公开(公告)号：US08309714B2

公开(公告)日：2012-11-13

申请号：US12744675

申请日：2008-11-19

Applicant: Junichi Kugimoto ,  Joji Kawai ,  Hideo Shimomura ,  Ryouta Yasumatsu ,  Nobuhiro Ii

Inventor： Junichi Kugimoto ,  Joji Kawai ,  Hideo Shimomura ,  Ryouta Yasumatsu ,  Nobuhiro Ii

IPC: C07D201/04 ,  C07D225/02

CPC classification number: C07D201/04 ,  C07D225/02 ,  Y02P20/582

Abstract: Provided is a process for efficiently producing laurolactam by simple steps from cyclododecanone and hydroxylamine. This production process comprises the steps of: (a) reacting cyclododecanone with hydroxylamine in an aqueous solution in the presence of an oxime-formation solvent to produce cyclododecanone oxime; (b) separating the reaction mixture obtained after the oxime-forming step into an oil and an aqueous phases and collecting a solution of cyclododecanone oxime of the oil phase; (c) removing a part or all of the oxime-formation solvent and dissolved water from the solution of cyclododecanone oxime which is collected as an oil phase in the oil/aqueous phase separation step, whereby preparing a solution containing a rearrangement solvent to be used in a rearrangement reaction in a later step and the cyclododecanone oxime; (d) producing laurolactam from cyclododecanone oxime by rearrangement reaction using an aromatic-ring containing compound as a rearrangement catalyst; and (e) separating and removing the rearrangement solvent and the rearrangement catalyst from the reaction mixture after the rearrangement step, and purifying the laurolactam.

Abstract translation: 提供一种通过简单的步骤从环十二酮和羟胺有效地生产十二内酰胺的方法。 该制备方法包括以下步骤：（a）在肟形成溶剂存在下，使环十二酮与羟胺在水溶液中反应，生成环十二烷酮肟; （b）将在肟形成步骤后获得的反应混合物分离成油相和水相，并收集油相的环十二烷酮肟溶液; （c）从油/水相分离步骤中以油相收集的环十二烷酮肟溶液中除去部分或全部肟形成溶剂和溶解的水，由此制备含有使用的重排溶剂的溶液 在后续步骤中的重排反应和环十二酮肟; （d）使用含芳环的化合物作为重排催化剂，通过重排反应从环十二酮肟生产月桂内酰胺; 和（e）在重排步骤之后从反应混合物中分离和除去重排溶剂和重排催化剂，并纯化月桂内酰胺。

公开(公告)号：US08212028B2

公开(公告)日：2012-07-03

申请号：US12543022

申请日：2009-08-18

Applicant: Tatsuya Okubo ,  Yuki Suzuki ,  Tsuyoshi Matsushita ,  Tatsuya Suzuki

Inventor： Tatsuya Okubo ,  Yuki Suzuki ,  Tsuyoshi Matsushita ,  Tatsuya Suzuki

IPC: C07D201/04

CPC classification number: C07D201/04 ,  C01B37/02 ,  C01B39/36 ,  C01B39/40 ,  Y02P20/52

Abstract: The present invention provides a method which can produce ε-caprolactam with a good selectivity by reacting cyclohexanone oxime with a good conversion in a vapor phase Beckmann rearrangement reaction. Disclosed is a method for producing ε-caprolactam, which comprises performing a vapor phase Beckmann rearrangement reaction of cyclohexanone oxime in the presence of a pentasil type zeolite, wherein the pentasil type zeolite is a zeolite obtained by subjecting a mixture containing a silicon compound, water, and a compound represented by formula (I): [(R1)3N+—(CH2)m—N+(R1)2—(CH2)m—N+(R1)3]·3/n(A)  (I) wherein R1 represents an alkyl group having 1 to 4 carbon atoms, A represents an n-valent anion, m represents an integer of 5 to 7, and n represents an integer of 1 to 3, to a hydrothermal synthesis reaction.

