公开(公告)号：US06774083B2

公开(公告)日：2004-08-10

申请号：US10426803

申请日：2003-05-01

Applicant: Daniel Thiebaut ,  Carl Patois ,  Lise Layeillon ,  Daniel Marchand

Inventor： Daniel Thiebaut ,  Carl Patois ,  Lise Layeillon ,  Daniel Marchand

IPC: B01J2104

CPC classification number: C07C51/353 ,  C07C51/12 ,  C07C67/36 ,  Y02P20/127 ,  Y02P20/584 ,  Y10S502/50 ,  C07C53/08 ,  C07C69/14

Abstract: A process for improving the stability and/or preventing the deactivation of catalyst in processes of continuous manufacture of acetic acid and/or methyl acetate includes a first, reaction step wherein at least one methyl formate isomerization reaction is carried out in a liquid phase reaction medium, in the presence of carbon monoxide and of a catalytic system including at least one halogenated promoter and at least one iridium-based catalytic compound, and, a second, flash step in which partial vaporization of a reaction medium originating from the first step is carried out in a flash separator. In a non-vaporized liquid fraction resulting from the partial vaporization in the flash separator, an overall content of formic acid and methyl formate is maintained at least equal to 1% by weight of said non-vaporized liquid fraction.

Abstract translation: 在连续制造乙酸和/或乙酸甲酯的方法中改进稳定性和/或防止催化剂失活的方法包括第一反应步骤，其中至少一种甲酸甲酯异构化反应在液相反应介质中进行 在一氧化碳和包括至少一种卤化促进剂和至少一种铱基催化剂的催化体系的存在下，以及第二个闪蒸步骤，其中进行源自第一步骤的反应介质的部分蒸发 在闪光分离器中。 在由闪蒸分离器中的部分汽化产生的非汽化液体馏分中，甲酸和甲酸甲酯的总含量保持至少等于所述非汽化液体馏分的1重量％。

公开(公告)号：US06617472B1

公开(公告)日：2003-09-09

申请号：US09926755

申请日：2001-12-13

Applicant: Daniel Thiebaut ,  Carl Patois ,  Lise Layeillon ,  Daniel Marchand

Inventor： Daniel Thiebaut ,  Carl Patois ,  Lise Layeillon ,  Daniel Marchand

IPC: C07C6736

CPC classification number: C07C51/353 ,  C07C51/12 ,  C07C67/36 ,  Y02P20/127 ,  Y02P20/584 ,  Y10S502/50 ,  C07C53/08 ,  C07C69/14

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US06395927B1

公开(公告)日：2002-05-28

申请号：US09142175

申请日：1998-09-23

Applicant: Carl Patois ,  Robert Perron ,  Daniel Thiebaut

Inventor： Carl Patois ,  Robert Perron ,  Daniel Thiebaut

IPC: C07C5110

CPC classification number: C07C51/353 ,  C07C67/293 ,  C07C53/08 ,  C07C69/14

Abstract: A method for preparing acetic acid and/or methyl acetate by simultaneous isomerization and carbonylation reactions. A reaction mixture is provided containing at least one reagent which provides formyl radicals and at least one further reagent which provides methyl radicals, together with water in an amount of at most 5% by weight, carbon monoxide at a partial pressure between 0.1·105 Pa and 25·105 Pa, a solvent and a catalytic system which contains at least one halogenated promoter and at least one iridium-based compound. In a typical reaction mixture, methyl formate is isomerized to form acetic acid according to the reaction: HCOOCH3CH3COOH while methanol undergoes carbonylation to form acetic acid according to the reaction: CH3OH+COCH3COOH The reagent which provides the formyl radicals is kept at or below 20% by weight of the reaction mixture, while the molar ratio of methyl radicals to formyl radicals in the mixture is greater than 1.

