NOVEL BASIC LIGANDS FOR HOMOGENEOUS CATALYTIC METHANOL CARBONYLATION .20. KINETICS OF METHANOL CARBONYLATION TO ACETALDEHYDE, USING AN ETHER-PHOSPHANE-MODIFIED COBALT CATALYST

被引:17
作者
LINDNER, E [1 ]
BADER, A [1 ]
BRAUNLING, H [1 ]
JIRA, R [1 ]
机构
[1] WACKER CHEM GMBH,W-8263 BURGHAUSEN,GERMANY
来源
JOURNAL OF MOLECULAR CATALYSIS | 1990年 / 57卷 / 03期
关键词
D O I
10.1016/0304-5102(90)85003-Z
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Methanol is hydrocarbonylated to acetaldehyde by means of a catalytic system consisting of CoI2 and [C4H7O2-CH2- P(Ph)-CH2-]2, (C4H7O2 = 1,4-dioxanyl) with synthesis gas. The rate of this reaction in terms of the decrease of the molar fraction of methanol can be expressed by the following equation:. The activation energy and the standard activation entropy are 48 kJ mol-1 and -216 J mol-1 K-1, respectively. Whereas excess ligand (CoI2/ ligand = 1 2) and admixture of water results in a drastic decrease in the reaction rate, addition of iodide in the form of LiI has no effect on it. The conversions reach approximately 90%. For the industrial application of this process in a continuously working plant, converions of 20 - 30% would be advantageous. In this latter range the selectivities with respect to acetaldehyde including its dimethylacetal ('total aldehyde') are higher than 80%. At 270 bar, MeOH/ligand/CoI2 = 800/1/1 and 190 °C, a space-time yield of 6.1 kg of total aldehyde per m3 of MeOH per minute is achieved. © 1990.
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页码:291 / 300
页数:10
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