Abstract translation: 本发明提供了一种通过在气相贝克曼重排反应中使环己酮肟与良好的转化率反应，能够以良好的选择性生产“己内酰胺”的方法。 公开了一种生产ε-己内酰胺的方法，其包括在pentasil型沸石存在下进行环己酮肟的气相Beckmann重排反应，其中pentasil型沸石是通过使含有硅化合物的混合物， 水和由式（I）表示的化合物：[（R1）3N + - （CH2）m-N +（R1）2-（CH2）m-N +（R1）3]·3 / n（A） 其中，R1表示碳原子数1〜4的烷基，A表示n价阴离子，m表示5〜7的整数，n表示1〜3的整数。

公开(公告)号：US07238803B2

公开(公告)日：2007-07-03

申请号：US10883822

申请日：2004-07-06

Applicant: Masashi Yokota ,  Yoshinori Kobayashi ,  Masaru Kitamura

Inventor： Masashi Yokota ,  Yoshinori Kobayashi ,  Masaru Kitamura

IPC: C07D201/04

CPC classification number: C07D201/04 ,  Y02P20/52

Abstract: ε-Caprolactam is produced by the method comprising the step of introducing a gas comprising cyclohexanone oxime into a layer of solid catalyst particles through a plurality of holes of a gas diffusion plate so that the solid catalyst particles are brought into contact with the gas, while fluidizing the catalyst layer, wherein the holes have an average diameter of about 3 mm or smaller. In accordance with the production method, ε-caprolactam can be produced from a raw material gas comprising cyclohexanone oxime with a high conversion of cyclohexanone oxime and a high selectivity to ε-caprolactam.

Abstract translation: ε-己内酰胺通过包括以下步骤的方法制备：包括环己酮肟的气体通过气体扩散板的多个孔引入固体催化剂颗粒层中，使得固体催化剂颗粒与气体接触，同时 使催化剂层流化，其中孔的平均直径为约3mm或更小。 根据制造方法，ε-己内酰胺可以由包含环己酮肟的高转化率和对ε-己内酰胺的高选择性的环己酮肟的原料气体制备。

公开(公告)号：US20070149778A1

公开(公告)日：2007-06-28

申请号：US11614726

申请日：2006-12-21

Applicant: Stacey Zones ,  Allen Burton

Inventor： Stacey Zones ,  Allen Burton

IPC: C07D201/04

CPC classification number: C07D201/04 ,  B01J29/035 ,  B01J29/70

Abstract: The present invention relates to new crystalline molecular sieve SSZ-74 prepared using a hexamethylene-1,6-bis-(N-methyl-N-pyrrolidinium) dication as a structure-directing agent, and its use in catalysts for Beckmann rearrangement.

Abstract translation: 本发明涉及使用六亚甲基-1,6-双 - （N-甲基-N-吡咯烷鎓）双键作为结构导向剂制备的新型结晶分子筛SSZ-74及其用于贝克曼重排用催化剂。

公开(公告)号：US07090817B2

公开(公告)日：2006-08-15

申请号：US10483077

申请日：2002-07-11

Applicant: Arno Herald Benneker ,  Johannes A. L. Brouwers ,  Godefridus M. Van Dortmont

Inventor： Arno Herald Benneker ,  Johannes A. L. Brouwers ,  Godefridus M. Van Dortmont

IPC: C01B21/20 ,  C07D201/04

CPC classification number: C01B21/1418 ,  C01B21/1463 ,  C01B21/1472 ,  C01B21/1481

Abstract: The invention relates to a process for the preparation of hydroxylammonium, said process comprising the steps of: a) feeding gaseous hydrogen to a reaction mixture, said reaction mixture comprising an aqueous reaction medium and a gaseous phase; b) catalytically reducing, in said reaction mixture, nitrate or nitrogen oxide with hydrogen to form the hydroxylammonium; c) withdrawing a gas mixture from the reaction mixture, said gas mixture comprising gaseous hydrogen and gaseous non-hydrogen compounds; d) separating at least part of the gaseous non-hydrogen compounds from the gas mixture to obtain a hydrogen-enriched gas; and e) passing the hydrogen-enriched gas to a hydrogenation zone.

