公开(公告)号：US5212302A

公开(公告)日：1993-05-18

申请号：US811627

申请日：1991-12-23

Applicant: Masaru Kitamura ,  Hiroshi Ichihashi ,  Hideto Tojima

Inventor： Masaru Kitamura ,  Hiroshi Ichihashi ,  Hideto Tojima

IPC: B01J29/035 ,  B01J29/86 ,  B01J29/87 ,  B01J29/88 ,  B01J29/90 ,  B01J38/12 ,  B01J38/66 ,  C07D201/04

CPC classification number: B01J29/90 ,  B01J29/035 ,  B01J29/86 ,  B01J29/87 ,  B01J29/88 ,  B01J38/12 ,  B01J38/66 ,  C07D201/04 ,  Y02P20/52 ,  Y02P20/584

Abstract: In the production of .epsilon.-caprolactam from cyclohexanon oxime in gaseous phase in the presence of solid catalysts, the catalysts, no matter whether they may have worked, are brought into contact with either aqueous solution of ammonium salts and at least one basic material or ammonia water.

公开(公告)号：US4717769A

公开(公告)日：1988-01-05

申请号：US019851

申请日：1987-02-27

Applicant: Hiroshi Sato ,  Kenichi Hirose ,  Masaru Kitamura ,  Youichi Umada ,  Norio Ishii ,  Hideto Tojima

Inventor： Hiroshi Sato ,  Kenichi Hirose ,  Masaru Kitamura ,  Youichi Umada ,  Norio Ishii ,  Hideto Tojima

IPC: B01J27/00 ,  B01J29/04 ,  B01J29/86 ,  B01J29/87 ,  B01J29/88 ,  B01J29/89 ,  C07B61/00 ,  C07D201/04

CPC classification number: C07D201/04 ,  B01J29/04 ,  Y02P20/52

Abstract: .epsilon.-caprolactam is produced by gas phase catalytic synthesis with high selectivity of lactam wherein cyclohexanone oxime is brought into contact with a crystalline metallo-silicate catalyst having Si/metal atomic ratio is more than 500. The metal moiety in the catalyst is Ga, Fe, B, Zr, Bi, Nb, Zn, Be, Cr, La, Ti, Hf, V and/or Cu.

Abstract translation: ε-己内酰胺通过气相催化合成以内酰胺的高选择性制备，其中环己酮肟与具有Si /金属原子比的结晶金属硅酸盐催化剂接触超过500.催化剂中的金属部分是Ga，Fe ，B，Zr，Bi，Nb，Zn，Be，Cr，La，Ti，Hf，V和/或Cu。

公开(公告)号：US4689412A

公开(公告)日：1987-08-25

申请号：US919466

申请日：1986-10-16

Applicant: Hans Rademacher ,  Heinz-Werner Voges

Inventor： Hans Rademacher ,  Heinz-Werner Voges

IPC: C07D201/04

CPC classification number: C07D201/04

Abstract: The present invention is a process for preparing lactams having 8 to 15 carbon atoms by the Beckmann rearrangement of the corresponding oximes in a solution of an organic solvent by means of 0.5 to 10% by weight referred to the oxime of an acid derivative acting as a catalyst. The anhydrides of organic sulfonic acids or of sulfuric acid half esters or mixed anhydrides of organic sulfonic acid and anhydrides of sulfuric acid half esters are used as the catalysts.

Abstract translation: 本发明是通过相对于肟的Beckmann重排在有机溶剂的溶液中制备具有8至15个碳原子的内酰胺的方法，其中0.5至10重量％，称为肟酸作为 催化剂。 使用有机磺酸或硫酸半酯或硫酸半酯的有机磺酸和酸酐的混合酸酐的酸酐作为催化剂。

公开(公告)号：US4359421A

公开(公告)日：1982-11-16

申请号：US225157

申请日：1981-01-15

Applicant: Weldon K. Bell ,  Clarence D. Chang

Inventor： Weldon K. Bell ,  Clarence D. Chang

IPC: C07D201/04

CPC classification number: C07D201/04

Abstract: Process for preparing caprolactam from cyclohexanone oxime by passing the oxime, preferably dissolved in a solvent, over a zeolite having a SiO.sub.2 /Al.sub.2 O.sub.3 of at least 12 and a Constraint Index of from 1 to 12.

