OH自由基引发的甲烷光化学氧化体系中有机过氧化物的研究

在１．０１３２５×１０＾５Ｐａ,２９８Ｋ,Ｏ２－Ｎ２气氛下,采用长光路付立叶红外光谱仪跟踪反应进程,高压液相色谱仪测定反应产物中有机过氧化物,研究了ＯＨ自由基基引发的甲烷光化学反应体系,证实反应产物中有Ｈ２Ｏ２、甲基过氧化氢（ＣＨ３Ｏ２Ｈ,ＭＨＰ）和过氧甲醚（ＣＨ３Ｏ２ＣＨ３）,并发现羟甲基过氧化氢（ＨＯＣＨ２ＯＯＨ,ＨＭＨＰ）和一未知有机过氧化物,ＨＭＨＰ的发现表明ＣＨ４氧化过程中可能存在过氧甲     

ZrO2负载过渡金属氧化物催化剂对CO＋NO（O2）反应的影响

本文运用固定床微反技术考察了Ｃｕ,Ｆｅ,Ｍｎ,Ｃｒ,Ｃｏ和Ｎｉ负载（ＺｒＯ２载体）氧化物对ＣＯ＋ＮＯ（Ｏ２）反应的催化活性。研究了ＮＯ和ＣＯ在不同比例时,催化剂对Ｎ２Ｏ和Ｎ２生成的影响。结果表明,在ＮＯ＋ＣＯ反应中,ＮＯ和ＣＯ的比例对催化剂活性和Ｎ２Ｏ,Ｎ２生成均有明显的影响,ＣｕＯｘ／ＺｒＯ２催化剂的活性最高;Ｎ２Ｏ是ＮＯ＋ＣＯ反应的中间产物,低温或ＮＯ过量时有利于生成Ｎ２Ｏ,高温或ＮＯ不足时有     

烟气中N2O生成反应的动力学研究

采用静态法 模拟道气中对Ｎ２Ｏ生成有影响的组分ＮＯ，ＳＯ２和Ｈ２Ｏ，以及温度进行了动力学研究。结果表明，随着ＮＯ，ＳＯ２和Ｈ２Ｏ浓度的增加反反应时间的加长，Ｎ２Ｏ的生态量增加，反应温升高，Ｎ２Ｏ的生成速率下降。将实验数据用尝试法和微分法进行处理，得到如下结果在Ｎ２Ｏ的生成反中对ＮＯ，ＳＯ２和Ｈ２Ｏ均为一级反应，反应速率常数分别为：２．０＊１０＾－５，８．９＊１０＾－６，８．８＊１０＾－８ｍ＾３．ｍ     

SO2在Co—Mo／AC催化剂上的还原

本文研究了活性焦（ＡＣ）担载Ｃｏ－Ｍｏ催化剂对ＳＯ２还原的催化性能。考查了催化剂不同的预处理方法,Ｈ２／ＳＯ２摩尔比和还原温度对还原过程硫产率的影响,并就硫化后的Ｃｏ－Ｍｏ和活性焦在催化床不同的构成对硫产率的影响进行了研究。结果表明,经硫化后的催化剂在ＳＯ２＋２Ｈ２→Ｓ＋２Ｈ２Ｏ反应有较高的催化活性,在最佳反应温度３００℃,Ｈ／ＳＯ摩尔比为３,空速６０００Ｌ;ｋｇ＾－１．ｈ＾－１条件下,生成硫的产     

大气中PAN的测定及其与前体物的关系

对北京中关村地区大气ＰＡＮ的监测结果表明：在强日照条件下，ＰＡＮ浓度随汽车等排放和ＮＯ２浓度的增加而增加，高ＰＡＮ浓度水平与高Ｏ３浓度相关联；夏季的ＰＡＮ浓度明显高于春季。模拟实验的结果证实：Ｃ３Ｈ６是大气中重要的ＰＡＮ前体物，在一定范围内，其浓度越高，ＰＡＮ浓度越大；Ｃ２Ｈ４生成ＰＡＮ是困难的，Ｈ２Ｏ２的存在对Ｃ２Ｈ４反应生成ＰＡＮ有促进作用；大气中ＳＯ２的存在可降低ＰＡＮ的生成速率。在〈４００     

NOx分解还原催化研究进展

介绍和评价了ＮＯ_ｘ分解还原的３类催化剂：贵金属催化剂、氧化物催化剂、金属离子置换的分子筛。在ＮＯ_ｘ的碳氢化合物选择性催化还原反应（ＨＣ－ＳＣＲ反应）中，同样有３类催化剂，即金属氧化物、贵金属和分子筛。由于Ｃｕ－ＺＳＭ－５是目前最有希望投入实际使用的一种，故本文重点介绍了它对ＮＯ_ｘ的ＨＣ－ＳＣＲ反应的催化机理，以及温度、Ｏ_２含量、Ｃｕ~（２＋）的置换度、不同种类ＨＣ及ＨＣ含量等各种因素对Ｃｕ－ＺＳＭ－５的影响，并对其工作台试验进行了评价，指出了其存在的问题及当前的研究热点。     

