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WO 2012/067711 Al 24 May 2012 (24.05.2012) P O P C T

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WO 2012/067711 Al 24 May 2012 (24.05.2012) P O P C T (12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (10) International Publication Number (43) International Publication Date WO 2012/067711 Al 24 May 2012 (24.05.2012) P O P C T (51) International Patent Classification: AO, AT, AU, AZ, BA, BB, BG, BH, BR, BW, BY, BZ, C07C 37/08 (2006.01) CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT, HN, (21) International Application Number: HR, HU, ID, IL, IN, IS, JP, KE, KG, KM, KN, KP, KR, PCT/US201 1/052474 KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME, (22) International Filing Date: MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, 2 1 September 201 1 (21 .09.201 1) OM, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR, (25) Filing Language: English TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW. (26) Publication Language: English (84) Designated States (unless otherwise indicated, for every (30) Priority Data: kind of regional protection available): ARIPO (BW, GH, 61/4 14,042 16 November 20 10 ( 16.11.20 10) US GM, KE, LR, LS, MW, MZ, NA, SD, SL, SZ, TZ, UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, (71) Applicant (for all designated States except US): EXXON¬ TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK, MOBIL CHEMICAL PATENTS INC. [US/US]; A Cor EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV, poration Of The State Of Delaware, 5200 Bayway Drive, MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM, Baytown, TX 77520 (US). TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW, ML, MR, NE, SN, TD, TG). (72) Inventors; and (75) Inventors/Applicants (for US only): WANG, Kun Declarations under Rule 4.17 : [US/US]; 5 Burr Street, Bridgewater, NJ 08807 (US). — as to applicant's entitlement to apply for and be granted a GARCIA, Roberto [US/US]; 109 N. 3rd Street, Apt. 208, patent (Rule 4.1 7(H)) Easton, PA 18042 (US). — as to the applicant's entitlement to claim the priority of the (74) Agents: SULLIVAN, Jamie L. et al; Exxonmobil Chem earlier application (Rule 4.1 7(in)) ical Company, P.O. Box 2149, Baytown, TX 77522-2149 (US). Published: (81) Designated States (unless otherwise indicated, for every — with international search report (Art. 21(3)) kind of national protection available): AE, AG, AL, AM, (54) Title: PROCESS FOR PRODUCING PHENOL Figure 1 so m ■ ■ ■ o ■ o o ■ o o © (57) Abstract: In a process for producing phenol, cyclohexylbenzene is contacted with an oxygen- containing compound in the pres - o ence of a first catalyst under oxidation conditions effective to produce an oxidation product comprising cyclohexylbenzene hydrop - eroxide. At least part of the oxidation product and a polar solvent are then supplied to a cleavage reaction zone, where the said oxid - ation product and the polar solvent are contacted in the presence of a second catalyst under cleavage conditions including a temper - o ature in excess of 50°C effective to convert at least a portion of the cyclohexylbenzene hydroperoxide into phenol and cyclohexan - one. PROCESS FOR PRODUCING PHENOL PRIORITY CLAIM TO RELATED APPLICATIONS [0001] This application claims priority to U.S. Provisional Application Serial No. 61/414,042 filed November 16, 2010, the disclosure of which is fully incorporated herein by reference. FIELD [0002] The present invention relates to a process for producing phenol. BACKGROUND [0003] Phenol is an important product in the chemical industry and is useful in, for example, the production of phenolic resins, bisphenol A, ε-caprolactam, adipic acid, and plasticizers. [0004] Currently, the most common route for the production of phenol is the Hock process via cumene. This is a three-step process in which the first step involves alkylation of benzene with propylene in the presence of an acidic catalyst to produce cumene. The second step is oxidation, preferably aerobic oxidation, of the cumene to the corresponding cumene hydroperoxide. The third step is the cleavage of the cumene hydroperoxide in the presence of heterogeneous or homogeneous catalysts into equimolar amounts of phenol and acetone, a co- product. [0005] It is known that phenol and cyclohexanone can be co-produced by a variation of the Hock process in which cyclohexylbenzene is oxidized to obtain cyclohexylbenzene hydroperoxide and the hydroperoxide is decomposed in the presence of an acid catalyst to the desired phenol and cyclohexanone. Although various methods are available for the production of cyclohexylbenzene, a preferred route is disclosed in U.S. Patent No. 6,037,513, which discloses that cyclohexylbenzene can be produced by contacting benzene with hydrogen in the presence of a bifunctional catalyst