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(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Orga 2 NET International Bureau , i 2 (10) International Publication Number 4) International Pabliation Date ‘ 9 May 2016 (19.0! 2016) ‘ WIPO! PCT Oe (1) International Patent Classification (74) Agent: COHAUSZ & FLORACK; Bleichstr, 14, 40211 €07C 29/20(2006.01)— CO7C 45/82 (2006.01) Dilsseldort (DE), €07C 29/80(2006.01)——_CO7C.49/403 2006.01) i 4 ‘ (81) Designated States (uriess otherwise indicated, for every Seca pecnae cacaeee cea lind of national protection available): AB, AG, AL, AM, 21) International Application Number: AO, AT, AU, AZ, BA, BB, BG, BH, BN. BR, BW, BY, PCT/EP2015,075951 BZ, CA; CH, CL, CN, CO, CR, CU; CZ, DE, DK,'DM, DO, DZ, EC, FE, FG, ES, FI, GB, GD, GE, GH, GM, GT, -5015(05.11 2015 HIN, HR, HU, ID; TL, IN, TR, iS, JP, KE, KG, KN, KP, KR, 6 November 2015 (06.11.2015) Kz" LA. LC, LK, LR, LS, LU, LY, MA, MD, ME,'MG, 25) Filing Language: English MK, MN, MW, MX, MY, MZ, NA, NG, NIL NO, NZ, OM, PA, PE, PG, Pit, PL, PT. QA, RO, RS, RU, RW, SA, SC, (22) International Filing Date: (26) Publication Language: English $b, SF, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN (G4) Priority Data ‘TR,TT, TZ, UA, UG, US, UZ, VC, VN. ZA, ZM, ZW 141924233 10 November 2014 (10.11.2014) EP (84) Designated States (unless otherwise indicated, for every POTEPZOISIO7SUS ae kind of regional protection available): ARIPO (BW, Gil, 39 October 2015 (29.10.2015) EP GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, (71) Applicants: CAP IE BY. INLINE Postsaat 1, NE- TZ, UG, ZM, ZW), Burisian (AM, AZ, BY, KG, KZ, RU, G15 KR Sita (NL), DSMETP-ASSETS BN, [NLL TH, TM), Ewopean (AL, AT, BE, BG, CH, CY, CZ, DE Ta OPN Afr ues DK, FE,ES, FL, FR, GB, GR, HR, HU, IE, iS, IT, LT, LU, LV, MC, Mi, MT, NL, NO, PL, PT, RO, RS, SE, SL SK, (7) Inventors: TINGE, Johan Thomas; P.O. Box 4, NL6100 $M, TR), OAPI (BF, Bl, CF, CG, Cl, CM, GA, GN, GQ, [AA Feht (NL). DAGUENET, Corinne; P.O. Box 4, NL- GW, KM, ML, MR, NE, SN, TD, TG), 6100 AA Echt (NL), VERSCHUREN, Iris; P.O, Box 4, NL-6100 AA Felt (NL). MARTENS, Wilhelmus Rudolf Published: Marfa; P.O. Box 4, NL-6100 AA Fcht (NL). BRANDS, — with international search report (Art. 21(3)) Rocland Wilhelmus Theodorus Maria; P.O, Box 4, NL 6100 AA Feht (NL). KORTE, DE, Robert Jan; P.O. Box: 4, NL-6100 AA Echt (NL), < 5 x S w rg s S e7 absent: Anns sce eonians pees othe detn ad never eosin om pol a yds, Ce eee each yan Spat gaia sare orci etiaeanentten stdoeeeed & rota sven pre pts coin tea tenses en teatro ee © Binnie esue! he ht hen tan af eal pac of seaman wl i ‘Mio sfsjebhcsnons peel ht arlene mas hom O05 sander whe emer Se ee ee eee ee ema wornais (64 Title: PROCESS FOR THE PRODUCTION OF CYCLOHEXANONE FROM PHENOL, 10 15 20 25 30 WO 2016/075047 PCT/EP2015/075951 PROCESS FOR THE PRODUCTION OF CYCLOHEXANONE FROM PHENOL The invention relates to a continuous process for the preparation of cyclohexanone from phenol on an industrial scale and to a chemical plant suitable for carrying out the process according to the invention on an industrial scale. The vast majority of cyclohexanone is consumed in the production of caprolactam, which is an intermediate in the manufacture of nylon 6. Mixtures of cyclohexanone and cyclohexanol are used for the production of adipic acid, which is mainly converted into nylon 6.6. In addition cyclohexanone can be employed as an industrial solvent or as an activator in oxidation reactions. It can also be used as an intermediate for the production of cyclohexanone resins. In the 1930's the production of cyclohexanone started on an industrial scale, in parallel with the commercial production of caprolactam and nylon 6. Ever since the