公开(公告)号：US5587056A

公开(公告)日：1996-12-24

申请号：US490231

申请日：1995-06-14

Applicant: Philippe Denis ,  Carl Patois ,  Robert Perron

Inventor： Philippe Denis ,  Carl Patois ,  Robert Perron

IPC: C07D309/10 ,  B01J27/04 ,  B01J29/06 ,  B01J31/02 ,  C07B61/00 ,  C07C51/245 ,  C07C51/42 ,  C07C51/487 ,  C07C51/573 ,  C07C55/14 ,  B01D3/34

CPC classification number: C07C51/487

Abstract: At least a fraction of at least one branched, saturated aliphatic diacid having 6 carbon atoms, for example 2-methylglutaric acid and/or 2-ethylsuccinic acid and/or dimethylsuccinic acid, is separated from admixtures thereof with adipic acid, by at least partially converting such at least one aliphatic diacid into the corresponding anhydride thereof, and removing the corresponding anhydride or the adipic acid from the medium of conversion/anhydridization, for example by contemporaneous or subsequent distillation, or by crystallization.

Abstract translation: 至少一部分具有6个碳原子的至少一种支链饱和脂族二酸，例如2-甲基戊二酸和/或2-乙基琥珀酸和/或二甲基琥珀酸，与己二酸的混合物至少部分地分离 将这样的至少一种脂肪族二酸转化成其相应的酸酐，以及例如通过同时或随后的蒸馏或通过结晶从转化/脱水的介质中除去相应的酸酐或己二酸。

公开(公告)号：US5380938A

公开(公告)日：1995-01-10

申请号：US201020

申请日：1994-02-24

Applicant: Philippe Denis ,  Francois Metz ,  Carl Patois ,  Robert Perron

Inventor： Philippe Denis ,  Francois Metz ,  Carl Patois ,  Robert Perron

IPC: B01J31/22 ,  C07B61/00 ,  C07C51/10 ,  C07C51/12 ,  C07C57/03 ,  C07C67/38 ,  C07C69/44 ,  C07C57/02

CPC classification number: C07C51/12

Abstract: Unsaturated carboxylic acids, e.g., pentenoic acids, are prepared by carbonylating an allylic butenol and/or carboxylate ester thereof with carbon monoxide, in the presence of a catalytically effective amount of an iridium catalyst and an iodinated or brominated promoter therefor, and optionally, a copromoter, notably wherein the promoter/Ir molar ratio ranges from 0.1:1 to 20:1. The final product acids, e.g., 3-pentenoic acid, are themselves readily hydroxycarbonylated, for example, into adipic acid, via reaction with carbon monoxide and water.

Abstract translation: 不饱和羧酸，例如戊烯酸，通过在催化有效量的铱催化剂和其碘化或溴化促进剂存在下，用一氧化碳羰基化烯丙基丁烯醇和/或其羧酸酯，以及任选地， 共促进剂，特别是其中启动子/ Ir摩尔比为0.1:1至20:1。 最终产物酸，例如3-戊烯酸本身通过与一氧化碳和水反应而容易地被羟基羰基化，例如，转化成己二酸。

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：US06222069B1

公开(公告)日：2001-04-24

申请号：US09194924

申请日：1999-03-17

Applicant: Eric B. Henriet ,  Philippe Leconte ,  Carl Patois ,  Robert Perron

Inventor： Eric B. Henriet ,  Philippe Leconte ,  Carl Patois ,  Robert Perron

IPC: C07C5500

CPC classification number: C07C51/43 ,  C07C55/14

Abstract: The invention discloses a method for purifying adipic acid in water. More precisely it discloses an improvement in adipic acid crystallization or recrystallization in water, characterised in that the said crystallization or recrystallization is effected in presence of a strong proton acid and/or in the presence of carbon monoxide. This crystallization or recrystallization particularly enables the content of metal catalyst traces in the adipic acid to be reduced.

