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||||||||||||||||| US005312915A United States Patent (19) 11 Patent Number: 5,312,915 Yashima et al. (45) Date of Patent: May 17, 1994 54 PROCESS FOR PRODUCING tion of Carbon Resources, 1992 with our English trans EPSILON-CAPROLACTAM lation, The Society of Polymer Science, Japan. (75) Inventors: Tatsuaki Yashima; Takayuki 64th Autumn Annual Meeting of the Chemical Society Komatsu, both of Tokyo, Japan of Japan, Preliminary Contributions for the Lectures I, Symposium, Chemical Society of Japan, Union Confer 73 Assignee: Sumitomo Chemical Company, ence of Chemistry-relating Societies and Associations. Limited, Osaka, Japan Manuscripts for slide viewers use by K. Miura et all at 21 Appl. No.: 118,721 “Lectures for publishing Research on the Chemical Utilization of Carbon Resources', with our English (22 Filed: Sep. 10, 1993 translation, 1992. 30 Foreign Application Priority Data Manuscripts for slide viewers use by Mr. K. Miura et al Mar. 4, 1993 JP Japan .................................. 5-04384.5 at 64th Autumn Annual Meeting of the Chemical Soci ety of Japan with our English translation. 51) Int. Cl. ............................................ E07D 201/04 52 U.S. Cl. .................................................... 540/536 Primary Examiner-Robert T. Bond 58) Field of Search ......................................... 540/536 Attorney, Agent, or Firm-Cushman, Darby & Cushman 56) References Cited (57) ABSTRACT U.S. PATENT DOCUMENTS e-Caprolactam is produced efficiently with high selec 3,503,958 3/1970 Landis ................................. 540/536 tivity by contacting cyclohexanone oxime in gas phase 4,359,421 l 1/1982 Bell et al. ............................ 540/536 with a solid catalyst which is a crystalline zeolite having 4,709,024 11/1987 Sato et al. ........................... 540/536 a pore size smaller than molecular size of cyclohexa 4,927,924 5/1990 Bell et al. ............................ 540/536 none oxime or a crystalline zeolite having closed pores. OTHER PUBLICATIONS Lectures for publishing Research on Chemical Utiliza 11 Claims, 3 Drawing Sheets U.S. Patent May 17, 1994 Sheet 1 of 3 5,312,915 F. G. OO CONVERSION SELECTIVITY A 5O 8 -CAPROLACTAM CYCLOHEXANONE, CYCLOHEXENONE 1-CYANOPENTANE, i-CYANOPENTENE O IO 2O 3O W/F g-h mo. NFLUENCE OF W/F IN BECKMANN REARRANGEMENT OF CYCLOHEXANONE OX ME CATALYST: HZSM-5 REACTION TEMPERATURE: 32OC F. G. 2 OO SELECTIVITY 5 O O 25O 3OO 35O 4OO REACTION TEMPERATURE C NFLUENCE OF REACTION TEMPERATURE N BECKMANN REARRANGEMENT OF CYCLOHEXANONE OX ME CATALYST : HZSM-5 W/F: O.2gh moti U.S. Patent May 17, 1994 Sheet 2 of 3 5,312,915 F. G. 3 n o E 40 n H-MORDENITE a d C Z O 20 s -H-FERRERITE 3 C o: 2 4. 6 ADSORPTION h ADSORPTION CURVE OF CYCLOHEXANONE OX ME ADSORPTION TEMPERATURE: 2OC 6O p CYCLOHEXANONE OXIME O 4o s Z O O > C Z hO 20 - &-CAPROLACTAM O (f O C ADSORPTION TIME h ADSORPTION CURVE TO ZSM-5 ADSORPTION TEMPERATURE: 2O C U.S. Patent 5,312,915 c=(C):-() G--WSZ 5,312,915 1. 2 a crystalline zeolite having closed pores. When a crys PROCESS FOR PRODUCING talline zeolite having a pore size not smaller than the EPSILON-CAPROLACTAM molecular size of cyclohexanone oxime is used, ring opened compounds such as 1-cyanopentane and 1 BACKGROUND OF THE INVENTION 5 cyanopentene are produced in large amounts as by-pro The present invention relates to a process for produc ducts in addition to cyclic ketones such as cyclohexa ing e-caprolactam and more particularly, to a process none and cyclohexenone and the selectivity for the for producing e-caprolactam from cyclohexanone ox desired e-caprolactam formation lowers. Therefore, the ime, characterized by using a crystalline Zeolite having specific crystalline zeolites as mentioned above which a specific pore size or a crystalline zeolite having closed O selectively bring about the reaction outside the pores pores. are used in the present invention. e-Caprolactam is an important raw material for nylon The crystalline zeolites having a pore size smaller and the like and has, hitherto, been produced by liquid than molecular size of cyclohexanone oxime include, phase Beckmann rearrangement of cyclohexanone for example, ferrierite, A-type zeolite, chabazite, erio oxime using fuming sulfuric acid or concentrated sulfu 15 nite, zeolite p, EU-1 and zeolite 81. Among them, ferri ric acid as a catalyst. erite and A-type zeolite are preferred. Furthermore, the However, this process suffers from the problems such crystalline zeolites having closed pores include, for as need of fuming sulfuric acid in a large amount and example, proton-type crystalline zeolites filled with by-production of ammonium sulfate in a large amount. template and crystalline zeolites having pores in which For solving these problems, it has been proposed to an oxide of magnesium, phosphorus, boron or the like is carry out gas-phase rearrangement using solid catalysts produced by