度和氨氮比对NO转化率影响显著,100~150℃温度范围内,NO转化率随温度升高快速上升;当[NH3]/[NO]1.1时,随着[NH3]/[NO]的增加,NO转化率很快上升。反应体系中适当的O2浓度可促进NO还原为N2。空速大于10 000 h-1时,NO转化率随着空速的增大而降低。     

汽车尾气中NOx再燃烧过程的动力学

为了阐明汽车尾气中ＮＯｘ再燃烧的动力学进程,以甲醛和ＮＯ２作为探针分子,通过ＦＴ－ＩＲ跟踪研究了反应体系不听民 ＨＣＯ自由基与ＮＯ２反应的动力学。结果表明,反应的主要产物中包括ＣＯ、ＣＯ２、ＮＯ、ＨＯＮＯ和Ｈ２Ｏ等分子,经长时间的反应,当体系中的ＮＯ２基本耗尽时,才有少量的Ｎ２Ｏ生成,这些产物分子分别是在几个不同的途径的连串反应在形成的。从体系中ＣＯ和ＣＯ２的生成量,测定了主反应的歧化反应速率比,     

微波辐照活性炭还原氮氧化物

为提高烟气脱硝效率,构建了微波辐照活性炭还原氮氧化物体系,通过对微波功率(温度)、反应空速、NO浓度、活性炭种类及粒径等影响因素的考察,研究了微波辐照活性炭还原NO体系的性能,通过反应动力学实验确定了活性炭还原NO反应的速率方程。研究结果表明,增大微波功率、减小反应空速均会提高NO还原效率,而改变NO浓度、活性炭种类以及粒径对NO还原效率无明显影响,微波功率为800 W,反应空速为2 000 h~(-1)时,对2 412 mg·m~(-3)的NO去除率可达99.8%,当NO浓度增至29 000 mg·m~(-3)时NO还原效率仍高达98.2%。通过反应动力学研究确定了反应的速率方程,其中反应级数为0.568 3,反应速率常数为14.71 s~(-1)。     

4种高级氧化法处理高浓度正丙醇废水的动力学比较

研究了1%和10%(V/V)模拟正丙醇废水在UV/TiO2体系、UV/H2O2体系、Fe2+/H2O2体系和UV/TiO2/Fe2+/H2O2体系等4种工艺条件下的降解动力学过程,对比了降解动力学特点及工艺参数对动力学常数的影响,优化工艺参数。结果表明,UV/TiO2体系和Fe2+/H2O2体系的降解过程可分为零级反应阶段和一级反应阶段,转折点分别在反应开始后2 h和氧化剂浓度为6.7 g/L,UV/H2O2体系和UV/TiO2/Fe2+/H2O2体系分别符合零级反应和一级反应规律;相同工艺参数条件下,6 h反应后,组合工艺UV/TiO2/Fe2+/H2O2体系在处理效率达85%,比前3个体系分别高52.0%、8.3%和32.0%,与UV/TiO2体系和Fe2+/H2O2体系的处理效率之和持平,其协同效应提高了速率常数,在目标物浓度降低时依然可维持较高降解速率。而目标物浓度提高10倍后,UV能量利用率提高35.5倍,氧化剂用量是Fe2+/H2O2体系的1/7.1。     

Effect of nitrogen amendment on respiration and respiratory quotient (RQ) in three hydrocarbon contaminated soils of different type

Three soil types (sandy gravel, silty clay and sandy loam) from sites historically contaminated with total petroleum hydrocarbon (TPH) were amended with NH(4)NO(3) at concentrations ranging from 16 to 2133 mg/kg soil(dry weight). Microbial activity was measured as O(2) consumption and CO(2) production in order to assess nitrogen limitation. Although activity was stimulated in all three soils under NH(4)NO(3) amendment (after 72 h), the level of nitrogen required was soil specific. For the sandy gravel and silty clay soils, O(2) consumption and CO(2) production both showed enhanced microbial activity when amended with 16 mg/kg soil(dry weight) NH(4)NO(3), whereas, these two parameters gave differing results for the sandy loam soil. Specifically, CO(2) production and O(2) consumption were stimulated with 66 mg/kg and 133 mg/kg soil(dry weight) of NH(4)NO(3) respectively. In addition, respiratory quotient kinetic analysis suggested different decomposition processes occurring in this soil under different NH(4)NO(3) amendment concentrations.     

