公开(公告)号：US06683179B2

公开(公告)日：2004-01-27

申请号：US10258941

申请日：2002-10-29

Applicant: Peter Bassler ,  Dieter Baumann ,  Rolf-Hartmuth Fischer ,  Eberhard Fuchs ,  Johann-Peter Melder ,  Frank Ohlbach

Inventor： Peter Bassler ,  Dieter Baumann ,  Rolf-Hartmuth Fischer ,  Eberhard Fuchs ,  Johann-Peter Melder ,  Frank Ohlbach

IPC: C07D20108

CPC classification number: C07D201/08

Abstract: A process for the preparation of caprolactam is provided, wherein a) a mixture (I) containing 6-aminocapronitrile and water is reacted in the gas phase, in the presence of a catalyst, to give a mixture (II) containing caprolactam, ammonia, water, high-boiling components and low-boiling components, b) ammonia is then removed from the mixture (II) to give a mixture (III) containing caprolactam, water, high-boiling components and low-boiling components, c) water is then removed from the mixture (III) to give a mixture (IV) containing caprolactam, high-boiling components and low-boiling components, and d) a solid (V) containing caprolactam is then obtained from the mixture (IV) by crystallization, the proportion by weight of caprolactam in the solid (V) being greater than in the mixture (IV).

Abstract translation: 提供了制备己内酰胺的方法，其中a）含有6-氨基己腈和水的混合物（I）在催化剂存在下在气相中反应，得到含己内酰胺，氨，水的混合物（II） ，高沸点组分和低沸点组分，b）然后从混合物（II）中除去氨，得到含有己内酰胺，水，高沸点组分和低沸点组分的混合物（III），c）然后将水 从混合物（III）中除去，得到含有己内酰胺，高沸点组分和低沸点组分的混合物（IV），然后通过结晶从混合物（IV）获得含有己内酰胺的固体（V），比例 的固体（V）中的己内酰胺的量大于混合物（IV）中的。

公开(公告)号：US06677449B2

公开(公告)日：2004-01-13

申请号：US10258942

申请日：2002-10-29

Applicant: Peter Bassler ,  Dieter Baumann ,  Rolf-Hartmuth Fischer ,  Eberhard Fuchs ,  Johann-Peter Melder ,  Frank Ohlbach

Inventor： Peter Bassler ,  Dieter Baumann ,  Rolf-Hartmuth Fischer ,  Eberhard Fuchs ,  Johann-Peter Melder ,  Frank Ohlbach

IPC: C07D20102

CPC classification number: C07D201/08 ,  C07D201/16

Abstract: A process for the preparation of caprolactam is provided, wherein a) a mixture (I) containing 6-aminocapronitrile and water is reacted in the liquid phase, in the presence of a catalyst, to give a mixture (II) containing caprolactam, ammonia, water, high-boiling components and low-boiling components, b) ammonia is then removed from the mixture (II) to give a mixture (III) containing caprolactam, water, high-boiling components and low-boiling components, c) water is then removed from the mixture (III) to give a mixture (IV) containing caprolactam, high-boiling components and low-boiling components, and d) a solid (V) containing caprolactam is then obtained from the mixture (IV) by crystallization, the proportion by weight of caprolactam in the solid (V) being greater than in the mixture (IV).

Abstract translation: 提供了制备己内酰胺的方法，其中a）含有6-氨基己腈和水的混合物（I）在液相中在催化剂存在下反应，得到含有己内酰胺，氨，水的混合物（II） ，高沸点组分和低沸点组分，b）然后从混合物（II）中除去氨，得到含有己内酰胺，水，高沸点组分和低沸点组分的混合物（III），c）然后将水 从混合物（III）中除去，得到含有己内酰胺，高沸点组分和低沸点组分的混合物（IV），然后通过结晶从混合物（IV）获得含有己内酰胺的固体（V），比例 的固体（V）中的己内酰胺的量大于混合物（IV）中的。

公开(公告)号：US06663844B1

公开(公告)日：2003-12-16

申请号：US09486488

申请日：2000-02-29

Applicant: Eberhard Fuchs ,  Klemens Flick

Inventor： Eberhard Fuchs ,  Klemens Flick

IPC: C01G2307

CPC classification number: B01J21/063 ,  B01J37/06 ,  C07D201/08

Abstract: Shaped materials useful as catalyst for preparing cyclic lactams by reacting aminocarbonitriles with water in the liquid phase in a fixed bed reactor and which have no soluble constituents under the reaction conditions, comprising pyrogenic titanium dioxide as essential constituent, these compositions being obtainable by shaping the pyrogenic titanium dioxide into shaped articles and, before or after the shaping, treating the pyrogenic titanium dioxide with from 0.1 to 30% by weight, based on the pyrogenic titanium dioxide, of an acid in which pyrogenic titanium dioxide is sparingly soluble.