Abstract translation: 通过同时异构化和羰基化反应制备乙酸和/或乙酸甲酯的方法。 提供了含有至少一种提供甲酰基的试剂和至少一种其它试剂的反应混合物，所述试剂在0.1.105Pa的分压下，以至多5重量％的量与水一起提供一氧化碳 和25.105Pa，溶剂和含有至少一种卤化助催化剂和至少一种铱基化合物的催化体系。 在典型的反应混合物中，甲酸甲酯根据反应异构化形成乙酸，而甲醇根据反应进行羰基化形成乙酸：提供甲酰基的试剂保持在或低于20％（重量） 反应混合物中甲基与甲酰基的摩尔比大于1。

公开(公告)号：US20070225384A1

公开(公告)日：2007-09-27

申请号：US11569592

申请日：2005-06-23

Applicant: Daniel Thiebaut

Inventor： Daniel Thiebaut

IPC: C07C51/12 ,  C01B3/32 ,  C07C67/05 ,  C01B3/50

CPC classification number: F25J3/0223 ,  C01B3/025 ,  C01B3/32 ,  C01B2203/0255 ,  C01B2203/046 ,  C01B2203/047 ,  C01B2203/0475 ,  C01B2203/06 ,  C01B2203/068 ,  C01B2203/1223 ,  C01B2203/1288 ,  C01B2203/148 ,  C07C51/12 ,  F25J3/0252 ,  F25J3/0261 ,  F25J3/04527 ,  F25J3/04539 ,  F25J3/04587 ,  F25J2290/80 ,  Y02P20/152 ,  C07C53/08

Abstract: A method for the production of syngas from methanol feedstock is disclosed. The methanol feed (110) is supplied to a partial oxidation reactor (112) with oxygen (114) and optionally steam (116) to yield a mixed stream (118) of hydrogen carbon monoxide, and carbon dioxide. The carbon dioxide (122) is separated out and the hydrogen and carbon monoxide mixture (124) is fed to a cold box (126) where it is separated into hydrogen-rich and carbon monoxide-rich streams (130, 128). The separated carbon dioxide (122) can be recycled back to the partial oxidation reactor (112) as a temperature moderator if desired. The carbon monoxide-rich stream (128) can be reacted with methanol (134) in an acetic acid synthesis unit (132) by a conventional process to produce acetic acid (136) or an acetic acid precursor. Optionally, an ammonia synthesis unit (144) and/or vinyl acetate monomer synthesis unit (156) can be integrated into the plant.

Abstract translation: 公开了一种从甲醇原料生产合成气的方法。 将甲醇进料（110）用氧气（114）和任选的蒸汽（116）供应到部分氧化反应器（112），以产生氢气一氧化碳和二氧化碳的混合物流（118）。 将二氧化碳（122）分离出来并将氢气和一氧化碳混合物（124）进料到冷箱（126）中，在此将其分离成富氢和一氧化碳浓缩物流（130,128）。 如果需要，分离的二氧化碳（122）可以作为温度调节剂循环回部分氧化反应器（112）。 一氧化碳富流（128）可以通过常规方法在乙酸合成装置（132）中与甲醇（134）反应生产乙酸（136）或乙酸前体。 任选地，氨合成单元（144）和/或乙酸乙烯酯单体合成单元（156）可以整合到设备中。

公开(公告)号：US06232490B1

公开(公告)日：2001-05-15

申请号：US09142176

申请日：1998-09-23

Applicant: Carl Patois ,  Robert Perron ,  Daniel Thiebaut

Inventor： Carl Patois ,  Robert Perron ,  Daniel Thiebaut

IPC: C07C5116

CPC classification number: C07C51/353 ,  C07C67/293 ,  C07C53/08 ,  C07C69/14

Abstract: A method for the preparation of acetic acid and/or methyl acetate by isomerization of methyl formate in a reaction mixture which includes water, a solvent and a catalytic system containing a halogenated promoter and an iridium-based compound. Carbon monoxide is present in the reaction mixture at a partial pressure between 0.1.105 Pa and 25.105 Pa, methyl formate is maintained below 20% by weight of the reaction mixture and water is maintained in an amount which is at most 5% by weight of the reaction mixture. In a typical system, method formate isomerizes to acetic acid according to the reaction: HCOOCH3CH3COOH.

Abstract translation: 一种通过在包含水，溶剂和含有卤化促进剂和铱基化合物的催化体系的反应混合物中异构化甲酸甲酯来制备乙酸和/或乙酸甲酯的方法。 一氧化碳在0.1.105Pa和25.105Pa之间的分压下存在于反应混合物中，甲酸甲酯维持在反应混合物重量的20％以下，水的量保持在至少5重量％ 反应混合物。 在典型的系统中，方法甲酸酯根据以下反应异构化成乙酸：

公开(公告)号：US07009070B2

公开(公告)日：2006-03-07

申请号：US10433474

申请日：2002-02-05

Applicant: Daniel Thiebaut ,  Daniel Marchand ,  Philippe Kalck ,  Carole Le Berre ,  Philippe Serp

Inventor： Daniel Thiebaut ,  Daniel Marchand ,  Philippe Kalck ,  Carole Le Berre ,  Philippe Serp

IPC: C07C67/36 ,  C07C53/08

CPC classification number: C07C67/36 ,  C07C51/10 ,  C07C51/12 ,  C07C67/37 ,  Y02P20/582 ,  C07C53/08 ,  C07C69/14

Abstract: 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.