Abstract translation: 本发明涉及一种制备羟铵的方法，所述方法包括以下步骤：a）将氢气送入反应混合物中，所述反应混合物包含含水反应介质和气相; b）在所述反应混合物中用氢气还原硝酸盐或氮氧化物以形成羟基铵; c）从反应混合物中取出气体混合物，所述气体混合物包含气态氢气和非氢氢化合物; d）从气体混合物中分离至少部分气态非氢化合物以获得富氢气体; 和e）将富氢气体通入氢化区。

公开(公告)号：US07060645B2

公开(公告)日：2006-06-13

申请号：US11165538

申请日：2005-06-24

Applicant: Masahiro Hoshino ,  Masaru Kitamura ,  Keisuke Sugita

Inventor： Masahiro Hoshino ,  Masaru Kitamura ,  Keisuke Sugita

IPC: B01J29/40 ,  C07D201/04

CPC classification number: C07D201/04 ,  B01J29/035 ,  B01J37/06 ,  B01J2229/38 ,  B01J2229/40 ,  C01B37/02

Abstract: The present invention provides a method for manufacturing a zeolite comprising following steps of: (1): calcining crystals obtained by hydrothermal synthesis reaction of a silicon compound; (2): contact treating a calcined product obtained by the step (1) with an aqueous solution including an amine and/or a quaternary ammonium compound; (3): calcining a treated product obtained by the step (2); and (4): contact treating the calcined product obtained by the step (3) with an aqueous solution including ammonia and/or an ammonium salt. According to the present invention, a method is also provided wherein ε-caprolactam is manufactured by Beckmann rearrangement reaction of cyclohexanone oxime in a gaseous phase in the presence of the zeolite manufactured by the above-described method.

Abstract translation: 本发明提供一种制造沸石的方法，包括以下步骤：（1）：煅烧通过硅化合物的水热合成反应获得的晶体; （2）：用包含胺和/或季铵化合物的水溶液接触步骤（1）得到的煅烧产物; （3）：煅烧通过工序（2）得到的处理物; 和（4）：用包含氨和/或铵盐的水溶液接触处理由步骤（3）获得的煅烧产物。 根据本发明，还提供了一种方法，其中ε-己内酰胺通过在通过上述方法制造的沸石存在下，在气相中通过环己酮肟的贝克曼重排反应制造。

公开(公告)号：US07026474B2

公开(公告)日：2006-04-11

申请号：US11055101

申请日：2005-02-11

Applicant: Keisuke Sugita ,  Masaru Kitamura ,  Masahiro Hoshino

Inventor： Keisuke Sugita ,  Masaru Kitamura ,  Masahiro Hoshino

IPC: C07D201/04

CPC classification number: B01J38/08 ,  B01J29/90 ,  B01J38/12 ,  B01J38/66 ,  C07D201/04 ,  Y02P20/52 ,  Y02P20/584

Abstract: A method for producing ε-caprolactam and a method for reactivating a zeolite catalyst for the production are provided. In the reactivation step, a zeolite catalyst is allowed to contact a gas containing a carboxylic acid, water and a compound selected from ammonia and amines. In accordance with the present invention, the catalytic activities of a zeolite catalyst used for the Beckmann rearrangement reaction of cyclohexanone oxime can be effectively restored. Consequently, ε-caprolactam may be produced with a high production yield for a long period of time by reusing the catalyst by the method described above.