Abstract translation: 成型材料可用作制备环状内酰胺的催化剂，其通过在固定床反应器中使氨基碳腈与液相中的水反应，并且在反应条件下不含可溶性成分，其包含热解二氧化钛作为必要组分，这些组合物可通过将热解法 二氧化钛成型制品，并且在成形之前或之后，以热解二氧化钛为基准，以热解二氧化钛为基准，以热解二氧化钛微溶于其中的酸为基础，以0.1至30重量％的量处理热解二氧化钛。

公开(公告)号：US06353101B1

公开(公告)日：2002-03-05

申请号：US09555606

申请日：2000-05-31

Applicant: Matthias Eiermann ,  Thomas Narbeshuber

Inventor： Matthias Eiermann ,  Thomas Narbeshuber

IPC: C07D20108

CPC classification number: B01J23/007 ,  C07D201/08

Abstract: The invention relates to a process for preparing lactams by cyclizing hydrolysis of amino nitriles with water in the gas phase on catalysts which comprise oxides or mixed oxides of the metals of groups 3, 4, 5, 13 and/or 14 of the Periodic Table, where appropriate in addition a metal oxide of groups 6, 7, 8, 9 and/or 10, and further comprise a phosphate, carbonate, silicate, arsenite, arsenate, antimonite, antimonate and/or nitrate of said metals and/or, if metal oxides of groups 6, 7, 8, 9 or 10 are present, a sulfate of the abovementioned metals.

Abstract translation: 本发明涉及一种制备内酰胺的方法，该方法通过在气相中用水环化水解氨基腈，在包含周期表第3,4,5,13和/或14族金属的氧化物或混合氧化物的催化剂上， 另外还可以含有第6,7,8,9和/或10族金属氧化物，并且还包含所述金属的磷酸盐，碳酸盐，硅酸盐，亚砷酸盐，砷酸盐，锑酸盐，锑酸盐和/或硝酸盐和/或如果 存在第6,7,8,9或10族的金属氧化物，是上述金属的硫酸盐。

公开(公告)号：US20020007058A1

公开(公告)日：2002-01-17

申请号：US09795706

申请日：2001-03-01

Inventor： Robert Pestman ,  Lambertus H.W.M. Van Lieshout

IPC: C07D223/10 ,  C07C229/08

CPC classification number: C07C227/08 ,  C07C231/14 ,  C07D201/08 ,  Y02P20/52

Abstract: Process for preparing an aqueous mixture of null-caprolactam and 6-aminocaproic acid and/or 6-aminocaproamide which involves, as the reductive amination step, contacting 5-formylvaleric acid and/or an alkyl 5-formylvalerate in water as solvent with hydrogen and an excess of ammonia in the presence of a ruthenium on carrier, as a catalyst, wherein the carrier is titanium oxide, zirconium oxide, graphite or carbon and the catalyst also contains at least one of the metals of group 8-11, or a compound of these metals. The aqueous mixture can be used to prepare null-caprolactam.

Abstract translation: 制备ε-己内酰胺和6-氨基己酸和/或6-氨基己酰胺的水性混合物的方法，其涉及作为还原胺化步骤，将5-甲酰基戊酸和/或作为溶剂的5-甲酰基戊酸烷基酯与氢气和/ 在载体上的钌存在下的过量氨，作为催化剂，其中载体是氧化钛，氧化锆，石墨或碳，并且催化剂还含有至少一种第8-11族的金属或化合物 的这些金属。 含水混合物可用于制备ε-己内酰胺。

公开(公告)号：US20020004609A1

公开(公告)日：2002-01-10

申请号：US09886215

申请日：2001-06-22

Applicant: Mitsubishi Chemical Corporation

Inventor： Masaru Fujii ,  Tohru Setoyama

IPC: C07C051/16 ,  C07C051/245

CPC classification number: C07D201/08 ,  B01J29/061 ,  B01J29/072 ,  B01J29/14 ,  C07C51/313 ,  Y02P20/588 ,  C07C59/147 ,  C07C55/14

Abstract: A process of producing an aliphatic aldehyde-acid (e.g., adipaldehyde-acid) and/or an aliphatic dicarboxylic acid (e.g., adipic acid) comprising oxidizing a cyclic ketone (e.g., cyclohexanone) with molecular oxygen in the presence of a fixed catalyst which comprises a composite of a carrier and at least one metal element belonging to the groups 4 to 11 of the Periodic Table supported on the carrier and has an acid amount of 0.06 mmol/g or more per unit weight of the carrier.

