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    • 1. 发明授权
    • Modification of the catalytic system in an industrial process for making acetic and/or methyl acetate acid
    • 在制造乙酸和/或乙酸甲酯的工业过程中改性催化体系
    • US07009070B2
    • 2006-03-07
    • US10433474
    • 2002-02-05
    • Daniel ThiebautDaniel MarchandPhilippe KalckCarole Le BerrePhilippe Serp
    • Daniel ThiebautDaniel MarchandPhilippe KalckCarole Le BerrePhilippe Serp
    • C07C67/36C07C53/08
    • C07C67/36C07C51/10C07C51/12C07C67/37Y02P20/582C07C53/08C07C69/14
    • The invention relates to a continuous process for the manufacture of acetic acid and/or methyl acetate, characterized in that, during the continuous operation of the installation for a continuous industrial process, called the initial process, for the carbonylation of methanol or a carbonylatable derivative of methanol such as dimethyl ether, methyl halides or methyl acetate, in the homogeneous liquid phase and under carbon monoxide pressure, in the presence of a catalyst system comprising a rhodium-based homogeneous catalyst and a halogenated promoter, and in the presence of a concentration of water greater than or equal to 14% in the reaction medium, the composition of said homogeneous catalyst is modified gradually by adding an iridium compound over time.This process makes it possible on the one hand to modify the composition of the catalyst system so as to change from a homogeneous catalyst based on rhodium alone to a catalyst based on rhodium and iridium, or even iridium alone, without stopping the installation, and on the other hand to reduce the water content of the reaction medium once the iridium additions have been effected.
    • 本发明涉及一种用于制造乙酸和/或乙酸甲酯的连续方法,其特征在于,在用于连续工业过程的连续操作(称为初始方法)中,用于羰基化甲醇或可羰基化衍生物 在均相液相和一氧化碳压力下,在包含铑基均相催化剂和卤化助催化剂的催化剂体系存在下,在浓度为1的存在下,在甲醇,甲基卤化物或乙酸甲酯中, 的水在反应介质中大于或等于14%,通过随时间加入铱化合物逐渐改变所述均相催化剂的组成。 该方法可以一方面改变催化剂体系的组成,从而将基于单独的铑的均相催化剂改变为仅基于铑和铱的催化剂,或者甚至不停止安装,并且在 另一方面,一旦实施了铱添加,就降低了反应介质的含水量。
    • 5. 发明授权
    • Process for improving the stability and/or preventing the deactivation of the catalyst during the manufacture of acetic acid and/or of methyl acetate
    • 在乙酸和/或乙酸甲酯的制造期间提高稳定性和/或防止催化剂失活的方法
    • US06617472B1
    • 2003-09-09
    • US09926755
    • 2001-12-13
    • Daniel ThiebautCarl PatoisLise LayeillonDaniel Marchand
    • Daniel ThiebautCarl PatoisLise LayeillonDaniel Marchand
    • C07C6736
    • C07C51/353C07C51/12C07C67/36Y02P20/127Y02P20/584Y10S502/50C07C53/08C07C69/14
    • The present invention relates to process for improving the stability and/or preventing the deactivation of the catalyst in processes of manufacture of acetic acid and/or of methyl acetate according to which processes, in a first step, referred to as the reaction step, at least one methyl formate isomerization reaction is carried out in liquid phase, in the presence of carbon monoxide and of a catalytic system comprising at least one halogenated promoter and at least one iridium-based catalytic compound, and, in a second step, referred to as the flash step, the partial vaporization of the reaction medium originating from the first step is carried out in a separator referred to as the flash separator, characterized in that it consists in maintaining an overall content of formic acid and of methyl formate at least equal to 1% by weight of said liquid fraction, preferably between 1 and 50%, preferably between 1 and 30%, by weight with respect to said liquid fraction, in the non-vaporized liquid fraction originating from said flash separator. The invention also relates to a complete process of manufacture acetic acid and/or of methyl acetate which incorporates this improvement. The invention enables preparing acetic acid and/or methyl acetate with an increased stability of the catalytic system, even in the presence of contents of water which are particularly low, and of particularly low carbon monoxide pressures in the reaction zone, and is applied more particularly to processes of manufacture of acetic acid and/or of methyl acetate in which process the first step further comprises a methanol carbonylation reaction.
    • 本发明涉及在制备乙酸和/或乙酸甲酯的方法中提高稳定性和/或防止催化剂失活的方法,根据该方法,在第一步骤中称为反应步骤,在 在一氧化碳和包含至少一种卤化促进剂和至少一种铱基催化化合物的催化体系的存在下,在液相中至少一种甲酸甲酯异构化反应进行,在第二步中,称为 闪蒸步骤,来自第一步骤的反应介质的部分蒸发在称为快速分离器的分离器中进行,其特征在于其保持甲酸和甲酸甲酯的总含量至少等于 所述液体馏分的1重量%,优选1至50重量%,优选1至30重量%,相对于所述液体馏分,在未汽化的l 来自所述闪蒸分离器的鱿鱼级分。 本发明还涉及制备乙酸和/或乙酸甲酯的完整方法,其包括该改进。 本发明能够制备具有提高的催化体系稳定性的乙酸和/或乙酸甲酯,即使在特别低的水含量和反应区中一氧化碳压力特别低的情况下,更具体地使用 涉及乙酸和/或乙酸甲酯的制备方法,其中第一步还包括甲醇羰基化反应。