共查询到18条相似文献,搜索用时 171 毫秒
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[顺—二羰基(N—2—(2—吡啶)乙基芳胺)铑]的四苯硼酸盐的合成及其催化… 总被引:2,自引:0,他引:2
〔顺-二羰基(N-2-(2-吡啶)乙基对取代苯胺)铑〕的四苯硼酸盐作为催化剂,用于催化甲醇羰基化反应,在温和的条件下,可顺利催化甲醇羰基化反就得到乙酸和乙酸甲酯而无其它副产物。若以甲醇和乙本乡的混合液作反应物,则得到乙酸酐和乙酸甲酯,即使在大量水存在下,也仅有微量的水煤气转换反应发生。实验证明对位取代基团的电子效应对铑配合物的催化活性影响甚微在不同位置以不同链长相联的二吡啶配体对铑阳离子配合物性能 相似文献
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[顺-二羰基(N-2-(2-吡啶)乙基对取代苯胺)铑]的四苯硼酸盐作为催化剂,用于催化甲醇羰基化反应,在温和的条件下,可顺利催化甲醇羰基化反应得到乙酸和乙酸甲酯而无其它副产物.若以甲醇和乙酸的混合液作反应物,则得到乙酸酐和乙酸甲酯.即使在大量水存在下,也仅有微量的水煤气转换反应发生.实验证明对位取代基团的电子效应对铑配合物的催化活性影响甚微.在不同位置以不同链长相联的二吡啶配体对铑阳离子配合物性能的影响是明显的.其中α,α'-联吡啶铑阳离子结构不利于催化反应的进行.由此证明,作为催化剂活性物种除必须的Rh-CO键存在外,配体的空间结构是影响配合物活性的决定因素.羰基化发生在碘甲烷的氧化加成与乙酰碘的还原消除之间,同时还伴有一个在配位的乙酰基与铑的顺-空配位之间甲基的1,2移动变化. 相似文献
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稀土添加剂对高分子铑配合物催化甲醇羰基基化反应的促进作用 总被引:1,自引:0,他引:1
稀土添加剂对高分子铑配合物催化甲醇羰基基化反应的促进作用彭文庆,袁国卿(中国科学院化学研究所北京100080)关键词甲醇,添加剂,羰基化稀土金属化合物作为催化剂的研究,由于其在某些反应中具有比过渡金属更优良的性能,引起了人们的普遍重视。对于甲醇羰基化... 相似文献
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螯合型羰基铑配合物催化甲醇羰基化反应的机理研究 总被引:2,自引:0,他引:2
报道了螯合型正方平面羰基铑配合物催化甲醇羰基化反应的机理研究. 通过含有两种与铑具有不同配位能力的授体的配体, 与四羰基二氯二铑形成螯合型正方平面阳离子配合物. 研究证明, 该类配合物在催化甲醇羰基化反应过程中, 其活性物种区别于文献报道的[Rh(CO)2I2]-阴离子. 配合物中铑与吡啶环上共轭N形成的N→Rh配键, 在羰基化反应过程中并非通常认为的断裂而是形成新的活性物种, 即配体与铑作为整体参与了CH3I的氧化加成及CH3COI的生成过程. 通过对相应的聚合物配体铑催化剂的研究, 进一步证实了这个反应机理. 这一结果, 对该类催化剂分子设计, 以及克服其工业使用中的催化剂沉淀失活等现象均有重要意义. 相似文献
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螯合型高分子铑配合物催化甲醇羰基化反应的机理探讨 总被引:4,自引:0,他引:4
螯合型高分子铑配合物催化甲醇羰基化反应的机理探讨潘平来,柳忠阳,王晓筠,黄茂开,袁国卿(中国科学院化学研究所,北京100080)1引言甲醇在铑催化剂的作用下,与一氧化碳反应羰基化为乙酸,是一个重要的基本有机合成,反应。在为数众多的催化剂中,锗的配合物... 相似文献
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顺二羰基铑(Ⅰ)共聚物催化剂的合成,结构与催化甲醇羰基化反应性能的研究 总被引:4,自引:0,他引:4
我们曾报道一系列含有两种不同配位基团的高分子共聚物与四羰基二氯二铑形成的顺二羰基铑(Ⅰ)配合物。这些配合物在催化甲醇羰基化反应中显示出高催化活性和高稳定性。本文采用4-乙烯吡啶(Y)和丙烯酸甲酯(B)共聚物为配体,对其与四羰基二氯二铑形成的配合物(YBRh)进行了表征。对该系列配合物催化甲醇羰基化生成乙酸的性能进行了评价。 相似文献
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The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked copolymer of methyl acrylate (M) and 2-vinylpyddine (V)shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction. Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system. A mechanism similar to that of soluble rhodium catalyst was proposed. 相似文献
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合成了一系列丙烯酰胺-丙烯酸甲酯共聚物铑配合物,采用X-射线光电子能谱(XPS)和IR光谱研究了其中存在的配位结构,通过催化甲醇羰基化反应制备乙酸,考察了它们作为该反应的催化剂的性能,并证明了该催化剂体系具有高活性,高选择性和低腐蚀性。 相似文献
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PENG Feng 《高等学校化学研究》2000,16(2):188-190