Abstract translation: 通过使优选溶解在溶剂中的肟超过SiO 2 / Al 2 O 3至少为12且约束指数为1至12的沸石，从环己酮肟制备己内酰胺的方法。

公开(公告)号：US4257950A

公开(公告)日：1981-03-24

申请号：US79329

申请日：1979-09-27

Applicant: Peter Horn ,  Otto-Alfred Grosskinsky ,  Richard Thoma ,  Hugo Fuchs

Inventor： Peter Horn ,  Otto-Alfred Grosskinsky ,  Richard Thoma ,  Hugo Fuchs

IPC: C07D201/04

CPC classification number: C07D201/04

Abstract: A process for the continuous preparation of .epsilon.-caprolactam by Beckmann rearrangement of cyclohexanone-oxime, dissolved in a solvent which is inert toward oleum and is immiscible with oleum and water, at an elevated temperature, with removal of the heat of rearrangement by evaporation of the solvent, wherein oleum containing caprolactam is circulated successively through a conveying zone, a mixing zone, a boiling zone and a separating zone, upstream of the conveying zone oleum is added at the rate at which it is consumed, in the mixing zone cyclohexanone-oxime dissolved in solvent is added under turbulent conditions, in the boiling zone the heat of rearrangement is removed in a conventional manner by evaporating the solvent and recycling the condensate, and in the separating zone the reaction mixture is separated into a solvent phase, from which solvent is withdrawn at the rate at which the phase is formed, and a caprolactam-containing oleum phase, which is removed at the rate at which it is formed.

Abstract translation: 通过贝克曼重排环己酮 - 肟连续制备ε-己内酰胺的方法，该方法在升高的温度下溶解在对发烟硫酸是惰性的且与发烟硫酸和水不混溶的溶剂中，通过蒸发除去重排热 将其中含有发烟硫酸的己内酰胺在输送区上游的输送区，混合区，沸点区和分离区连续循环的溶剂以其消耗的速率在混合区中加入环己酮 - 在湍流条件下加入溶解在溶剂中的肟，在沸腾区中，以常规方式通过蒸发溶剂并再循环冷凝物来除去重排热，并且在分离区中将反应混合物分离成溶剂相，从其中 溶剂以形成相的速率被抽出，含己内酰胺的发烟硫酸相以 它是形成的。

公开(公告)号：US3944542A

公开(公告)日：1976-03-16

申请号：US413435

申请日：1973-11-07

Applicant: Abraham H. de Rooij ,  Jan Elmendorp ,  Willem J. Wassen

Inventor： Abraham H. de Rooij ,  Jan Elmendorp ,  Willem J. Wassen

IPC: C07D201/04

CPC classification number: C07D201/04

Abstract: Organic sulfoxides such as dimethylsulfoxide are used in the transformation of alicyclic ketoximes into the corresponding lactams according to the Beckmann rearrangement in the presence of a strong acid cation exchange resin as disclosed. Thus cyclohexanone is dissolved in DMSO and contacted with a sulfonated copolymer of styrene and divinyl benzene to produce caprolactam in a continuous process.

Abstract translation: 在公开的强酸阳离子交换树脂的存在下，有机亚砜如二甲亚砜用于将脂环酮肟转化成相应的内酰胺，根据Beckmann重排。 因此将环己酮溶解在DMSO中并与苯乙烯和二乙烯基苯的磺化共聚物接触以在连续方法中制备己内酰胺。

公开(公告)号：US3914217A

公开(公告)日：1975-10-21

申请号：US52330374

申请日：1974-11-13

Applicant: ALLIED CHEM

Inventor： SMITH JOSEPH A

IPC: C07D201/04

CPC classification number: C07D201/04

Abstract: This invention relates to a process for the production of lactams by catalytic rearrangement of cycloketoximes in the presence of oleum. More specifically the invention relates to improving yields of lactam while reducing undesirable by-product formation by use of three stages of rearrangement with correlated adjustment of reaction conditions in each stage. Critical variables in each stage include acid concentration, free SO3 concentration, percent oxime added, reaction temperature and extent of mixing. Normally, the oxime fed to the process contains up to 6 percent water.