comprising a molecular sieve of the MCM-22 family and at least one hydrogenation metal selected from palladium, ruthenium, nickel, cobalt and mixtures thereof. The '513 patent also discloses that the resultant cyclohexylbenzene can be oxidized to the corresponding hydroperoxide which is then decomposed to the desired phenol and cyclohexanone co-product. [0006] In the cumene-based Hock process, dilute cumene hydroperoxide from the cumene oxidation step is first concentrated to greater than 80% by removing unreacted cumene under vacuum, and the resultant concentrate is then sent to the cleavage reactor. In addition to the hazards associated with handling concentrated hydroperoxide, the cleavage poses safety concerns due to the rapid and highly exothermic nature of the reaction. Further, significant amounts of by-products may be generated from the concentrated oxidation products. In practice, therefore, the concentrated cumene hydroperoxide is often diluted with solvents, such as acetone, in order to better manage the heat of reaction and to control by-product formation. For example, U.S. Patent No. 5,254,751 discloses a method of producing phenol and acetone by decomposing cumene hydroperoxide in a non-isothermal manner in the presence of excess acetone whereby the molar ratio of acetone to phenol in a decomposition reactor is from about 1.1: 1 to 1.5:1. [0007] In producing phenol from cyclohexylbenzene, the problems are different. Firstly, oxidation of cyclohexylbenzene to cyclohexylbenzene hydroperoxide is much more difficult than oxidation of cumene and requires elevated temperatures, e.g., 90°C or higher. As a result, the cyclohexylbenzene oxidation effluent is also generally at elevated temperatures so that cooling this stream back to ambient temperature would incur additional operating cost. Also, in view of the high boiling point of cyclohexylbenzene, concentration of the cyclohexylbenzene hydroperoxide by evaporation of the unreacted cyclohexylbenzene is difficult and can lead to unwanted decomposition of the hydroperoxide. Thus, with cyclohexylbenzene hydroperoxide cleavage, the feed contains about 80% hydrocarbon and has very different solubility for the cleavage catalyst, typically sulfuric acid. Consequently, the cleavage products for cyclohexylbenzene hydroperoxide generally contain about 20% polar components which significantly affects the cleavage rate. In addition, the cleavage chemistry for cyclohexylbenzene hydroperoxide is much more complicated than that for cumene hydroperoxide, particularly since more routes for by-product formation exist with cyclohexylbenzene hydroperoxide cleavage. In addition, cyclohexanone is much more prone to acid-catalyzed aldol condensation reactions than acetone so that significant yield loss is possible unless the cyclohexylbenzene hydroperoxide cleavage is closely controlled. [0008] Research has now shown that cyclohexylbenzene can be converted into phenol and cyclohexanone in high yield by oxidizing the cyclohexylbenzene in the presence of a catalyst, such as N-hydroxyphthalimide (NHPI), and then, optionally without concentrating the oxidation product or removing the NHPI catalyst, cleaving the resultant hydroperoxide in the presence of a polar solvent, such as acetone, at a temperature in excess of 50°C. [0009] U.S. Patent No. 3,959,381 discloses a method of producing phenol and cyclohexanone by contacting cyclohexylbenzene, preferably in the presence of a member selected from the group consisting of cumene and cumene hydroperoxide, with an oxygen containing gas to form 1-phenylcyclohexyl hydroperoxide containing intermediate product, optionally purifying said intermediate, contacting the 1-phenylcyclohexyl hydroperoxide intermediate product with an acid cleavage catalyst in the presence of an alkanone of from 3 to 6 carbons at a temperature of 20°C to 50°C, and recovering the formed phenol and cyclohexanone. The oxidation is conducted in the absence of a catalyst. [0010] U.S. Patent No. 4,480,141 discloses a process in which secondary alkyl-substituted hydroperoxides, such as cyclohexylbenzene hydroperoxide, are cleaved to phenols and ketones by contacting the secondary alkyl-substituted benzene hydroperoxide with boron phosphate, at a temperature of about 20°C to 200°C. The cleavage reaction can be carried out in the presence of a solvent, such as acetone and methylethyl ketone. [0011] U.S. Patent No. 4,487,970 discloses a process in which secondary-alkyl substituted benzene hydroperoxides, such as cyclohexylbenzene hydroperoxide, are cleaved to form phenols and ketones by contacting the secondary-alkyl substituted benzene hydroperoxide with a catalyst consisting essentially of about 3:1 to 1:10 by weight of SbFs and graphite in the presence of an aromatic or ketone solvent
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