IntroductionThe carbonylation of alcohols via homogenous catalysis is important in manufacturingacetic acid and higher carboxylic acids and their esters[1 ,2 ] . The main route to produce aceticacid is to make methanol carbonylated by means of the Monsanto and BP process in which ahomogeneous rhodium catalystis used.Although the homogeneous carbonylation ofmethanolis a highly selective process,itisaffected by the disadvantagesassociated with a highly corro-sive reaction medium due to the use … 相似文献
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A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces the investment on the equipment. 相似文献
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A series of square planar cis-dicarbonyl polymer coordinated rhodium complexes with uncoordinated donors near the central
rhodium atoms for carbonylation of methanol to acetic acid are reported. Data of IR, XPS and thermal analysis show that these
complexes are very stable. The intramolecular substitution reaction is proposed for their high stability. These complexes
show excellent catalytic activity, selectivity and less erosion to the equipment for the methanol carbonylation to acetic
acid. The distillation process may be used instead of flash vaporization in the manufacture of acetic acid, which reduces
the investment on the equipment.
Project supported by the National Natural Science Foundation of China (Grant No. 29574186). 相似文献
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Anatta Wahyu Budiman Ji Su Nam Jae Hyun Park Ryan Indra Mukti Tae Sun Chang Jong Wook Bae Myoung Jae Choi 《Catalysis Surveys from Asia》2016,20(3):173-193
Acetic acid (AA) has been largely used with a wide range of applications such as a raw material for a synthesis of vinyl acetate monomer, cellulose acetate or acetate anhydrate, acetate ester and a solvent for a synthesis of terephthalic acid and so on. The present paper briefly summarizes the commercialized chemical processes with their Rh or Ir-based catalytic systems in a liquid-phase carbonylation reaction such as Monsanto, Cativa and Acetica processes. In addition, some alternative catalytic systems such as heterogeneous catalysts to produce AA by direct oxidation or indirect carbonylation of dimethyl ether through BP-SaaBre process in a gas-phase reaction to solve some problems such as a difficult separation of homogeneous catalysts in a corrosive reaction medium. Some home-made heterogeneous catalysts such as a rhodium incorporated graphitic carbon nitride (Rh-g-C3N4) and some heterogenized homogeneous catalysts using the supports of tungsten carbide, iron oxide or graphitic carbon nitride containing rhodium complexes were also introduced for the synthesis of AA through a liquid-phase methanol carbonylation reaction to effectively solve the leaching problem of active rhodium metal as well as to mitigate the separation problem of homogeneous catalysts. 相似文献