Abstract translation: 本发明涉及在发烟硫酸存在下通过环酮肟催化重排生产内酰胺的方法。 更具体地，本发明涉及通过使用三个阶段的重排与各阶段中的反应条件的相关调整来提高内酰胺的产率，同时减少不期望的副产物形成。 每个阶段的关键变量包括酸浓度，游离SO3浓度，加入的肟百分比，反应温度和混合程度。 通常，喂给该方法的肟含有高达6％的水。

公开(公告)号：US3879380A

公开(公告)日：1975-04-22

申请号：US31363872

申请日：1972-12-11

Applicant: STAMICARBON

Inventor： DE ROOIJ ABRAHAM H ,  GOETTSCH REIJER

IPC: B01D11/04 ,  B01D9/02 ,  C07D201/04 ,  C07D201/16 ,  C07D41/06

CPC classification number: C07D201/16 ,  C07D201/04

Abstract: A process for recovering lactams from a mixture of one or more lactams and sulphuric acid is disclosed, wherein the sulphuric acid is neutralized with ammonia or an ammonium salt to ammonium hydrogen sulfate in the presence of a lactam solvent. The neutralization produces a melt of ammonium hydrogen sulfate and a solution of lactam in the organic solvent, and the melt is readily separated from the solution. The lactam can then be recovered from the organic solvent. The process allows the lactam to be recovered in good yield without producing, as by-product, ammonium sulfate.

Abstract translation: 公开了一种从一种或多种内酰胺和硫酸的混合物中回收内酰胺的方法，其中硫酸在内酰胺溶剂存在下用氨或铵盐中和至硫酸氢铵。 中和产生硫酸氢铵的熔体和内酰胺在有机溶剂中的溶液，并且熔体容易从溶液中分离出来。 然后可以从有机溶剂中回收内酰胺。

公开(公告)号：US3852273A

公开(公告)日：1974-12-03

申请号：US24972772

申请日：1972-05-02

Applicant: STAMICARBON

Inventor： DE ROOIJ A H

IPC: C07D201/04 ,  C07D201/16 ,  C07D41/06

CPC classification number: C07D201/16 ,  C07D201/04

Abstract: A process for preparing and recovering lactams by the so-called Beckmann rearrangement of the corresponding ketoximes in a sulfuric acid medium is disclosed, wherein the mixture of lactam and sulfuric acid medium obtained from the Beckmann rearrangement is mixed with an aqueous solution of ammonium sulfate obtained as a by-product in the synthesis of hydroxylammonium sulfate in the preparation of said ketoximes. The lactam is then extracted from the resulting less acidic solution and the remaining acid solution, comprising an aqueous solution of ammonium hydrogen sulfate, is thermally decomposed to produce recoverable sulphur dioxide. The process of this invention can be used in the production of lactams while avoiding the production of ammonium sulfate byproduct.

Abstract translation: 公开了通过在硫酸介质中相应酮肟的所谓贝克曼重排制备和回收内酰胺的方法，其中将从贝克曼重排得到的内酰胺和硫酸介质的混合物与得到的硫酸铵水溶液混合 作为在制备所述酮肟时合成羟基硫酸铵的副产物。 然后从所得的较少酸性溶液中提取内酰胺，并将包含硫酸氢铵水溶液的剩余酸溶液热分解以产生可回收的二氧化硫。

公开(公告)号：US3833560A

公开(公告)日：1974-09-03

申请号：US17027671

申请日：1971-08-09

Applicant: BAYER AG

Inventor： IMMEL O ,  SCHWARZ H

IPC: B01J21/02 ,  B01J27/24 ,  B01J31/12 ,  B01J37/00 ,  C07D201/04 ,  C07D41/06

CPC classification number: C07D201/04 ,  B01J21/02 ,  B01J27/24 ,  B01J37/00

Abstract: THE PROCESS OF REARRANGING CYCLIC KETOXIMES IN THE GASEOUS PHASE IN THE PRESENCE OF BORIC ACID CATALYST TO THE CORRESPONDING LACTAMS IS IMPROVED BY USING THE BORIC ACID CATALYST WHICH ARE MORE ABRASION RESISTANT BY PARTIALLY NITRIDING THE CATALYST WITH A NITROGEN-CONTAINING MATERIAL E.G. AMMONIA UREA.