(12) INTERNATIONAL APPLICATION PUBLISHED UNDER TH (19) World Intellectual Property ANOKA EA 2 “ 4) International Pabliation Date ‘ it ‘April 2013 (11.04.2013) ‘ WIPO! PCT Ozer ie22 1621 E PATENT COOPERATION TREATY (PCT) (1) International Patent Classification (81) Designated States (uriess otherwise indicated, for every CO7C 37/8 (2006.01) CO7C 45/82 (2006.01) ind of national protection available): AE, AG, AL, AM, €07C 37/74,(2006.01)—— CO7C.49/403 2006.01) AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, €07C 377 (2008.01) CO7C 409/14 (2006.01) BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM, C07 39/4 (2006.01) CO7C 2774 2006.01) DO, DZ, EC, FE, FG, ES, FL, GB, GD, GE, GH, GM, GT, '3(2006.01)— CU7C 13/28 2006.01) HIN, HR, HU, 1D, TL, IN, IS, JP, KF, KG, KM, KN) KP, C070 455 s KR, KZ) LA, LC, Lk, IR, LS, LT, LU, LY, MA, MD, en haa usz01280 ME, MG, Mik, MN, MW, MX, MY, MZ, NA, NG, NI PCTIUS20121052876 NX" NZ, OM, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, (22) tmcernational Fiting Date SC, SD, SE, SG, SK, SL, SM, ST, SV. SY, TH, TJ, TM, 29 August 2012(29.08,2012) TN, TR, TE, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, WN, 25) Filing Language: English ees (a) Designated States (unless otherwise indicated, for every (26) Publication Language: English "kindof regional protection availabe): ARIPO (BW, Gl, (64) Priocty Data GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ, GUSH4I37 7 October 2011 (07.10.2011) us UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TI, TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DR. (70) Applicant (forall designated Staves except US): EXNON- EE, ES, FER, GB, GR. HR. HU, IE, iS, If, LT, LU, LV, MOBIL CHEMICAL PATENTS INC [USUS]; ACor MC, Mi, MT, NL, NO, PL, PT, RO, RS, SE, SE SK, SM, poration Of The State Of Delaware, $200 Bayway Drive, TR), OAPI (BE, BJ, CF, CG, Cl, CM, GA. GN, GQ, GW, Baytown, TX 77520-2101 (US). ML, MR, NE, SN, TD, 76) (72) Inventors: a Declarations under Rule 4.17 (75) Inventors! Applicants (or US only): KUECHLER, Keith, «sro applicants enilemens to apply for and be granted a H. [US'US]; 912. Applewood Drive, Friendswood, TX LX jceoppdee 77546 (US). LATTNER, James, R. [USUSI 10 Bay Per (Rule 4.170) (Oaks, La Porte, TX 77571 (US). BECKER, Christopher, — 4s to the applicant's entitlement to claim the priority of the L. [US/US]; 3109 Driffwood Drive, Manhattan, KS 66503. earlier application (Rule 4.174) (ws), Published: (74) Agents: CHEN, Siwen et al; Exxonmobil Chemical Com- pany, Law Technology, P.O, Box 2149, Baytown, TX 77822-2149 (US). with international search report (are 21(3)) (64) Title: PROCESS FOR PRODUCING PHENOL FROM CYCLOHEXYLBENZENE HYDROPEROXIDE Figure 1 (57) Abstract: Ina process for producing pheno, eyclohexylbenzene hydroperoxide is cleaved to produce a cleavage effluent stream ‘comprising phenol and cyclohexanone and at least portion ofthe cleavage eluent stream is fractionated to price a first fraction richer in eyelohexanone than the cleavage effluent stteam portion and a second fraction richer in phenol and depleted in cyelohexan ‘one as compared with said cleavage eluent stream portion. At lest a portion of the second fraction is then contacted with a debyd ogenation catalyst in a dehydrogenation reaction zone under dehydrogenation conditions effective to convert atleast a portion of the eyelohexanone in said second fraction portion into phenol and cyclohexanol In another embodiment, a composition of cyelohexan ‘one (°99 0%) and impurities of methyley-clopentanone, eyelohexenol, eyelohexanedione of hydroxyeyelohex-anone and eyelobes ‘aol is claimed,WO 2013/052216 PCT/US2012/052876 PROCESS FOR PRODUCING PHENOL FROM CYCLOHEXYLBENZENE HYDROPEROXIDE PRIORITY CLAIM [0001] This application claims priority to U.S. Provisional Application Serial No. 61/544,337 filed October 7, 2011, the disclosure of which is fully incorporated herein by reference. FIELD 10002] The present invention relates to a process for producing phenol. BACKGROUND 10 [0003] Phenol is an important product in the chemical industry and is useful in, for example, the production of phenolic resins, bisphenol A, s-caprotactam, adipic acid, and plasticizers [0004] Currently, the most common route for the production of phenol is the Hock process. This is @ three-step process in which the first step involves alkylation of benzene with 18 propylene to produce cumene, followed by oxidation of the cumene to the