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21. 发明授权

US5312979A Preparation of adipic acid by hydrocarboxylation of pentenoic acids 失效
标题翻译：通过戊烯酸的氢化羧酸制备己二酸
公开(公告)号：US5312979A
公开(公告)日：1994-05-17
申请号：US88353
申请日：1993-07-09
申请人： Philippe Denis , Francois Metz , Robert Perron
发明人： Philippe Denis , Francois Metz , Robert Perron
IPC分类号： C07C51/14 , C07C55/14
CPC分类号： C07C55/14 , C07C51/14
摘要： Adipic acid is selectively prepared via hydrocarboxylation of pentenoic acids, by reacting water and carbon monoxide with at least one pentenoic acid, in the presence of a catalytically effective amount of a rhodium-based catalyst and at least one iodinated promoter therefor, at a temperature ranging from 100.degree. to 240.degree. C. and a pressure greater than atmospheric, and wherein (a) such reaction is carried out in the absence of a third reaction solvent and (b) the carbon monoxide partial pressure, measured at 25.degree. C., is less than or equal to 20 bar.
摘要翻译：在催化有效量的铑基催化剂和至少一种碘化促进剂的存在下，通过水和一氧化碳与至少一种戊烯酸反应，在温度范围内通过氢过羧酸选择性制备己二酸 100℃至240℃，压力大于大气压，其中（a）该反应在不存在第三反应溶剂的情况下进行，（b）在25℃下测得的一氧化碳分压，小于或等于20巴。

22. 发明授权

US4997978A Preparation of alkyl carboxylates by hydrocarbonylation 失效
标题翻译：通过烃基制备羧酸烷基酯
公开(公告)号：US4997978A
公开(公告)日：1991-03-05
申请号：US261635
申请日：1988-10-24
申请人： Jean Gauthier-Lafaye , Robert Perron
发明人： Jean Gauthier-Lafaye , Robert Perron
IPC分类号： C07C67/36 , B01J27/00 , B01J31/00 , C07B61/00 , C07C27/00 , C07C51/12 , C07C67/00 , C07C69/14
CPC分类号： C07C51/12
摘要： Alkyl carboxylates of the formula:R--CO--O--CH.sub.2 R'are prepared by hydrocarbonylating a compound of the formula:R--CO--O--R'in the simultaneous presence, in the reaction medium, of cobalt, ruthenium, an alkyl iodide and an ionic iodide, the atomic ratio Co/Ru being less than or equal to 1, and the total amount of iodine-containing promoters present in the medium being such that I/Ru is greater than or equal to 5.
摘要翻译：式R-CO-O-CH 2 R'的烷基羧酸盐通过在反应介质中同时存在钴，钌，烷基碘和离子碘化物，原子比Co / Ru小于或等于1，介质中存在的含碘促进剂的总量使得I / Ru大于或等于5。

23. 发明授权

US4927957A Catalytic dimerization of alkyl acrylates 失效
标题翻译：烷基丙烯酸酯的催化二聚
公开(公告)号：US4927957A
公开(公告)日：1990-05-22
申请号：US234154
申请日：1988-08-19
申请人： Robert Perron , Sylvain Mutez
发明人： Robert Perron , Sylvain Mutez
IPC分类号： C07C67/347 , B01J31/28 , C07B61/00 , C07C69/54 , C07C69/593
CPC分类号： C07C69/593
摘要： Alkyl acrylates are catalytically dimerized, e.g., to produce alkyl diesters of dihydromuconic acid, in the presence of a catalytically effective amount of palladium, tetrafluoroboric acid and a hydrogenophosphonium tetrafluoroborate, and wherein the palladium concentration ranges from 0.1 to 3 mmol per mole of said at least one alkyl acrylate, the reaction temperature ranges from 70.degree. to 150.degree. C. and the hydrogenophosphonium tetrafluoroborate concentration is at least 6 mmol per mole of said at least one alkyl acrylate.
摘要翻译：在催化有效量的钯，四氟硼酸和四氟硼酸氢鏻的存在下，丙烯酸烷基酯被催化二聚化，例如产生二氢葡聚糖酸的烷基二酯，其中钯浓度范围为每摩尔所述的至少一种丙烯酸烷基酯，反应温度为70-150℃，四氟硼酸氢鏻的浓度至少为每摩尔所述至少一种丙烯酸烷基酯6mmol。