过渡金属催化剂上CO还原NO反应性能的研究

在一系列负载型过渡金属催化剂上考察了ＣＯ－ＮＯ和ＣＯ－Ｏ２的反应性能。结果表明，催化剂的ＣＯ－Ｏ２反应活性高于ＣＯ－ＮＯ反应，催化剂表面ＮＯ解离是ＣＯ－ＮＯ反应的速率控制步骤。低温反庆有利于Ｎ２Ｏ的生成，高温有利于Ｎ２的生成。     

用过渡应答技术研究V2O5—TiO2上NO—NH3选择性还原反应的机理

在固定床、柱塞流反应器中，以浓度跃变方法进行过程应答实验，研究了在Ｖ２Ｏ５－ＴｉＯ２催化剂上，存在Ｏ２时ＮＯ与ＮＨ３进行的选择性还原反应。根据应答曲线提出了该过程的反应历程，认为：反应是在吸附态的ＮＨ３与ＮＯ物种之间进行的，其速率控制步骤是ＮＯ的吸附；催化剂表面Ｖｓ＾４＋—ＯＨ再氧化为Ｖ＾５＋＝０所需要的氧，可以从气相、也可以从体相骨架中逐层获得，而从Ｖ２Ｏ５体相骨架传递氧到表面是通过一个“氧空穴     

降解褐煤菌种选育及降解产物研究

通过对分离自洗煤厂的一株青霉菌进行人工诱变,选育出一株具有较强降解褐煤能力的突变株．将褐煤加到平板培养的该菌株上,经过３６ ｈ 开始被降解．将该菌株用摇瓶培养３ ｄ ,其培养液也能降解褐煤．元素分析结果表明,降解物中 Ｈ、 Ｏ、 Ｎ 的元素质量分数（ ｗ／ ％ ） 比原煤均有所升高,而ｗ（ Ｃ）／ ％ 明显下降．降解产物的经验分子式可写为 Ｃ１００ Ｈ１４４ Ｏ５８ ．２ Ｎ１０ ．０ Ｓ１ ．１８ ,经凝胶过滤法测,定其 Ｍｒ 分布在（２ ～８） ×１０４ 之间; 其红外吸收光谱与原煤相比也有一定的变化． 这些结果说明生物降解过程中褐煤的组成和结构发生了一定的变化     

固定燃烧源排放N2O的采样,分析方法及其监测

烟道气是一含有多种哗合物的复杂体系，除Ｎ２，Ｏ２外，还含有燃烧产物Ｈ２Ｏ，ＣＯ２ＣＯ，ＮＯｘ，ＳＯ２和Ｈ２Ｓ等，烟气样在贮放过程中它们之间相互影响，使各自的浓度发生变化，为了得到烟气中Ｎ２Ｏ含量的准确测定值，分别研究了Ｈ２Ｏ，ＳＯ２和ＮＯ的含量，放置时间对Ｎ２Ｏ生成量的影响，试验结果表明，玻璃注射器不适于贮放烟气样，样品中只有Ｈ２Ｏ，ＳＯ２和ＮＯ三种化合物同时存在时，才会有进一步的Ｎ２Ｏ的生成，其     

Effects of Pd doping on N<Subscript>2</Subscript>O formation over Pt/BaO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> during NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> storage and reduction process

N₂O is a powerful greenhouse gas and plays an important role in destructing the ozone layer. This present work investigated the effects of Pd doping on N₂O formation over Pt/BaO/Al₂O₃ catalyst. Three types of catalysts, Pt/BaO/Al₂O₃, Pt/Pd mechanical mixing catalyst (Pt/BaO/Al₂O₃ + Pd/Al₂O₃) and Pt-Pd co-impregnation catalyst (Pt-Pd/BaO/Al₂O₃) were prepared by incipient wetness impregnation method. These catalysts were first evaluated in NSR activity tests using H₂/CO as reductants and then carefully characterized by BET, CO chemisorption, CO-DRIFTs and H2-TPR techniques. In addition, temperature programmed reactions of NO with H2/CO were conducted to obtain further information about N₂O formation mechanism. Compared with Pt/BaO/Al₂O₃, (Pt/BaO/ Al₂O₃ + Pd/Al₂O₃) produced less N₂O and more NH3 during NO _x storage and reduction process, while an opposite trend was found over (Pt-Pd/BaO/Al₂O₃ + Al₂O₃). Temperature programmed reactions of NO with H₂/CO results showed that Pd/Al₂O₃ component in (Pt/BaO/Al₂O₃ + Pd/Al₂O₃) played an important role in NO reduction to NH₃, and the formed NH3 could reduce NO _x to N₂ leading to a decrease in N₂O formation. Most of N₂O formed over (Pt-Pd/BaO/Al₂O₃ + Al₂O₃) was originated from Pd/BaO/Al₂O₃ component. H₂-TPR results indicated Pd-Ba interaction resulted in more difficultto- reduce PdOx species over Pd/BaO/Al₂O₃, which inhibits the NO dissociation and thus drives the selectivity to N₂O in NO reduction.