Abstract translation: 提供了制备ε-己内酰胺的方法和用于再生催化剂的方法。 在再活化步骤中，使沸石催化剂与含有羧酸，水和选自氨和胺的化合物的气体接触。 根据本发明，可以有效地恢复用于环己酮肟的贝克曼重排反应的沸石催化剂的催化活性。 因此，通过上述方法重新使用催化剂，可以长期生产ε-己内酰胺。

公开(公告)号：US06946553B2

公开(公告)日：2005-09-20

申请号：US10367701

申请日：2003-02-19

Applicant: Keisuke Sugita ,  Tsuyoshi Matsushita ,  Hiroshi Ichihashi

Inventor： Keisuke Sugita ,  Tsuyoshi Matsushita ,  Hiroshi Ichihashi

IPC: B01J29/035 ,  B01J29/90 ,  B01J38/66 ,  C07D201/04

CPC classification number: B01J29/90 ,  B01J29/035 ,  B01J38/66

Abstract: Improved processes for producing an ε-caprolactam using a solid catalyst and for producing a catalyst which can be used in the production of ε-caprolactam are provided. In the present invention, a solid catalyst such as a zeolite is treated with an aqueous solution containing an ammonia and at least one compound selected from the group consisting of quaternary ammonium compounds and lower alkylamines. In accordance with the present invention, a zeolite having a high catalyst activity and a long lifetime is produced, and a solid catalyst which has been used in the production of ε-caprolactam can be re-activated. In the present invention, by using the thus obtained zeolite and/or the thus activated solid catalyst, an ε-caprolactam is produced in a high yield over the long period of time.

Abstract translation: 提供了使用固体催化剂生产ε-己内酰胺和用于生产可用于生产ε-己内酰胺的催化剂的改进方法。 在本发明中，使用含有氨和至少一种选自季铵化合物和低级烷基胺的化合物的水溶液处理沸石等固体催化剂。 根据本发明，产生具有高催化剂活性和长寿命的沸石，并且可以重新活化用于生产ε-己内酰胺的固体催化剂。 在本发明中，通过使用由此获得的沸石和/或由此活化的固体催化剂，可以长时间以高产率生产ε-己内酰胺。

公开(公告)号：US20040059108A1

公开(公告)日：2004-03-25

申请号：US10251335

申请日：2002-09-21

Inventor： Alan Levy ,  Gregory Cleotelis II ,  James Sawyer ,  Nolan Henrich III ,  Mohammed Loya ,  Matthew Warren ,  Gregory Moore

IPC: C07D201/04 ,  C07C231/00

CPC classification number: C07D201/04

Abstract: Methods are disclosed of producing and purifying at least one amide. In accordance with one of the methods disclosed herein, the at least one amide is produced by providing an organic liquid comprising at least one oxime, providing at least one catalyst, adding the at least one catalyst to the organic liquid to form a rearrangement mass, wherein the rearrangement mass comprises at least one amide, at least one impurity, and the at least one catalyst, and heating the rearrangement mass to a temperature of at least about 115null C. for a period of time in order to sulfonate, break down and/or reduce the concentration of some of the at least one impurity in the rearrangement mass.

Abstract translation: 公开了生产和纯化至少一种酰胺的方法。 根据本文公开的方法之一，通过提供包含至少一种肟的有机液体来提供至少一种酰胺，提供至少一种催化剂，将至少一种催化剂加入到有机液体中以形成重排质量， 其中所述重排质量包含至少一种酰胺，至少一种杂质和所述至少一种催化剂，并且将所述重排质量加热至至少约115℃的温度一段时间以便磺化，分解 和/或降低重排质量中的一些至少一种杂质的浓度。

公开(公告)号：US6051706A

公开(公告)日：2000-04-18

申请号：US309506

申请日：1999-05-11

Applicant: Wolfgang Holderich ,  Georg Philip Heitmann ,  Dietrich Arntz

Inventor： Wolfgang Holderich ,  Georg Philip Heitmann ,  Dietrich Arntz

IPC: C07D201/04 ,  B01J29/70 ,  C07D201/06

CPC classification number: C07D201/06 ,  B01J29/7007 ,  B01J2229/26 ,  B01J2229/42 ,  Y02P20/52

Abstract: A method is disclosed of producing .epsilon.-caprolactam by the Beckmann rearrangement of cyclohexanone oxime using (B) .beta. zeolites as catalyst.

Abstract translation: 公开了使用（B）β沸石作为催化剂的贝克曼重排环己酮肟来生产ε-己内酰胺的方法。