载体及助剂对铜锌系合成气制异丁醇催化剂影响的研究

通过改变铜锌系合成气制异丁醇催化剂的载体及添加不同助剂,以提高原料的利用率和目的产物异丁醇的选择性。以Cu,Zn,Zr等金属离子的硝酸盐为原料,采用并流共沉淀的方式制得铜锌系催化剂。在催化剂主要活性组分铜和锌摩尔比为1∶1的基础上,在反应压力5 MPa、反应温度350℃、空速8 000 h~(-1)、混合气组成中n(H_2)∶n(CO)=2、催化剂装填量2.0 mL、反应时间10 h的条件下,考察了不同载体和助剂对异丁醇选择性的影响。结果表明:以Zr作为载体时,异丁醇的选择性最高,液相产物的时空收率也较高,异丁醇的时空收率最大;从提高异丁醇的选择性来考虑,Cu,Zn,Zr摩尔比为3∶3∶2的催化剂较合适;助剂Mn和Pd的加入有利于提高液相产物收率及异丁醇选择性。     

沉淀剂对Cu-Zn-Al-Mg甲醇合成催化剂性能的影响

采用二步共沉淀法,选取不同沉淀剂Na2 CO3、K2 CO3和NaHCO3制备Cu-Zn-Al-Mg合成甲醇催化剂,考察不同沉淀剂对催化剂性能的影响.采用N2低温吸附、XRD、H2-TPR和TG-DTG等对样品进行分析,结果表明,K2 CO3为沉淀剂时,催化剂前驱体中锌铝水滑石物相多且结晶好,Na2 CO3为沉淀剂时,...     

沉淀剂对Cu-Mn-Ce复合氧化物催化剂结构和性能的影响

为了避免柠檬酸溶胶-凝胶法制备过程中环境问题, 采用共沉淀法制备了Cu-Mn-Ce复合氧化物催化剂, 以催化燃烧甲苯为模型反应, 考察了沉淀剂对Cu-Mn-Ce催化结构和性能的影响。结果表明, 以NaOH作为沉淀剂催化剂效果最佳, 其次为NH₃·H₂O、K₂CO₃、Na₂C₂O₄。采用NaOH作为沉淀剂, 氢氧化物前体在焙烧活化过程中更易使Cu、Mn离子进入CeO₂的立方结构, 形成具有缺陷结构的CeO₂固溶体, 从而提高了表面氧浓度和活动性, 在燃烧反应中表现出更优异的催化特性。     

沉淀剂对Ru/MgO-CeO2氨合成催化剂催化性能的影响

以K<,2>RuO<,4>为钌前驱体,通过共沉淀法制备了Ru/MgO-CeO<,2>氨合成催化剂.考察了5种不同沉淀剂对Ru/MgO-CeO<,2>催化剂的结构和性能的影响,并运用X射线衍射(XRD)、CO吸附、N<,2>物理吸附和H<,2>程序升温还原(H<,2>-TPR)等技术对催化剂进行了表征,讨论了沉淀剂对氨合...     

氨合成催化剂母体相组成对还原性能的影响

采用Shimadzu DT-40型热分析仪,研究了不同原始铁氧化物组成对氨合成熔铁催化剂的还原性能的影响。发现催化剂的还原性能和活性与母体相组成的关系具有相似的规律性。当母体中两种物相共存时,催化剂的还原过程是按物相分阶段依次进行的,其结果使还原速度变慢,还原温度升高,亦使还原后催化剂的活性降低。氨合成催化剂的还原性能与其活性具有一致性,愈易还原的催化剂,其活性亦愈高。研究结果表明,在熔铁催化剂中,Fe_(1-x)O基氨合成催化剂还原速度最快、还原温度最低,其活性亦最高。     

合成气合成异丁醇的研究进展

异丁醇作为基本有机化工原料,在工业生产中有广泛的应用。由合成气直接合成异丁醇作为一种新的工艺思路对世界各国科学家都有强大的吸引力。该文章讨论了合成气合成异丁醇反应过程中的动力学、热力学以及反应机理,并分析了合成过程中所需催化剂的研究现状,对合成气直接合成异丁醇的工艺开发和催化剂的制备有指导意义。     

TiSi复合氧化物性质对NiMo基催化剂加氢脱氧性能的影响

分别以机械混合法与溶胶凝胶法所得的钛硅氧化物TiO_2SiO_2与TiO_2-SiO_2为载体制备了NiMo基催化剂,以含20%小桐子油的正辛烷溶液为原料,在连续流动固定床反应器中考察了催化剂的加氢脱氧性能,并采用X射线衍射(XRD)、氮气物理吸附(BET)、扫描电镜(SEM)和NH3程序升温脱附(NH_3-TPD)等技术对催化剂和TiSi复合氧化物载体进行了表征。结果表明,与TiO_2-SiO_2相比,机械混合法制得的TiO_2SiO_2具有双介孔结构特征、较规则的表面形貌和较多的L酸性中心;溶胶凝胶法制得的TiO_2-SiO_2的表面形貌规则性则较差,负载Ni、Mo的孔道堵塞导致所得催化剂的比表面积和孔容急剧减小,在高温反应条件下TiO_2-SiO_2中的Ti—OH—Si键结构形成的B酸中心对催化剂HDO性能的促进作用较小。催化剂性能的评价结果表明NiMo/TiO_2SiO_2催化剂的加氢脱氧活性优于NiMo/TiO_2-SiO_2催化剂的加氢脱氧性能。     