Open image in new window

     

Effect of Cu-ZSM-5 catalysts with different CuO particle size on selective catalytic oxidation of N,N-Dimethylformamide

● A series of Cu-ZSM-5 catalysts were tested for DMF selective catalytic oxidation. ● Cu-6 nm samples showed the best catalytic activity and N₂ selectivity. ● Redox properties and chemisorbed oxygen impact on DMF catalytic oxidation. ● Isolated Cu²⁺ species and weak acidity have effects on the generation of N₂. N, N-Dimethylformamide (DMF), a nitrogen-containing volatile organic compound (NVOC) with high emissions from the spray industry, has attracted increasing attention. In this study, Cu-ZSM-5 catalysts with different CuO particle sizes of 3, 6, 9 and 12 nm were synthesized and tested for DMF selective catalytic oxidation. The crystal structure and physicochemical properties of the catalyst were studied by various characterization methods. The catalytic activity increases with increasing CuO particle size, and complete conversion can be achieved at 300–350 °C. The Cu-12 nm catalyst has the highest catalytic activity and can achieve complete conversion at 300 °C. The Cu-6 nm sample has the highest N₂ selectivity at lower temperatures, reaching 95% at 300 °C. The activity of the catalysts is determined by the surface CuO cluster species, the bulk CuO species and the chemisorbed surface oxygen species. The high N₂ selectivity of the catalyst is attributed to the ratio of isolated Cu²⁺ and bulk CuO species, and weak acidity is beneficial to the formation of N₂. The results in this work will provide a new design of NVOC catalytic oxidation catalysts.     

六铝酸盐负载CuO催化还原NO性能

采用共沉淀法制备了LaAl12O19六铝酸盐载体,采用等体积浸渍法制备了不同负载量的CuO/LaAl12O19催化剂,并对其进行了XRD、H2-TPR和BET表征,考察了催化剂对CH4选择催化还原NO的性能.结果表明,CuO的负载并未改变六铝酸盐载体的结构,Cu在载体上以Cu2+的形式存在,活性组分CuO与载体LaAl12O19之间存在协同作用;CuO/LaAl12O19催化剂对CH4选择催化还原NO表现出良好活性,所制备的催化剂均能使NO的转化率达到99%;其中负载量为1.0 wt%的CuO/LaAl12O19催化剂的活性最好,完全反应温度T99%为560℃,且在80 h稳定性试验中表现出了良好的高温活性和热稳定性.     

Al_2O_3负载Pd-Cu催化剂催化1,2-二氯乙烷加氢脱氯性能

采用共浸渍法制备了一系列Al2O3负载金属Pd、Cu催化剂.通过元素分析（ICP）、氮气吸脱附（BET）、X射线粉末衍射（XRD）、透射电镜（TEM）等技术对催化剂进行了表征,并以1,2-二氯乙烷气相加氢脱氯为探针反应,考察了Pd-Cu/Al2O3催化剂的钯铜比、反应温度、反应时间等因素对催化活性以及反应产物乙烯选择性的影响.结果发现,提高Cu负载量可在催化剂中形成Pd-Cu合金,并促进催化剂对乙烯的选择性.此外,当温度为250℃,Pd、Cu负载量分别为0.78%和1.9%时的Pd-Cu/Al2O3催化剂对1,2-二氯乙烷的催化加氢脱氯效果最佳,最终产物乙烯的选择性可达到80%以上.     

PM-support interfacial effect and oxygen mobility in Pt,Pd or Rh-loaded (Ce,Zr,La)O2 catalysts