Mineralization of CCl4 by the UVC-photolysis of hydrogen peroxide in the presence of methanol

A method for a photochemically induced mineralization of CCl4 is described in which use is made of reductive radicals. The UVC-photolysis (254 nm) of H2O2 added to aqueous solutions of CCl4 is leading to the homolysis of the oxidant yielding hydroxyl radicals (HO) that subsequently react with added methanol to generate hydroxymethyl radicals (CH2OH). The latter radicals initiate mineralization of CCl4 by reductive C-Cl bond splitting. CHCl3, C2Cl4 and C2Cl6 were found as reaction intermediates, but are quantitatively depleted in a parallel oxidative reaction manifold leading to mineralization. Carbon dioxide radical anion, CO2(-), an intermediate in the mineralization pathway of methanol, is also shown to initiate the mineralization of CCl4 by reductive dechlorination. A reaction mechanism is proposed and validated with computer simulations of all the experimental results.     

Assessment of the photochemistry of OH and NO3 on Jeju Island during the Asian-dust-storm period in the spring of 2001

In this study, we examined the influence of the long-range transport of dust particles and air pollutants on the photochemistry of OH and NO3 on Jeju Island, Korea (33.17 degrees N, 126.10 degrees E) during the Asian-dust-storm (ADS) period of April 2001. Three ADS events were observed during the periods of April 10-12, 13-14, and 25-26. Average concentration levels of daytime OH and nighttime NO3 on Jeju Island during the ADS period were estimated to be about 1x10(6) and 2x10(8) moleculescm(-3) ( approximately 9 pptv), respectively. OH levels during the ADS period were lower than those during the non-Asian-dust-storm (NADS) period by a factor of 1.5. This was likely to result from higher CO levels and the significant loading of dust particles, reducing the photolysis frequencies of ozone. Decreases in NO3 levels during the ADS period was likely to be determined mainly by the enhancement of the N2O5 heterogeneous reaction on dust aerosol surfaces. Averaged over 24 h, the reaction between HO2 and NO was the most important source of OH during the study period, followed by ozone photolysis, which contributed more than 95% of the total source. The reactions with CO, NO2, and non-methane hydrocarbons (NMHCs) during the study period were major sinks for OH. The reaction of N2O5 on aerosol surfaces was a more important sink for nighttime NO3 during the ADS due to the significant loading of dust particles. The reaction of NO3 with NMHCs and the gas-phase reaction of N2O5 with water vapor were both significant loss mechanisms during the study period, especially during the NADS. However, dry deposition of these oxidized nitrogen species and a heterogeneous reaction of NO3 were of no importance.     

微量Pd对CrOx／ZrO2催化剂催化活性的影响

运用微反技术考察了ＣｒＯＸ负载型催化剂对ＣＯ＋Ｏ２和ＣＯ＋ＮＯ反应的催化活性。研究了微量Ｐｄ加和ＣｒＯＸ基双组元催化剂对上述反应的催化活性,中间产物Ｎ２Ｏ生成和Ｎ２生成的影响。     

低温等离子体法去除苯和甲苯废气性能研究

对低温等离子体法去除苯和甲苯废气的性能进行了探讨,在理论分析的基础上进行实验研究。低温等离子体法去除苯和甲苯的机理是放电反应产生的高能电子与苯和甲苯分子发生非弹性碰撞并将能量全部或部分传递给目标分子,使其裂解、激化。被裂解、激化的分子与臭氧、活性基团发生一系列物理、化学反应后生成二氧化碳、一氧化碳和水。实验结果表明,苯和甲苯的去除率随着电场强度的增强而增大,随着气体流速的增大而减小。在较高电场强度下,有钛酸钡填料的反应器比无填料的反应器对苯和甲苯的去除率高得多,苯最高去除率可达92 6%,甲苯可达到96 8%。相同条件下甲苯比苯更容易去除。     

