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Method for Production of Laurolactam Verfahren Zur Herstellung Von Laurolactam Procédé De Fabrication De Laurolactame

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Method for Production of Laurolactam Verfahren Zur Herstellung Von Laurolactam Procédé De Fabrication De Laurolactame (19) TZZ ¥___T (11) EP 2 223 911 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) Int Cl.: of the grant of the patent: C07D 201/04 (2006.01) C07D 225/02 (2006.01) 24.09.2014 Bulletin 2014/39 C07B 61/00 (2006.01) (21) Application number: 08853278.3 (86) International application number: PCT/JP2008/071044 (22) Date of filing: 19.11.2008 (87) International publication number: WO 2009/069522 (04.06.2009 Gazette 2009/23) (54) METHOD FOR PRODUCTION OF LAUROLACTAM VERFAHREN ZUR HERSTELLUNG VON LAUROLACTAM PROCÉDÉ DE FABRICATION DE LAUROLACTAME (84) Designated Contracting States: • SHIMOMURA, Hideo AT BE BG CH CY CZ DE DK EE ES FI FR GB GR Ube-shi HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT Yamaguchi 755-8633 (JP) RO SE SI SK TR • YASUMATSU, Ryouta Ube-shi (30) Priority: 29.11.2007 JP 2007308746 Yamaguchi 755-8633 (JP) • II, Nobuhiro (43) Date of publication of application: Ube-shi 01.09.2010 Bulletin 2010/35 Yamaguchi 755-8633 (JP) (73) Proprietor: Ube Industries, Ltd. (74) Representative: Cabinet Plasseraud Ube-shi 52, rue de la Victoire Yamaguchi 755-8633 (JP) 75440 Paris Cedex 09 (FR) (72) Inventors: (56) References cited: • KUGIMOTO, Junichi WO-A1-2007/125002 WO-A1-2007/125002 Ube-shi WO-A1-2008/096873 WO-A1-2008/096873 Yamaguchi 755-8633 (JP) GB-A- 1 148 013 JP-A- 2003 081 930 • KAWAI, Joji JP-A- 2003 081 930 JP-A- 2003 321 453 Ube-shi JP-A- 2006 219 470 JP-B1- 43 012 153 Yamaguchi 755-8633 (JP) Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). EP 2 223 911 B1 Printed by Jouve, 75001 PARIS (FR) 1 EP 2 223 911 B1 2 Description Furthermore, since cyclododecanone reacts with con- centrated sulfuric acid to form a byproduct, the oxime- TECHNICAL FIELD forming reaction must be completed for eliminating re- sidual cyclododecanone, butdue to hydrophobicity of iso- [0001] The present invention relates to a process for 5 propylcyclohexane, a mass transfer rate is low in an oil- producing laurolactam from cyclododecanone and hy- water interface, leading to a longer oxime-forming reac- droxylamine by an industrially convenient process. tion. As a whole, the process involves many steps of sep- aration, recovery and recycling of solvents and, there- BACKGROUND ART fore, requires considerably large equipment expenses 10 and energy. [0002] A common industrial process for producing an [0005] Another industrial process is that commercially amide compound involves Beckmann rearrangement of developed by Ube Industries-EMS. This process utilizes a corresponding oxime compound. For example,ε- the fact that cyclohexanone oxime and caprolactam are caprolactam which is industrially useful is produced by good solvents for cyclododecanone oxime and laurol- Beckmann rearrangement of cyclohexanone oxime. Re- 15 actam, respectively (for example, see Patent Reference arrangement catalysts used are generally concentrated 2). Specifically, a mixture of cyclododecanone and cy- sulfuric acid and oleum. Since these strong acids must clohexanone is blended with an aqueous solution of hy- be used in the stoichiometric amounts or more, they form droxylamine to produce oximes. Cyclohexanone oxime a large amount of ammonium sulfate as a byproduct dur- produced has a low melting point and is a good solvent ing neutralization. Although laurolactam, which is a start- 20 for cyclododecanone oxime, so that the reaction can be ing material for Nylon 12, is also produced in a similar conducted at 100 °C or lower and at an ambient pressure. manner, the process is more complex because cyclodo- Furthermore, cyclohexanone oxime is adequately hy- decanone oxime as an intermediate product has a high drophilic for the oxime-forming reaction to quickly pro- meltingpoint. In producing ε-caprolactam, both cyclohex- ceed, and the mixture is transferred to the rearrangement anone oxime and ε-caprolactam have a relatively lower 25 step without residual cyclohexanone or cyclododecan- melting point, so that oxime formation or rearrangement one. A rearrangement catalyst used is concentrated sul- can be conducted in a solvent-free system, but produc- furic acid or oleum. Whereas laurolactam produced has tion of laurolactam requires a reaction solvent. This re- a high melting point, it is highly soluble in caprolactam action solvent must be able to substantially dissolve cy- having a low melting point. Therefore, the reaction can clododecanone oxime and be inert to concentrated sul- 30 be carried out even at a temperature of 100 °C or lower. furic acid or oleum, and therefore the selection of the The resulting rearrangement reaction solution is neutral- solvent is considerably restricted. ized with ammonia water and then extracted with an or- [0003] Only two processes are known for industrially ganic solvent. Caprolactam can be dissolved in water