Abstract translation: 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。

公开(公告)号：US06916952B1

公开(公告)日：2005-07-12

申请号：US09807434

申请日：1999-10-29

Applicant: Carole Le Berre ,  Philippe Kalck ,  Philippe Serp ,  Lise Layeillon ,  Daniel Thiebaut

Inventor： Carole Le Berre ,  Philippe Kalck ,  Philippe Serp ,  Lise Layeillon ,  Daniel Thiebaut

IPC: B01J27/13 ,  B01J31/20 ,  C07B61/00 ,  C07C51/09 ,  C07C51/12 ,  C07C51/353 ,  C07C53/08 ,  C07C67/36 ,  C07C69/14

CPC classification number: C07C51/353 ,  C07C51/12 ,  C07C67/36 ,  C07C53/08 ,  C07C69/14

Abstract: The invention relates to a process for the preparation of acetic acid and/or methyl acetate in the liquid phase by the carbonylation of methanol and/or the isomerization of methyl formate in the presence of water, a solvent, a homogeneous catalyst system comprising iridium and a halogen-containing promoter, and carbon monoxide, wherein said catalyst system also comprises platinum.

Abstract translation: 本发明涉及通过甲醇的羰基化和/或甲酸甲酯在水，溶剂，包含铱的均相催化剂体系的存在下在液相中制备乙酸和/或乙酸甲酯的方法和 含卤素促进剂和一氧化碳，其中所述催化剂体系还包含铂。

公开(公告)号：US06642413B2

公开(公告)日：2003-11-04

申请号：US09950819

申请日：2001-09-13

Applicant: Daniel Thiebaut

Inventor： Daniel Thiebaut

IPC: C07C5110

CPC classification number: C07C67/36 ,  C07C51/12 ,  C07C67/37 ,  C07C53/08 ,  C07C69/14

Abstract: A continuous preparative process, including monitoring production, for acetic acid, methyl acetate or a mixture thereof, by carbonylation, in an industrial installation, of methanol or a carbonylatable derivative of methanol with carbon monoxide in a liquid phase in the presence of water and a homogeneous catalyst system. In a reaction zone I, the carbonylation is carried out in the liquid phase at a temperature of 150 to 250° C., under a pressure of 5·105 to 200·105 Pa and with venting of part of a gaseous canopy above a liquid phase level in said reactor. Then, in a vaporization or flash zone II, a liquid originating from the zone I at a pressure below that of zone I is partially vaporized to form a liquid fraction which is recycled into the reactor, and in a purification zone III, a vaporized fraction originating from flash zone II is distilled on a distillation column. At an outlet of the column, the product is recovered, other constituents of the vaporized fraction being at least partially recycled into said reactor. In the process, the reactor temperature and feed rate of the methanol or carbonylatable derivative in said reactor are brought under control of the carbon monoxide feed rate and of at least one of the parameters defining the composition of the reaction medium, or of the venting or of both the reaction medium and of the venting.

Abstract translation: 一种连续的制备方法，包括在工业装置中通过羰基化，乙酸，乙酸甲酯或它们的混合物在甲醇或甲醇的可羰基化衍生物与一氧化碳在液体存在下在水和 均相催化剂体系。 在反应区域I中，羰基化在液相中在150〜250℃的温度下，在5.10〜5.0×10 5 Pa的压力下进行，并且将部分气体顶盖排出 在所述反应器中的液相水平。 然后，在蒸发或闪蒸区域II中，来自区域I的压力低于区域I的液体的液体被部分蒸发以形成再循环到反应器中的液体馏分，并且在净化区域III中，蒸发馏分 来自闪蒸区II的蒸馏塔在蒸馏塔上蒸馏。 在塔的出口处，产物被回收，蒸发馏分的其它组分至少部分地再循环到所述反应器中。 在此过程中，所述反应器中的甲醇或羰基化衍生物的反应器温度和进料速率受到一氧化碳进料速率以及限定反应介质的组成或排放或 的反应介质和排气。