OH-initiated oxidation of DMS/DMSO: reaction products at high NOx levels

Dimethylsulphide (DMS) gas phase oxidation with OH radicals was investigated by long path FT-IR spectroscopy and by ion chromatography (IC) and HPLC-MS2 to quantify the reaction products and evaluate heterogeneous processes. The experiments were performed considering two different NOx (NO2+NO) levels. The initial concentration of NO2 was varied from 24 ppbV (NOx=1 ppmV) to 953 ppbV (NOx=10 ppmV). Photolysis of H2O2 was used as the OH-radical source. SO2, dimethylsulphoxide (DMSO), dimethylsulphone (DMSO2), methanesulphonic acid (MSA), methanesulphinic acid (MSIA) and methane sulphonyl peroxynitrate (MSPN) were identified as the main sulphur-containing products. The results indicate that higher NOx levels play a significant role in the chemistry of CH3S(O)x radical, influencing both the SO2/MSPN ratio and the amount of the sulphur species in the condensed phase, and that the NO2/NO ratio could influence the trends in the molar yields of the different products. For this reason the NOx content results a limiting parameter when on measure DMS in atmospheric environment.     

Experimental and modeling study of the effect of CH(4) and pulverized coal on selective non-catalytic reduction process

The reduction of nitric oxide using ammonia combined with methane and pulverized coal additives has been studied in a drop tube furnace reactor. Simulated flue gas with 1000ppm NO(x) and 3.4% excess oxygen was generated by cylinder gas. Experiments were performed in the temperature range of 700-1200 degrees C to investigate the effects of additives on the DeNO(x) performance. Subsequently, a kinetic mechanism was modified and validated based on experimental results, and a computational kinetic modeling with CHEMKIN was conducted to analyze the secondary pollutants. For both methane and pulverized coal additives, the temperature window is shifted towards lower temperatures. The appropriate reaction temperature is shifted to about 900 and 800 degrees C, respectively with 1000ppm methane and 0.051gmin(-1) pulverized lignite coal. The addition of methane and pulverized coal widens the temperature window towards lower temperature suggesting a low temperature application of the process. Furthermore, selective non-catalytic reduction (SNCR) reaction rate is accelerated evidently with additives and the residence time to complete the reaction is shortened distinctly. NO(x) reduction efficiency with 80% is achieved in about 0.3s without additive at 1000 degrees C. However, it is achieved in only about 0.2s with 100ppm methane as additive, and only 0.07 and 0.05s are needed respectively for the cases of 500 and 1000ppm methane. The modified kinetic modeling agrees well with the experimental results and reveals additional information about the process. Investigation on the byproducts where NO(2) and N(2)O were analyzed by modeling and the others were investigated by experimental means indicates that emissions would not increase with methane and pulverized coal additions in SNCR process and the efficacious temperature range of SNCR reaction is widened approximately with 100 degrees C.     

O3/H2O2处理嘧啶废水的研究

采用O3/H2O2法对嘧啶废水进行处理,考察了不同反应条件对嘧啶和COD去除率的影响,并对O3/H2O2降解嘧啶的反应机制和动力学进行了初步探讨。实验结果表明,在pH值为11,反应时间为70 min,O3流量为4 g/h,H2O2投加量为50 mmol/L的条件下,废水的嘧啶和COD的去除率分别达到86.46%和74.97%。嘧啶的去除率随自由基抑制剂叔丁醇增加而降低,说明O3/H2O2降解嘧啶主要为体系中.OH的贡献。同时动力学研究表明,O3/H2O2对嘧啶的降解符合一级反应动力学模型。