氮掺杂石墨烯负载金属双原子催化剂对合成气合成C2氧化物性能调控

负载型金属催化剂的催化性能主要取决于金属活性中心的设计.本工作采用密度泛函理论计算研究了氮掺杂石墨烯(NC)负载不同金属活性中心,即同核双原子(CuCu@NC,RhRh@NC和CoCo@NC)和异核双原子催化剂(CuRh@NC,RhCo@NC和CuCo@NC)上合成气合成C2氧化物反应.结果 表明:6类双原子催化剂均具...     

载体对Cu-Co催化剂催化CO_2加氢合成乙酸反应的影响

采用等体积浸渍法制备了以TiO2、Al2O3、SiO2为载体的Cu-Co基双金属催化剂,在固定床反应器上,考察了其催化CO2加氢合成乙酸的性能,并用X射线衍射、NH3-TPD、H2-TPR等对催化剂进行了表征。结果表明,以TiO2为载体的Cu-Co基催化剂有最好的催化活性和选择性,乙酸生成速率可达16.41 mg/(gcat.h),选择性为81.3%。研究认为,催化剂表面适量的中强酸性、金属良好的分散性以及CuCo2O4的生成是影响催化性能的关键因素。     

担载钌催化剂的CO吸附和加氢反应性能

通过ＣＯ脉冲化学吸附以及对吸附态ＣＯ和ｃｏ＋Ｈ＿２反应进行程序升温表面反应（ＴＰＳＲ），发现１％Ｒｕ／ｓｉＯ＿２和１％Ｒｕ／ＡＬ＿２Ｏ＿３催化剂的ＣＯ吸附量随焙烧温度的升高而降低。且根据５１３Ｋ和室温吸附ｃｏ的ＴＰＳＲ不同，认为存在两类不同活性中心。Ⅰ类中心：金属钌与载体的相互作用弱，易吸附ＣＯ；Ⅱ类中心：金属与载体的相互作用强，较难吸附ＣＯ。随焙烧温度升高，金属与载体作用增强，Ⅱ类中心增多。在微型流动反应器上ＣＯ中压加氢发现经６７３Ｋ焙烧的样品的活性及长链烃的生成量和烯／烷比均大于１２０℃烘干的样品，因此认为，Ⅰ类中心为加氢中心，Ⅱ类中心为链增长中心。     

Effect of Additives on the Physicochemical and Catalytic Properties of Oxide Catalysts in Selective Oxidation Reactions

This paper is a survey of the main facts and concepts concerning the effect of additives on the structure and physicochemical and catalytic properties of oxide catalysts in selective oxidation reactions. The phenomena occurring in monophasic and supported mixed oxides containing the additives, including modification of structure, solid state reactions, segregation, defect formation, and spill-over of the reactants, are briefly described. The effect of additives on acid--base and redox properties, and on their bearing on catalytic performance are discussed, with particular emphasis on alkali metal additives. The perspectives of further studies on the problem are proposed.     

CO Hydrogenation to Light Alkenes Over Mn/Fe Catalysts Prepared by Coprecipitation and Sol-gel Methods

CO hydrogenation to light alkenes was carried out on manganese promoted iron catalysts prepared by coprecipitation and sol-gel techniques. Addition of manganese in the range of 1–4 mol.% by means of coprecipitation could improve notably the percentage of C₂⁼~C₄⁼ in the products, but it was not so efficient when the sol-gel method was employed. XRD and H₂-TPR measurements showed that the catalyst samples giving high C₂⁼~C₄⁼ yields possessed ultrafine particles in the form of pure α-(Fe_1-xMn_x)₂O₃, and high quality in lowering the reduction temperature of the iron oxide. Furthermore, these samples displayed deep extent of carburization and different surface procedures to the others in the tests of Temperature Programmed Surface Carburization (TPSC). The different surface procedures of these samples were considered to have close relationship with the evolving of surface oxygen. It was also suggested that for the catalysts with high C₂⁼~C₄⁼ yields, the turnover rate of the active site could be kept at a relatively high level due to the improved reducing and carburizing capabilities. Consequently, there would be a large number of sites for CO adsorption/dissociation and an enhanced carburization environment on the catalyst surface, so that the process of hydrogenation could be suppressed relatively to a low level. As a result, the percentage of the light alkenes in the products could be raised.     