impregnating the zeolites with a com such as crystalline zeolites, for example, ZSM-5 (Japa pound of magnesium, phosphorus, boron or the like. nese Patent Application Kokai Nos. 57-139062 and The proton-type crystalline zeolites filled with template 62-123167). In this case, however, the selectivity for are preferred. e-caprolactam formation and the like are not enough 25 The crystalline zeolites used in the present invention and further improvement in this respect has been de may be converted into H form by subjecting them to manded. ion-exchange with aqueous ammonium chloride, dilute Under the circumstances, in order to find a further hydrochloric acid or the like or they may be converted improved process for producing e-caprolactam, the into polyvalent metalion exchanged-form by subjecting inventors have conducted intensive research on crystal 30 line zeolites as catalysts. As a result, it has been found them to ion-exchange with an aqueous solution contain that cyclohexanone oxime adsorbed into the pores of ing alkaline earth metal ions or lanthanoid metal ions the zeolites brings about side reaction to cause reduc such as Ca2+, Mg2+, Sr2+, Ba2+, La3+ and Ce3+. tion in the selectivity and it has been further found that Gas phase catalytic method in a fixed bed or fluidized the selectivity for e-caprolactam formation is remark 35 bed is generally used for reaction of cyclohexanone ably improved by using crystalline zeolites having a oxime. When a fixed bed is used, the starting material specific pore size or crystalline zeolites having closed cyclohexanone oxime is vaporized and then is brought into contact with the catalyst bed. When a fluidized bed pores. is used, cyclohexanone oxime may be directly intro SUMMARY OF THE INVENTION 40 duced into the catalyst bed without vaporization. That is, the present invention provides a superior Furthermore, the reaction can also be carried out in process for producing e-caprolactam by contacting the presence of a gas which is inert to the reaction. cyclohexanone oxime in gas phase with a solid catalyst, Examples of such gas are helium, nitrogen, carbon diox characterized in that a crystalline zeolite having a pore ide, benzene, toluene and cyclohexane. size smaller than the molecular size of cyclohexanone 45 Reaction temperature is usually 250-500° C., prefer oxime or a crystalline zeolite having closed pores is ably 300-450° C. used as the solid catalyst. The space velocity of the starting material cyclohexa none oxime is usually WHSV = 0.1-40 hr 1 (feeding BRIEF DESCRIPTION OF DRAWINGS speed of cyclohexanone oxime per 1 kg of the catalyst: FIG. 1 is a graph which shows the relations between 50 0.1-40 kg/hr), preferably 0.2-20 hrl, more preferably W/F and conversion, selectivity and yield on HZSM-5. 0.5-10 hr-l. FIG. 2 is a graph which shows the relations between Isolation of e-caprolactam from the reaction mixture reaction temperature and conversion and selectivity on can be effected by usual methods. For example, a reac HZSM-5. tion mixture gas is cooled and condensed and then evap FIG. 3 is a graph which shows the relation between 55 orated, extracted or crystallized to obtain a purified adsorption amount and adsorption time of cyclohexa e-caprolactam. none oxime in various zeolites. Thus, e-caprolactam is produced. According to the FIG. 4 is a graph which shows the relation between present invention, the selectivity for e-caprolactam for adsorption amount and adsorption time e-caprolactam mation can be improved and e-caprolactam can be ef and cyclohexanone oxime in ZSM-5. fectively produced by using a specific zeolite, namely, a FIG. 5 is a suppositive diagram of reaction of cyclo crystalline zeolite having a pore size smaller than mo hexanone oxime in ZSM-5. lecular size of cyclohexanone oxime or a crystalline zeolite having closed pores. DESCRIPTION OF THE INVENTION The present invention is explained by the following The present invention is explained in detail. 65 nonlimiting examples. The present invention is characterized by using as a The beckmann rearrangement reaction was effected solid catalyst a crystalline zeolite having a pore size by packing 0.87 g of powdered zeolite in a quartz glass smaller than molecular size of cyclohexanone oxime or tube of 72 cm in length and 1.7 cm in inner diameter, 5,312,915 3 4. heat treating the zeolite in a He stream at 450° C. for 1 hour, thereafter cooling the zeolite to a given tempera (3) H-borosilicate ZSM-5 type, Si/B =50 (charging ture and then feeding a 15 wt.% cyclohexanone oxime/- ratio), template in the pores was not removed) benzene solution to the tube. A solution comprising 50 g of deionized water and He was used as a carrier gas. Partial pressures were 5 13.5g of sodium carbonate was added dropwise to a 4.15 kPa for cyclohexanone oxime, 35.8 kPa for benzene solution comprising 650 g of deionized water and 60 g and 61.2 kPa for He.
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