to producing laurolactam from cyclododecanone and an some extent, but is extracted into an organic solvent due aqueous solution of hydroxylamine. One is a process 35 to salting-out effect of ammonium sulfate. Next, a large commercially developed by Degussa Company. This amount of water is added to the solution containing ex- method is as follows. Cyclododecanone is converted into tracted laurolactam and caprolactam, and caprolactam an oxime using isopropylcyclohexane as a solvent, and is extracted into the aqueous phase. From the separated after separating layers, a resulting solution of cyclodo- organic phase, the organic solvent is recovered and lau- decanone oxime in isopropylcyclohexane is slowly add- 40 rolactam is purified by distillation. The aqueous phase is ed to concentrated sulfuric acid at a low temperature to concentrated and after removing impurities, caprolactam prepare a solution of a cyclododecanone oxime sulfate is purified. adduct in sulfuric acid. After separating and recovering [0006] This process is excellent in that laurolactam and isopropylcyclohexane, the residual solution of cyclodo- caprolactam can be produced together. However, as a decanone oxime sulfate adduct in sulfuric acid is heated 45 process for producing laurolactam, it has the following to initiate Beckmann rearrangement of the oxime. After problems; (1) separation and purification of caprolactam the rearrangement reaction, water is added to the system requires large amounts of equipment expenses, resulting to dilute sulfuric acid, and then, the laurolactam produced in low investment efficiency and the process involves op- is extracted with an organic solvent. Here, the extraction erations of low energy efficiency such as concentration solvent may be isopropylcyclohexane or cyclododecan- 50 of an aqueous solution of caprolactam; (2) there is a re- one. The extraction solvent is recovered by distillation striction to a production ratio of laurolactam/caprolactam; from the resulting extraction solution and then laurol- and(3) caprolactamis a low-value-added productin com- actam in the residue is purified by distillation (see, Patent parison with laurolactam and an use efficiency of hydrox- Reference No. 1). ylamine is low. [0004] This process does not generate ammonium sul- 55 [0007] Recently, there have been intensely investigat- fate as a byproduct in the rearrangement reaction step, ed rearrangement catalysts which do not require a large but requires enormously large facilities and energy for amount of sulfuric acid or oleum. As a system containing treating a large amount of waste diluted sulfuric acid. a strong acid, there have been reported a mixture of rhe- 2 3 EP 2 223 911 B1 4 nium peroxide ammonium salt and trifluoromethane sul- removing catalyst and the like. Since it is highly miscible fonic acid (Non-Patent Reference 1), indium triflate (Non- with water, a process for dehydrating materials for rear- Patent Reference 2) and ytterbium triflate (Non-Patent rangement becomes complex. Therefore, for establish- Reference 3). Known methods utilizing a system contain- ing a practically feasible industrial process, solvents and ing an acid and a dehydrating agent include a method of 5 processes must be selected, in consideration of individ- conducting rearrangement reaction using phosphorous ual steps from starting materials to a final product includ- pentoxide or a condensed phosphoric acid compound ing an oxime-forming step. and a fluorine-free sulfonic anhydride or sulfocarboxylic [0011] anhydride in a N,N-disubstituted amide compound as a solvent (Patent References 3 and 4) and a method using 10 Patent Reference 1: Japanese examined patent a zeolite catalyst pretreated with an aqueous acid-con- publication No. S52-033118 (1977-033118). taining solution (Patent Reference 5). As methods that Patent Reference 2: Japanese Laid-open patent use no acids, there have been suggested a method of publication No. H05-4964 (1993-4964). conducting rearrangement reaction in the presence of a Patent Reference 3: Japanese Laid-open patent rhenium compound and a nitrogen-containing heterocy- 15 publication No. 2001-302602. clic compound (PatentReferences 6 and 7) and a method Patent Reference 4: Japanese Laid-open patent of using zinc oxide (Patent Reference 8). Patent Refer- publication No. 2001-302603. ence 9 has disclosed a method of reacting an oxime and Patent Reference 5: Japanese Laid-open patent a carboxylic acid in a carboxylic acid solvent using cya- publication No. 2001-072658. nuric chloride (trichlorotriazine) as a dehydrating agent, 20 Patent Reference 6: Japanese Laid-open patent whereby producing an ester which is then subjected to publication No. H09-301951 (1997-301951). rearrangement reaction. Patent Reference 10 has dis- Patent Reference 7: Japanese Laid-open patent closed a method where an oxime hydrochloride is sub- publication No. H09-301952 (1997-301952). jected to rearrangement using cyanuric chloride (trichlo- Patent Reference 8: Japanese Laid-open patent rotriazine) as an initiator.
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