production volume of cyclohexanone has been growing and nowadays the annual production of cyclohexanone is over 6 million tons, By industrial scale is meant a production rate of at least 1,000 kg of cyclohexanone per hour, more preferably at least 5,000 kg of cyclohexanone per hour and most preferably at least 10,000 kg of cyclohexanone per hour. Cyclohexanone is conventionally prepared from phenol by catalytic hydrogenation in a phenol hydrogenation reactor, e.g. using a platinum or a palladium catalyst. The reaction can be carried out in the liquid phase or the vapour phase. [Kirk-Othmer. Encyclopedia of Chemical Technology, e.g. 3rd Edition, Vol. 7 (1979) p. 410-416; |. Dodgson et al. "A low Cost Phenol to Cyclohexanone Process", Chemistry & Industry, 18, December 1989, p. 830-833; or MT. Musser "Cyclohexanol and Cyclohexanone”, Ullmann’s Encyclopedia of Industrial Chemistry (7th Edition, 2007), (hereafter "Musser”) The process for the hydrogenation of phenol to the two major products, cyclohexanone and cyclohexanol, can be described by the following stoichiometric equations: CsHsOH + 2He > Ceti phenol hydrogen cyclohexanone and CoHOH = + = 3H > CcHiOH phenol hydrogen cyclohexanol 10 15 20 25 30 WO 2016/075047 PCT/EP2015/075951 In conventional processes generally a compromise has to be made between the yield of the desired product (cyclohexanone and/or cyclohexanol formed as a percentage of, the phenol feed), and the selectivity of the reaction (cyclohexanone and/or cyclohexanol formed a8 a percentage of phenol that has been converted). As described in the above identified publications several factors play a role herein, including temperature, choice of catalyst, and the hydrogen/phenol feed ratio. A conventional process for the preparation and recovery of cyclohexanone from phenol feedstock is described in Musser or in US 3,305,586. Such a process consists of two or optionally three sections. Cyclohexanone is prepared in a phenol hydrogenation reaction section. In the phenol hydrogenation reaction section a fresh phenol stream is hydrogenated in a vapour phase process or in a liquid phase process. From this phenol hydrogenation reaction section a gaseous purge stream comprising hydrogen and optionally inerts like nitrogen and/or methane, and a phenol hydrogenation reaction section product stream comprising cyclohexanone and cyclohexanol, phenol and side-products are discharged. In a separation and purification section cyclohexanone is separated from the phenol hydrogenation reaction section product stream. Optionally co-produced cyclohexanol is converted to cyclohexanone in a cyclohexanol dehydrogenation reaction section The process for the dehydrogenation of cyclohexanol to cyclohexanone can be described by the following stoichiometric equation: CoHyOH > CoH + Hp cyclohexanol cyclohexanone hydrogen Generally, this endothermic dehydrogenation reaction is performed in the gas phase. Several catalysts can be applied for this dehydrogenation reaction including catalysts based on copper and/or zine, including catalysts comprising CuCrO.2Cu0.2H;0, CuMgO, CuZnO, CuCrO, CuCrMnV and ZnO. The cyclohexanone is typically recovered by a distillation process as a product rich in cyclohexanone (usually very rich 2 90 wt. %) or as an essentially pure product (2 99 wt. %). For the production of high grade nylon, a purity of at least 99.5 wt. % and more preferably at least 99.8 wt. % of cyclohexanone is desired In 2008 Alexandre C. Dimian and Costin Sorin Bildea (Chapter 5: "Phenol Hydrogenation to Cyclohexanone" in "Chemical Process Design: Computer-Aided Case Studies’, 2008, Wiley-VCH Verlag GmbH & Co. KGA, Weinheim, ISBN: 978-3-527-31403-4)

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