Abstract translation: 本发明公开了一种在水中纯化己二酸的方法。 更准确地说，它公开了己二酸结晶或水中的重结晶的改进，其特征在于所述结晶或重结晶在强质子酸存在下和/或在一氧化碳的存在下进行。 这种结晶或重结晶特别使得能够降低己二酸中的金属催化剂痕量的含量。

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：US5625096A

公开(公告)日：1997-04-29

申请号：US325077

申请日：1994-10-19

Applicant: Phillipe Denis ,  Carl Patois ,  Robert Perron

Inventor： Phillipe Denis ,  Carl Patois ,  Robert Perron

IPC: B01J31/22 ,  C07B61/00 ,  C07C51/14 ,  C07C57/03

CPC classification number: C07C51/14

Abstract: Butadiene or derivative thereof is selectively hydroxycarbonylated into at least one pentenoic acid (the pentenoic acids are themselves facilely converted, via hydroxycarbonylation, into adipic acid, a basic starting material for the production of nylon 66 polymers), by reacting same with carbon monoxide and water, at a pressure greater than atmospheric, in the presence of a catalytically effective amount of (1) a palladium catalyst which is soluble in the medium of reaction and (2) crotyl chloride, the amount of the crotyl chloride being at least two mol thereof per mole of palladium values and said palladium values/crotyl chloride at least in part comprising a palladium/crotyl pi-complex, and the amount of water present in the medium of reaction being no greater than about 20% by weight thereof.

Abstract translation: 丁二烯或其衍生物选择性羟基羰基化成至少一种戊烯酸（戊烯酸本身通过羟基羰基化方便地转化成己二酸，用于生产尼龙66聚合物的基本原料），通过与一氧化碳和水反应 在大于大气压的压力下，在催化有效量的（1）可溶于反应介质的钯催化剂和（2）巴洛西氯的存在下，巴淡罗丁氯的量为至少2摩尔 至少部分包含钯/巴豆基pi复合物，并且反应介质中存在的水的量不大于其约20重量％。

公开(公告)号：US06538156B1

公开(公告)日：2003-03-25

申请号：US09194925

申请日：1998-12-04

Applicant: Eric B. Henriet ,  Philippe Leconte ,  Carl Patois ,  Robert Perron

Inventor： Eric B. Henriet ,  Philippe Leconte ,  Carl Patois ,  Robert Perron

IPC: C07C5143

CPC classification number: C07C51/43 ,  C07C55/14

Abstract: The invention discloses a method for purifying adipic acid by crystallization or recrystallization in at least one carbolyxic acid. More precisely, it discloses an improvement in adipic acid crystallization or recrystallization, characterised in that the said crystallization or recrystallization is effected in at least one carboxylic acid with a melting point below 20° C. The presence of carbon monoxide during crystallization or recrystallization can have a favourable effect on the adipic acid purity, in particular by reducing the content of metal catalyst traces of the adipic acid. The adipic acid purity can also be improved when the crystallization or recrystallization is effected in presence of a strong proton acid.

Abstract translation: 本发明公开了一种通过在至少一种碳酸中结晶或重结晶来纯化己二酸的方法。 更准确地说，它公开了己二酸结晶或重结晶的改进，其特征在于所述结晶或重结晶在至少一种熔点低于20℃的羧酸中进行。结晶或重结晶过程中一氧化碳的存在可以具有 特别是通过降低己二酸的金属催化剂痕量的含量，对己二酸的纯度有利的效果。 当在强质子酸存在下进行结晶或重结晶时，己二酸的纯度也得到改善。

公开(公告)号：US06372942B1

公开(公告)日：2002-04-16

申请号：US09194969

申请日：1999-03-17

Applicant: Jacques Brivet ,  Eric B. Henriet ,  Carl Patois ,  Robert Perron

Inventor： Jacques Brivet ,  Eric B. Henriet ,  Carl Patois ,  Robert Perron

IPC: C07C5500

CPC classification number: C07C51/14 ,  C07C55/14

Abstract: The invention discloses pentenoic acid hydroxycarbonylation into adipic acid. More particularly, it concerns one pentenoic acid hydroxycarbonylation method involving reaction water and carbon monoxide, in the presence of a catalyst comprising at least rhodium and/or iridium and an iodinated or brominated catalytic promoter. In the method, the catalyst is derived at least in part from a previous pentenoic acid hydroxycarbonylation operation. The reaction is effected in the presence of an amount of branched carboxylic diacids having 6 carbon atoms not exceeding 200 grams per kilogram reaction mixture.

