Study of Pd-decorated MWCNT-promoted Pd-ZnO Catalysts for CO2 Hydrogenation to Methanol

温室效应对我们这个星球的环境和人类社会的生存发展已构成越来越严重的威胁，减少主要温室气体之一的CO2的排放已成为一个紧迫的问题.通过加氢转化，将CO2加工为有价值的燃料或化学品被认为是现时固定大量排放的CO2的较好方法.在诸多CO2加氢的可能产物中，甲醇因其既是非石油基洁净合成燃料，又是重要化工原料，还可作为燃料电池氢燃料的载体，因而成为首选的目标产物. 催化剂的研制开发是实现该过程实用化的关键.较早报道可用于催化CO2加氢制甲醇的催化剂是Cu基（尤其是CuO-ZnO-基和CuO-ZrO2-基）催化剂；负载型Pd催化剂对CO2加氢制甲醇也有相当高的催化活性和选择性，并以ZnO负载的Pd基体系...The greenhouse effect of carbon dioxide has been recognized to be one of the most serious problems in the world and a number of countermeasures have been proposed so far. Catalytic hydrogenation of carbon dioxide to produce various kinds of chemicals and fuels has received much attention. Among the options considered, methanol synthesis by CO2 hydrogenation has been also considered to play a role ...学位：理学博士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：1912005140309

碳纳米管作为合成气制低碳醇Co-Cu催化剂的高效促进剂

用自行制备的碳纳米管(CNTs)作为促进剂,制备一类共沉淀型CNTs促进Co-Cu基催化剂.实验发现,该类催化剂对CO加氢制低碳醇显示出异常高的转化活性和生成C2~4-含氧产物,尤其是丁醇(BuOH)和二甲醚(DME)的选择性;在Co3Cu1-11%CNTs催化剂上、5.0 MPa,573 K、V(H2)/V(CO)/V(CO2)/V(N2)=46/46/5/3,GHSV=10 000 mL(STP).h-1.g-cat.-1反应条件下,所观测到的CO转化率达到38.0%,是相同反应条件下不含CNTs的参比体系(Co3Cu1)上观察值(25.3%)的1.50倍;BuOH和DME成为两种最主要的产物,其C-基选择性分别达到45.0%和14.8%,两者的质量百分数合计占C1~4-含氧产物总量的~83%,展示其作为油品添加剂或代用合成燃料的应用前景.实验结果表明,对于CNTs促进的Co3Cu1体系,原料气中适量CO2的存在对CO的转化和含氧产物(尤其是BuOH)的选择生成有显著促进作用

Development of Novel Catalysts for Steam-reforming of Methanol or Ethanol to Generate Hydrogen

新型替代清洁能源的开发是大势所趋.氢能作为理想的清洁能源之一,已引起人们广泛重视.但氢能广泛地应用,尤其是用作电动车燃料电池的燃料,必须解决其储存和输运的技术问题.采用液体作为氢的载体,通过其重整即时产生燃料H2在商业上具有重要实用价值.在诸多可重整制H2的液体燃料中,甲醇、乙醇以其反应温度和压力低,H/C比高,无nOX、SOX排放,并可利用现行动力燃料输配系统等优点而占据优势.本文介绍甲醇、乙醇制氢技术的研发动态,重点报道本实验室在甲醇、乙醇经水蒸气重整制氢用高效高稳定性催化剂的研发进展.There is an ongoing trend to move toward exploitation of clean alternative energy sources.As one of the ideal energy sources,hydrogen has drawn great attention and been intensively studied.In order for hydrogen to be more widely used,especially serving as power-fuel for hydrogen-fuel-cell-driven vehicles,it is critical to solve issues associated with the storage and transportation of hydrogen.Liquid hydrogen-carriers,which can generate hydrogen in situ through conversion/reforming,are commercially important for practical applications.Among the many liquid-fuels that can generate hydrogen through reforming,methanol and ethanol have displayed some advantages in relatively lower reaction temperature and pressure,higher H/C ratio,no emission of NOxand SOxas by-products,and making use of the existing power-fuel transportation-distribution systems.In this article,we review recent developments in the hydrogen generation from methanol or ethanol,highlighting the progress in our lab on the development of catalysts for hydrogen generation from methanol or ethanol through steam reforming.国家重点基础研究发展计划(973计划)(2011CBA00508); 优秀国家重点实验室基金项目(20923004); 教育部创新团队项目(IRT1036