24. 发明授权

US4619791A Carbonylation of methyl acetate to acetic anhydride 失效
标题翻译：乙酸甲酯对乙酸酐的羰基化
公开(公告)号：US4619791A
公开(公告)日：1986-10-28
申请号：US435752
申请日：1982-10-21
申请人： Jean Gauthier-Lafaye , Robert Perron
发明人： Jean Gauthier-Lafaye , Robert Perron
IPC分类号： C07C53/12 , B01J31/00 , C07B61/00 , C07C51/00 , C07C51/12 , C07C51/56 , C07C67/00
CPC分类号： C07C51/56
摘要： Methyl acetate is carbonylated to acetic anhydride with carbon monoxide, in liquid phase, in an anhydrous reaction medium, in the presence of a catalytically effective amount of (i) nickel, (ii) methyl iodide, (iii) an alkali metal iodide, and (iv) a crown ether.
摘要翻译：在催化有效量的（ⅰ）镍，（ⅱ）甲基碘，（ⅲ）碱金属碘化物和（ⅲ）碱金属碘化物的存在下，乙酸甲酯与一氧化碳在液相中，在无水反应介质中，（iv）冠醚。

25. 发明授权

US4576809A Preparation of alkali or alkaline earth metal cobalttetracarbonylates and catalysts of carbonylation reactions therewith 失效
标题翻译：制备碱金属或碱土金属钴四羰基化物及其羰基化反应催化剂
公开(公告)号：US4576809A
公开(公告)日：1986-03-18
申请号：US549553
申请日：1983-11-07
申请人： Jean Gauthier-Lafaye , Robert Perron
发明人： Jean Gauthier-Lafaye , Robert Perron
IPC分类号： C01G51/00 , C10G1/04 , B01J21/18 , B01J27/20 , C07C51/10
CPC分类号： C01G51/006 , C01G51/02 , C01P2006/82
摘要： Alkali or alkaline earth metal cobalttetracarbonylates well suited for catalyzing carbonylation reactions, e.g., the carbonylation of organic compounds comprising halomethyl functions, are facilely prepared by reacting a cobalt (II) compound with carbon monoxide in the presence of (i) an inorganic base which comprises an alkali or alkaline earth metal hydroxide or an alkali or alkaline earth metal bicarbonate and (ii) at least one sulfur compound having at least one sulfur atom, the oxidation state of which being no greater than +3, and in a reaction medium comprising water, an alcohol, an ether, or admixture of water and an alcohol or an ether.
摘要翻译：非常适合催化羰基化反应的碱金属或碱土金属钴四钴酸盐，例如羰基化反应，例如包含卤代甲基官能团的有机化合物的羰基化，可以通过在（i）无机碱存在下使钴（II）化合物与一氧化碳反应来制备，所述无机碱包括碱金属或碱土金属氢氧化物或碱金属或碱土金属碳酸氢盐和（ii）至少一种具有至少一个硫原子的硫化合物，其氧化态不大于+3，并且在包含水的反应介质中，醇，乙醚或水和醇或醚的混合物。

26. 发明授权

US4436889A Preparation of carboxylic acids by carbonylation of alcohols 失效
标题翻译：通过羰基化醇制备羧酸
公开(公告)号：US4436889A
公开(公告)日：1984-03-13
申请号：US260810
申请日：1981-05-05
申请人： Jean Gauthier-Lafaye , Robert Perron
发明人： Jean Gauthier-Lafaye , Robert Perron
IPC分类号： C07C53/00 , B01J23/00 , B01J27/00 , B01J31/00 , C07C51/00 , C07C51/12 , C07C53/08 , C07C57/32 , C07C67/00 , C07C53/134 , C07C57/30
CPC分类号： C07C51/12
摘要： Carboxylic acids having the structural formula R.sup.1 COOH, wherein R.sup.1 is a linear, branched or cyclic chain alkyl radical of from 1 to 6 carbon atoms or a phenyl-C.sub.n H.sub.2n -radical wherein 1.ltoreq.n.ltoreq.6, are prepared by carbonylating an alcohol having the formula R.sup.1 -OH with carbon monoxide in liquid phase, in the presence of a catalytically effective amount of nickel and an alkyl or acyl halide promoter therefor, at a temperature of at least about 120.degree. C. and under a total pressure of less than 200 bars, and said carbonylation being carried out in the presence of at least one vanadium compound in which the vanadium is in an oxidation state of 4 or 5, and in an initial carboxylic acid reaction medium having the formula R.sup.2 -COOH, wherein R.sup.2 is defined as was R.sup.1 above, and further wherein R.sup.1 and R.sup.2 may be the same or different.
摘要翻译：具有结构式R 1 COOH的羧酸，其中R 1是具有1至6个碳原子的直链，支链或环状链烷基或苯基-C n H 2n - ，其中n 1 = n 6，是通过羰基化具有式R 1 -OH的醇与一氧化碳在液相中，在催化有效量的镍和其烷基或酰卤促进剂存在下，在至少约120℃的温度和总压力所述羰基化反应在至少一种钒化合物的存在下进行，其中钒处于4或5的氧化态，并且在具有式R2-COOH的初始羧酸反应介质中进行，其中 R2定义为上述R 1，并且其中R 1和R 2可以相同或不同。