Abstract translation: 本发明公开了戊烯酸羟基羰基化成己二酸。 更具体地说，它涉及一种包含反应水和一氧化碳的戊烯酸羟基羰基化方法，所述方法包括至少包含铑和/或铱的催化剂和碘化或溴化的催化促进剂。 在该方法中，催化剂至少部分地由先前的戊烯酸羟基羰基化操作得到。 反应在一定量的具有6个碳原子的不超过200克/千克反应混合物的支化羧酸二酸的存在下进行。

公开(公告)号：US5763655A

公开(公告)日：1998-06-09

申请号：US635493

申请日：1996-04-22

Applicant: Carl Patois ,  Robert Perron

Inventor： Carl Patois ,  Robert Perron

IPC: B01J27/13 ,  B01J23/46 ,  C07B61/00 ,  C07C51/14 ,  C07C57/03

CPC classification number: C07C51/14

Abstract: Pentenoic acids are selectively prepared via hydroxycarbonylation of butadiene with carbon monoxide and water, at a temperature above 30.degree. C., under a partial pressure of carbon monoxide, measured at 25.degree. C., equal to or greater than 0.5 bar, in the presence of a catalytically effective amount of an iridium-based catalyst and an iodine-containing or bromine-containing promoter therefor, in a solvent medium, wherein the iodine or bromine/iridium molar ratio is less than or equal to 20/1 and the concentration by weight of water in the reaction mixture is less than or equal to 8%.

Abstract translation: 戊烯酸通过丁二烯与一氧化碳和水的羟基羰基化反应，在高于30℃的温度下，在一氧化碳的分压下，在25℃，等于或大于0.5巴的条件下，在存在下 的催化有效量的铱基催化剂及其含碘或含溴促进剂，其中碘或溴/铱摩尔比小于或等于20/1，并且浓度由 反应混合物中的水重量小于或等于8％。

公开(公告)号：US5883289A

公开(公告)日：1999-03-16

申请号：US809706

申请日：1997-05-14

Applicant: Philippe Denis ,  Dominique Nobel ,  Robert Perron ,  Joel Andre Schwartz

Inventor： Philippe Denis ,  Dominique Nobel ,  Robert Perron ,  Joel Andre Schwartz

IPC: B01J31/20 ,  B01J35/12 ,  C07B61/00 ,  C07C51/12 ,  C07C53/08 ,  C07C55/10 ,  C07C55/14 ,  C07C67/36 ,  C07C69/14 ,  C07C69/24 ,  C07C69/40 ,  C07C69/44

CPC classification number: C07C51/12 ,  C07C67/36

Abstract: A method for preparing carboxylic acids including (n+1) carbon atoms, or the related esters, by liquid phase carbonylation of an alcohol including (n) carbon atoms, in the presence of a uniform catalytic system based on at least one iridium compound and at least one halogenated promoter. In particular, the method is characterised in that the content of ester related to said carboxylic acid and alcohol is kept between 15 and 35% in the medium during the reaction, while the halogenated promoter content is kept between 10 and 20%, and the partial carbon monoxide pressure is 40-200 bar. Said method enables both the rate of carbonylation and the acetic acid selectivity to be increased.

Abstract translation: PCT No.PCT / FR95 / 01283 Sec。 371日期1997年5月14日 102（e）日期1997年5月14日PCT提交1995年10月4日PCT公布。 公开号WO96 / 11179 日期：1996年4月18日在含有（n）碳原子的醇的液相羰基化的基础上，在基于 至少一种铱化合物和至少一种卤化促进剂。 特别地，该方法的特征在于，在反应过程中，介质中与所述羧酸和醇相关的酯含量保持在15至35％之间，而卤代促进剂含量保持在10至20％之间，部分 一氧化碳压力为40-200巴。 所述方法能够提高羰基化速率和乙酸选择性。