Abstract translation: 一种生产脂肪族醛酸（例如己二酸 - 酸）和/或脂族二羧酸（例如己二酸）的方法，包括在固定催化剂存在下用分子氧氧化环酮（例如环己酮） 包括载体和属于载体上的元素周期表第4至11族的至少一种金属元素的复合物，并且每单位重量载体的酸量为0.06mmol / g以上。

公开(公告)号：US06218535B1

公开(公告)日：2001-04-17

申请号：US09486642

申请日：2000-02-29

Applicant: Eberhard Fuchs ,  Klemens Flick

Inventor： Eberhard Fuchs ,  Klemens Flick

IPC: C07D20108

CPC classification number: C07D201/08 ,  B01J37/06 ,  C07D223/10 ,  Y02P20/52

Abstract: Cyclic lactams are prepared by reacting aminocarbonitriles with water in the liquid phase in a fixed bed reactor in the presence of a catalyst which comprises a catalytically active oxide, which has no soluble constituents under the reaction conditions and which consists of shaped articles obtainable by shaping the oxide into shaped articles and, before or after said shaping, treating the oxide with from 0.1 to 30% by weight, based on the oxide, of an acid in which the oxide is sparingly soluble.

Abstract translation: 环状内酰胺通过在固定床反应器中在液相存在下在液相中与水反应来制备，所述催化剂包含催化活性氧化物，所述催化活性氧化物在反应条件下不具有可溶性组分，并且可由成形制品 氧化物变成成型制品，并且在所述成形之前或之后，以0.1-30重量％的氧化物处理氧化物，其中氧化物微溶于其中的酸。

公开(公告)号：US06191274B1

公开(公告)日：2001-02-20

申请号：US09134756

申请日：1998-08-17

Applicant: Rudolf P. M. Guit ,  Yvonne H. Frentzen

Inventor： Rudolf P. M. Guit ,  Yvonne H. Frentzen

IPC: C07D20116

CPC classification number: C07D201/08 ,  C07D201/16

Abstract: Process to separate &egr;-caprolactam from an aqueous mixture containing &egr;-caprolactam and at least 0.5 wt % oligomers, wherein the separation is performed by extraction using an organic extraction agent. The aqueous mixture may be obtained in a process to prepare &egr;-caprolactam starting from 6-aminocapronitrile or in a process to prepare &egr;-caprolactam starting from 6-aminocaproic acid.

Abstract translation: 从含有ε-己内酰胺和至少0.5wt％低聚物的含水混合物中分离ε-己内酰胺的方法，其中通过使用有机萃取剂萃取进行分离。 含水混合物可以在从6-氨基己腈开始制备ε-己内酰胺或从6-氨基己酸开始制备ε-己内酰胺的方法中获得。

公开(公告)号：US6077955A

公开(公告)日：2000-06-20

申请号：US108728

申请日：1998-07-01

Applicant: Robert Di Cosimo ,  Robert Donald Fallon ,  John Edward Gavagan ,  Frank Edward Herkes

Inventor： Robert Di Cosimo ,  Robert Donald Fallon ,  John Edward Gavagan ,  Frank Edward Herkes

IPC: C07C255/19 ,  C07C255/23 ,  C07D201/08 ,  C07D207/26 ,  C07D211/76 ,  C07D223/10 ,  C12N9/78 ,  C12N9/88 ,  C12P13/00 ,  C12P17/10 ,  C07D211/60 ,  C07D207/00

CPC classification number: C07D211/76 ,  C07C255/19 ,  C07C255/23 ,  C07D201/08 ,  C07D207/26 ,  C07D223/10 ,  C12N9/78 ,  C12N9/88 ,  C12P13/002 ,  C12P13/02 ,  C12P17/10 ,  C12R1/01 ,  Y02P20/52

Abstract: A process for the preparation of five-membered or six-membered ring lactams from aliphatic .alpha.,.omega.-dinitriles has been developed. In the process an aliphatic .alpha.,.omega.-dinitrile is first converted to an ammonium salt of an .omega.-nitrilecarboxylic acid in aqueous solution using a catalyst having an aliphatic nitrilase (EC 3.5.5.7) activity, or a combination of nitrile hydratase (EC 4.2.1.84) and amidase (EC 3.5.1.4) activities. The ammonium salt of the .omega.-nitrilecarboxylic acid is then converted directly to the corresponding lactam by hydrogenation in aqueous solution, without isolation of the intermediate .omega.-nitrilecarboxylic acid or .omega.-aminocarboxylic acid. When the aliphatic .alpha.,.omega.-dinitrile is also unsymmetrically substituted at the .alpha.-carbon atom, the nitrilase produces the .omega.-nitrilecarboxylic acid ammonium salt resulting from hydrolysis of the .omega.-nitrile group with greater than 98% regioselectivity, thereby producing only one of the two possible lactam products during the subsequent hydrogenation. A heat-treatment process to select for desirable regioselective nitrilase or nitrile hydratase activities while destroying undesirable activities is also provided.