27. 发明授权

US4431835A Hydrocarbonylation/carbonylation of alkyl carboxylates 失效
标题翻译：羧酸烷基酯的羰基化羰基化
公开(公告)号：US4431835A
公开(公告)日：1984-02-14
申请号：US280218
申请日：1981-07-06
申请人： Jean Gauthier-Lafaye , Robert Perron
发明人： Jean Gauthier-Lafaye , Robert Perron
IPC分类号： C07C69/14 , B01J23/00 , B01J27/00 , B01J31/00 , C07B61/00 , C07C27/00 , C07C29/147 , C07C29/32 , C07C29/36 , C07C45/00 , C07C45/49 , C07C47/06 , C07C51/12 , C07C67/00 , C07C67/36
CPC分类号： C07C29/32 , C07C29/36 , C07C45/49 , C07C51/12 , C07C67/36
摘要： Alkyl carboxylates are hydrocarbonylated and/or carbonylated with carbon monoxide and hydrogen, in an aqueous medium, and in the presence of a catalytically effective amount of a catalyst system comprising (i) ruthenium, (ii) cobalt, (iii) at least one iodine-containing promoter, and (iv) chromium. The subject hydrocarbonylation/carbonylation is admirably well suited, e.g., for the preparation of acetaldehyde, ethanol, ethyl acetate and acetic acid, especially from a methyl carboxylate.
摘要翻译：在水性介质中，在催化有效量的催化剂体系存在下，羧酸烷基酯在一氧化碳和氢气下进行烃基化和/或羰基化，包括（ⅰ）钌，（ⅱ）钴，（ⅲ）至少一种碘（iv）铬。本发明的烃基化/羰基化是非常适合的，例如用于制备乙醛，乙醇，乙酸乙酯和乙酸，特别是甲酸甲酯。

28. 发明授权

US06538156B1 Method for purifying adipic acid by crystallization 失效
标题翻译：通过结晶纯化己二酸的方法
公开(公告)号：US06538156B1
公开(公告)日：2003-03-25
申请号：US09194925
申请日：1998-12-04
申请人： Eric B. Henriet , Philippe Leconte , Carl Patois , Robert Perron
发明人： Eric B. Henriet , Philippe Leconte , Carl Patois , Robert Perron
IPC分类号： C07C5143
CPC分类号： C07C51/43 , C07C55/14
摘要： 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.
摘要翻译：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。

29. 发明授权

US06372942B1 Pentenoic acid hydroxycarbonylation method 失效
标题翻译：戊烯酸羟基羰基化法
公开(公告)号：US06372942B1
公开(公告)日：2002-04-16
申请号：US09194969
申请日：1999-03-17
申请人： Jacques Brivet , Eric B. Henriet , Carl Patois , Robert Perron
发明人： Jacques Brivet , Eric B. Henriet , Carl Patois , Robert Perron
IPC分类号： C07C5500
CPC分类号： C07C51/14 , C07C55/14
摘要： 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.
摘要翻译：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。

30. 发明授权

US6008408A Process for the hydroxycarbonylation of pentenoic acids 失效
标题翻译：戊烯酸羟基羰基化方法
公开(公告)号：US6008408A
公开(公告)日：1999-12-28
申请号：US424335
申请日：1995-07-11
申请人： Philippe Denis , Francois Klinger , Jean-Claude Laurent , Robert Perron , Joel Schwartz , Francois Vachet
发明人： Philippe Denis , Francois Klinger , Jean-Claude Laurent , Robert Perron , Joel Schwartz , Francois Vachet
IPC分类号： B01J23/46 , B01J38/00 , C07B61/00 , C07C51/14 , C07C51/42 , C07C51/43 , C07C55/14
CPC分类号： C07C51/42 , C07C51/14 , C07C51/43 , Y02P20/584
摘要： The present invention relates to a process for the hydroxycarbonylation of pentenoic acids. By the process, one or a number of pentenoic acids are hydroxycarbonylated to adipic acid, by carbon monoxide and water, in the presence of a catalyst based on iridium and/or rhodium and of at least one iodinated promoter. The reaction mixture obtained is subjected to a refining operation, after having optionally been concentrated, making it possible to separate at least a part of the catalyst. The catalyst thus separated is recycled to an operation for the hydroxycarbonylation of pentenoic acids, of butadiene, or of butadiene derivatives.
摘要翻译： PCT No.PCT / FR93 / 01028 Sec。 371日期：1995年7月11日 102（e）日期1995年7月11日PCT提交1993年10月19日PCT公布。公开号WO94 / 08939 日期：1994年4月28日本发明涉及戊烯酸羟基羰基化的方法。通过该过程，一种或多种戊烯酸通过一氧化碳和水在基于铱和/或铑的催化剂和至少一种碘化促进剂的存在下被羟基羰基化成己二酸。所获得的反应混合物在任选地浓缩之后进行精制操作，使得可以分离至少一部分催化剂。将如此分离的催化剂再循环至戊烯酸，丁二烯或丁二烯衍生物的羟基羰基化操作。

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