A Novel Sc-promoted CuO-ZnO-Al_2O_3 Catalyst for Dehydrogenation of Cyclohexanol to Cyclohexanone

用SC2O3作为促进剂,研发出一种高效新型SC2O3促进的Cu-znO-Al2O3基催化剂(记为CuIznJAlk-XSCX),考察其对环己醇脱氢制环己酮的催化性能.实验结果显示,在组成经优化的Cu6zn3Al0.7SC0.3催化剂上,常压,523 k,n(C6H11OH)∶n(n2)=1∶19和空速(gHSV)=43 200Ml/(H·g)的反应条件下,环己醇脱氢的转化率达53.7%,产物环己酮的时空产率为5 344Mg/(H·g),这2个值均为不含SC2O3的基质催化剂Cu6zn3Al1的相应值(42.4%,4 222Mg/(H·g))的1.27倍.催化剂的表征结果显示,SC2O3的修饰调变作用可能是由于SC2O3在znO晶格中高的溶解度.少量SC2O3在znO晶格中的溶解在znO表面产生阳离子空位形式的SCHOTTky缺陷,通过这些表面阳离子空位接纳Cu+离子使Cuy0-Cu+原子簇得以稳定化.这有助于抑制催化活性Cuy0纳米颗粒的团聚烧结,保持Cu组分的高分散度,于是显著地提高催化剂的活性和操作稳定性.该催化剂具有应用前景.A type of Sc2O3-promoted Cu-ZnO-Al2O3 catalyst was developed.The catalyst displays excellent performance for dehydrogenation of cyclohexanol to cyclohexanone.Over a Cu6Zn3Al0.7Sc0.3catalyst under the reaction condition of atmospheric pressure,523 K,n(C6H11OH)∶n(N2)=1∶19and GHSV=43 200 mL/(h·g),the conversion of cyclohexanol dehydrogenation reached53.7%,with the STY of cyclohexanone being 5 344mg/(h·g);both values were 1.27 times of those obtained with the Cu-ZnOAl2O3 catalyst not containing Sc2O3,42.4% and 4 222 mg/(h·g).Characterization of the catalyst revealed that the pronounced modification action of Sc3+may be due to the high solubility of Sc2O3 in the ZnO lattice.Solution of a small amount of Sc2O3 in the ZnO lattice resulted in the formation of Schottky defects in the form of cationic vacancies at the surface of ZnO,where the Cuy0-Cu+clusters can be better stabilized through the Cu+accommodated at the surface vacant cation-sites.This would be conducive to inhibiting the aggregation and sintering of the catalytically active Cuy0nano-particles and preserving high dispersion degree of Cu composition,so that the activity and operating stability of the catalyst were markedly improved.国家重点基础研究发展计划(973)项目(2011CBA00508); 优秀国家重点实验室基金项目(20923004); 教育部创新团队项目(IRT1036

Research Progress in Catalytic Synthesis and Applications of Carbon Nanotubes

通信作者: [email protected][中文文摘]概述近10年来国内外在碳纳米管催化合成及其应用研究领域的发展动态,着重介绍本研究组在多壁碳纳米管的催化合成、规模化生产及其用作某些加氢过程催化剂的新型载体或促进剂等领域的研究进展. [英文文摘]In this review article,recent progresses in catalytic synthesis and production-commercialization of multi-walled carbon nanotubes(MWCNTs) and in applied research of MWCNTs in catalysis are summarized and briefly reviewed,with an emphasis on description of the research progress in our laboratory here.国家重点基础研究发展计划(973)项目(2011CBA00508);福建省重大专项专题项目(2009HZ0002-1);福建省发改委高技术项目(闽发改高技2009-1030