Abstract translation: 已经开发了从脂肪族α，ω-二腈制备五元或六元环内酰胺的方法。 在该方法中，使用具有脂族腈水解酶（EC 3.5.5.7）活性的催化剂或腈水合酶（EC 4.2）的组合，首先将脂族α，ω-二腈转化为ω-二硝基甲酸的铵盐 .1.84）和酰胺酶（EC 3.5.1.4）活性。 然后通过在水溶液中氢化将ω-二硝基羧酸的铵盐直接转化成相应的内酰胺，而不分离中间体ω-二硝基甲酸或ω-氨基羧酸。 当脂肪族α，ω-二腈在α-碳原子处也不对称取代时，腈水解酶产生由ω-腈基水解产生的ω-亚硝基羧酸铵盐，其具有大于98％的区域选择性，从而仅产生 在随后氢化期间两种可能的内酰胺产物。 还提供了在破坏不期望的活性的同时选择期望的区域选择性腈水解酶或腈水合酶活性的热处理方法。

公开(公告)号：US5908954A

公开(公告)日：1999-06-01

申请号：US108445

申请日：1998-07-01

Applicant: Robert Di Cosimo ,  Robert Donald Fallon ,  John Edward Gavagan ,  Frank Edward Herkes

Inventor： Robert Di Cosimo ,  Robert Donald Fallon ,  John Edward Gavagan ,  Frank Edward Herkes

IPC: C07C255/19 ,  C07C255/23 ,  C07D201/08 ,  C07D207/26 ,  C07D211/76 ,  C07D223/10 ,  C12N9/78 ,  C12N9/88 ,  C12P13/00 ,  C12P17/10 ,  C07C255/03 ,  C12P17/12

CPC classification number: C07D211/76 ,  C07C255/19 ,  C07C255/23 ,  C07D201/08 ,  C07D207/26 ,  C07D223/10 ,  C12N9/78 ,  C12N9/88 ,  C12P13/002 ,  C12P13/02 ,  C12P17/10 ,  C12R1/01 ,  Y02P20/52

Abstract: A process for the preparation of five-membered or six-membered ring lactams from aliphatic .alpha.,.omega.-dinitriles has been developed. In the process an aliphatic .alpha.,.omega.-dinitrile is first converted to an ammonium salt of an .omega.-nitrile-carboxylic acid in aqueous solution using a catalyst having an aliphatic nitrilase (EC 3.5.5.7) activity, or a combination of nitrile hydratase (EC 4.2.1.84) and arnidase (EC 3.5.1.4) activities. The ammonium salt of the .omega.-nitrilecarboxylic acid is then converted directly to the corresponding lactam by hydrogenation in aqueous solution, without isolation of the intermediate .omega.-nitrilecarboxylic acid or .omega.-aminocarboxylic acid. When the aliphatic .alpha.,.omega.-dinitrile is also unsymmetrically substituted at the .alpha.-carbon atom, the nitrilase produces the .omega.-nitrilecarboxylic acid ammonium salt resulting from hydrolysis of the .omega.-nitrile group with greater than 98% regioselectivity, thereby producing only one of the two possible lactam products during the subsequent hydrogenation. A heat-treatment process to select for desirable regioselective nitrilase or nitrile hydratase activities while destroying undesirable activities is also provided.

Abstract translation: 已经开发了从脂肪族α，ω-二腈制备五元或六元环内酰胺的方法。 在该方法中，首先使用具有脂族腈水解酶（EC 3.5.5.7）活性的催化剂或腈水合酶的组合（在水溶液中将ω-腈 - 羧酸的铵盐转化为ω-腈 - 羧酸的铵盐， EC 4.2.1.84）和arnidase（EC 3.5.1.4）活动。 然后通过在水溶液中氢化将ω-二硝基羧酸的铵盐直接转化成相应的内酰胺，而不分离中间体ω-二硝基甲酸或ω-氨基羧酸。 当脂肪族α，ω-二腈在α-碳原子处也不对称取代时，腈水解酶产生由ω-腈基水解产生的ω-亚硝基羧酸铵盐，其具有大于98％的区域选择性，从而仅产生 在随后氢化期间两种可能的内酰胺产物。 还提供了在破坏不期望的活性的同时选择期望的区域选择性腈水解酶或腈水合酶活性的热处理方法。