Synthesis and catalytic properties of eggshell cobalt catalysts for the Fischer-Tropsch synthesis

CO diffusional restrictions decrease C₅₊ synthesis rates and selectivity within large (1–3 mm) catalyst pellets often required in Fischer-Tropsch (FT) synthesis reactors. Eggshell catalysts, where Co is located preferentially near outer pellet surfaces, reduce the severity of these transport restrictions and lead to higher synthesis rates and C₅₊ selectivity. Maximum C₅₊ selectivities occur on catalysts with intermediate shell thickness, within which transport restrictions limit the removal of reactive olefins but not the arrival of reactants at catalytic sites. A new synthetic technique leads to sharp distributions of active sites near outer pellet surfaces by controlling the rate of imbibition of cobalt nitrate melts. Also, slow reduction of the impregnated salt leads to moderate Co dispersions (0.05–0.10) even at high local Co loadings present within shell regions.     

费托合成催化剂的研究进展

介绍了费托合成的研究现状,分析了费托合成催化剂的组成,重点评述了恬性组分、载体、助剂等因素在催化剂制备过程中对催化剂的活性、选择性等方面的影响,并对费托合成催化剂研究领域存在的问题进行了探讨。     

A Review of Molybdenum Catalysts for Synthesis Gas Conversion to Alcohols: Catalysts,Mechanisms and Kinetics

Recent literature on synthesis gas conversion to higher alcohols over Mo-based catalysts is reviewed. Density functional theory calculations show that Mo-CO adsorption is weakened by C, P, or S ligands and this facilitates CO dissociation, either directly on Mo₂C, or by H-assisted dissociation on MoS₂, Mo₂C, and MoP. Consequently, Mo-based catalysts have high hydrocarbon selectivity unless they are promoted with alkali metals and/or Group VIII metals. Promoted MoS₂ and MoP have alcohol selectivities of ～80 C atom % (CO₂-free basis) at typical operating conditions (5–8 MPa, H₂/CO = 2–1, 537–603 K), whereas on promoted Mo₂C, alcohol selectivities are ～60%. The kinetics of the synthesis gas conversion reactions over Mo-based catalysts have mostly been described by empirical power law models and the alcohol and hydrocarbon product distributions are consistent with a CO insertion mechanism for chain growth.     

贵金属加氢脱芳催化剂的复合氧化物载体的研究进展

催化剂载体是加氢脱芳（HDA）研究的重要内容,20世纪80年代以来,复合载体受到了极大的关注。综述了近年来贵金属深度加氢脱芳催化剂载体（负载贵金属Pd和Pt）的研究进展。主要介绍了含Al2O3、TiO2及SiO2的复合氧化物载体的催化剂在芳烃加氢过程中表现出的加氢活性和抗硫性。无论从催化剂的催化活性,还是抗硫性能方面比较,复合氧化物载体的催化剂都表现出良好的性能,尤其是三元复合氧化物载体的催化剂,比其他更加稳定,具有更好的催化性能。     

Synergism in methanol synthesis from carbon dioxide over gold catalysts supported on metal oxides

Gold deposited on various oxides with high dispersion was found to be active for the hydrogenation of CO₂ at temperatures between 150 and 400°C. Product selectivities greatly depended on the nature of support oxide. Acidic oxides like TiO₂ gave higher CO₂ conversions but low methanol yields. Zinc oxide component was indispensable for selective methanol synthesis. Significantly, large particle size effect of gold was observed and smaller gold particles gave higher methanol productivity per exposed surface area of gold. This can be explained by an increase in the perimeter area of gold particles with a decrease in particle size. Methanol yield was greatly enhanced in a Au/ZnO---TiO₂ catalyst probably due to an increase in gold-zinc oxide interface.     

Effect of Different Catalysts on the Synthesis of Bis(2-Hydroxyethyl) Terephthalate

Abstract

Transterification of Ethylene Glycol and DiMethyl Terephthalate, through the use of different acetates as catalysts, for producing Bis(2-HydroxyEthyl)Terephthalate under isothermal conditions, was studied from the point of view of the kinetics involved. Best results were obtained by employing zinc acetate and a second order reaction was determined from the experimental data.     

碱金属对CO加氢制备低碳醇Cu-Fe-Co基催化剂的影响

考察了碱金属(Li、Na、K、Cs)对CO加氢制备低碳醇Cu-Fe-Co基催化剂反应性能的影响.研究发现:碱金属的添加能明显降低甲烷化反应,提高催化剂活性,使醇分布向碳链增长方向转移;碱金属Na的添加对催化剂活性的提高影响最大,与未添加碱金属的催化剂相比,液体产物中总醇质量分数提高45.98%,其中C2+醇和C5+醇在总醇中的摩尔分数分别提高了21.88%和22.89%,尾气中CH4摩尔分数下降42.83%.XRD结果表明,碱金属的加入使Cu、Fe、Co三种组分在载体上分散性加强,增加了CO与活性组分的接触位点从而使碳链增长;FE-SEM结果表明,碱金属Na的添加提高了催化剂孔隙结构和活性组分的均匀性和稳定性,同时减轻了催化剂积炭现象,提高了醇收率.