• Pt/CZL exhibits the optimum catalytic performance for HC and NO_x elimination. • The strong PM-Ce interaction favors the oxygen mobility and DOSC. • Pd/CZL shows higher catalytic activity for CO conversion due to more O_latt species. • Great oxygen mobility at high temperature broadens the dynamic operation window. • The relationship between DOSC and catalytic performance is revealed. The physicochemical properties of Pt-, Pd- and Rh- loaded (Ce,Zr,La)O₂ (shorted for CZL) catalysts before/after aging treatment were systematically characterized by various techniques to illustrate the relationship of the dynamic oxygen storage/release capacity and redox ability with their catalytic performances for HC, NO_x and CO conversions. Pt/CZL catalyst exhibits the optimum catalytic performance for HC and NO_x elimination, which mainly contribute to its excellent redox ability and dynamic oxygen storage/release capacity (DOSC) at lower temperature due to the stronger PM (precious metals)-support interaction. However, the worse stability of Pt-O-Ce species and volatile Pt oxides easily result in the dramatical decline in catalytic activity after aging. Pd/CZL shows higher catalytic activity for CO conversion by reason of more O_latt species as the active oxygen for CO oxidation reaction. Rh/CZL catalyst displays the widest dynamic operation window for NO_x elimination as a result of greater oxygen mobility at high temperature, and the ability to retain more Rh-O-Ce species after calcined at 1100°C effectively restrains sintering of active RhO_x species, improving the thermal stability of Rh/CZL catalyst.     

Pt/Mg-Ce-O catalyst for NO/H<Subscript>2</Subscript>/O<Subscript>2</Subscript> lean de-No<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reaction

The NO/H₂/O₂ reaction was studied under oxidizing conditions in the 100-400 °C range over 0.1 wt% Pt supported on various metal oxides such as MgO, CeO₂, SiO₂, La₂O₃, CaO, Y₂O₃ and TiO₂. The Pt/MgO and Pt/CeO₂ catalysts showed good catalytic behaviours. Here, we find that the Pt/Mg-Ce-O catalyst, prepared from MgO and CeO₂ by the sol-gel method, is a very active and selective catalyst towards N₂ formation in the whole 100–400 °C range. This catalyst appears to be the most active, selective and stable one ever reported in the literature for the NO/H₂/O₂ reaction, even in the presence of 5%v H₂O or 20 ppmv of SO₂ in the feed stream.Selected article from the Regional Symposium on Chemistry and Environment, Krusevac, Serbia, June 2003, organised by Dr. Branimir Jovancicevic.     

Pd/MCM-41催化水溶液中碘苯Ullmann反应的研究

以水溶剂中Ullmann反应为目标反应,设计具有纳米介孔结构的Pd/MCM-41作为其高效催化剂.与传统SiO2载体负载的Pd催化剂比较,该催化剂在以水为介质的碘苯偶合（Ullmann反应）中显示出优良的催化活性和对联苯的选择性.     

易挥发有机化合物在Pt/Al_2O_3-Si纤维催化剂上的低温氧化

本文合成了一种新型的Pt负载在Al_2O_3涂膜强力富硅纤维载体的催化剂,研究低温下催化易挥发有机化合物的行为.用四种有机化合物检验实验参数对催化剂分解有机化合物分解率的影响.讨论了流速、浓度、有机物的本性、预热温度、反应热等参数的影响,并给出了催化剂对苯、甲苯在特定实验条件下的活化能、反应级数和指前因子的数值.     

全Pd三效催化剂研究涂层材料的研究

制备了作为Pd三效催化剂涂层材料组成的活性Al2O3/金属氧化物添加剂试样，用BET法、XRD法及H2－TPR法对这些涂层原材料体系进行表征。结果表明：金属氧化物添加剂提高了活性Al2O3的热稳定性；添加ZrO2改善了CeO2的热稳定性；与含Ca的试样不同，含La试样没有贮氧能力。用含有Al2O3-CeO2/ZrO2和Al2O3-La2O3/BaO的涂层材料制备的Pd催化剂有好的CO，HC和NOx同时净化的三效性能和低的起燃活性。加入0．003％（V／V）SO2降低了催化剂活性，含La2O3/BaO涂层材料的Pd催化剂上NOx反应易被SO2中毒。     

Simultaneous removal of NOx and chlorobenzene on V2O5/TiO2 granular catalyst: Kinetic study and performance prediction

• A V₂O₅/TiO₂ granular catalyst for simultaneous removal of NO and chlorobenzene. • Catalyst synthesized by vanadyl acetylacetonate showed good activity and stability. • The kinetic model was established and the synergetic activity was predicted. • Both chlorobenzene oxidation and SCR of NO follow pseudo-first-order kinetics. • The work is of much value to design of multi-pollutants emission control system. The synergetic abatement of multi-pollutants is one of the development trends of flue gas pollution control technology, which is still in the initial stage and facing many challenges. We developed a V₂O₅/TiO₂ granular catalyst and established the kinetic model for the simultaneous removal of NO and chlorobenzene (i.e., an important precursor of dioxins). The granular catalyst synthesized using vanadyl acetylacetonate precursor showed good synergistic catalytic performance and stability. Although the SCR reaction of NO and the oxidation reaction of chlorobenzene mutually inhibited, the reaction order of each reaction was not considerably affected, and the pseudo-first-order reaction kinetics was still followed. The performance prediction of this work is of much value to the understanding and reasonable design of a catalytic system for multi-pollutants (i.e., NO and dioxins) emission control.