corresponding hydroperoxide and then cleavage of the hydroperoxide to produce equimolar amounts of phenol and acetone. However, the world demand for phenol is growing more rapidly than that for acetone. In addition, the cost of propylene is likely to increase, due to a developing shortage of propylene. Thus, a process that uses higher alkenes instead of propylene as feed 20 and coproduces higher ketones, rather than acetone, may be an attractive alternative route to the production of phenols, 10005] For example, oxidation of the cyclohexylbenzene (analogous to cumene oxidation) could offer an alternative route for phenol production without the problem of acetone co- production, ‘This altemmative route proceeds through eyctohexylbenzene hydroperoxide, which 25. iscleaved to produce phenol and cyclohexanone in substantially equimolar amounts, [0006] However, one problem in producing phenol by way of the cleavage of cyclohexylbenzene hrydroperuxide is that the cyclohexanone and phenol produce an azeotrupic mixture composed of 28 wi% cyclohexanone and 72 w1% phenol. Thus, one cannot recover all of the eyclohexanone, or any of the phenol, from the cleavage effluent as & saleable produet by simple distillation. Moreover, although cyclohexanone is a valuable product with a growing market, there is currently no large worldwide merchant market for cyclohexanone; most cyclohexanone is made as an intermediate and consumed on the spot. In some cases, therefore,10 20 25 WO 2013/052216 PCT/US2012/052876 it may be desirable to increase the amount of phenol in the product mix from the cleavage of cyclohexylbenzene hydroperoxide or even produce all phenol with no cyclohexanone. 10007} For example, U.S. Published Patent Application No, 2011/0105805 discloses a process for producing phenol by oxidation of eyclohexylbenzene 10 cyclohexylbenzene hydroperoxide followed by cleavage of the cyclohexylbenzene hydroperoxide, in which some oor all of the effluent from the cleavage step is subjected to a selective dehydrogenation step to convert at least a portion of the cyclohexanone in the effluent portion into phenol and hydrogen. Where only part of the cleavage effluent is dehydrogenated, the effluent is initially subjected to at least a first separation step to recover some or alf of the phenol from the effluent, typically so that the effluent stream fed to said dehydrogenation reaction contains less than 50 wt %, for example less than 30 wt %, such as less than 1 wt %, phenol. Additional distillation steps can be used to remove components boiling below 155 °C (as measured at 101 kPa), such as benzene and cyclohexene, and/or components boiling above 185 °C (as measured at 101 kPa), such as 2-pheny! phenol and dipheny! ether, prior to feeding the effluent stream to the dehydrogenation reaction. [0008] One problem with the process proposed in U.S. Published Patent Application No. 20110105805 is that expensive vacuum andjor extractive distillation methods are required to recover the phenol before the remainder of the effluent is fed to the dehydrogenation reaction, ‘To address this problem, the present invention proposes alternative approach to increasing the amount of phenol in the product mix from the cleavage of cyclohexylbenzene hydroperoxide. ‘Thus, in accordance with the invention, cyclohexanone is separated from the cleavage effluent, typically by conventional distillation and preferably to reduce the cyclohexanone content of the effluent to approach the azeotropic amount of 28 wi%. According to market conditions, the cyclohexanone can then be recovered as a usable product or dehydrogenated to produce phenol, whereas the remainder of the cleavage effluent, potentially an azeottopic mixture of phenol and cyclohexanone, is subjected to selective dehydrogenation to convert the cyclohexanone to phenol [0009] Cyclohexanone is typically produced by the oxidation of cyclohexane, or the hydrogenation of phenol, These methods can also generate various contaminants that are Jifficult to separate from the desired produet, and that can render the cyclohexanone product substandard or unusable to downstream processes, for example in the manufscture of caprolactam or adipic acid, or further using those derivatives in the production of one or10 20 25 WO 2013/052216 PCT/US2012/052876 another type of nylon. Such contaminants include butyleyclohexylether, pentyleyclohexane, cyclohexyl acetate, pentanal, valerie acid and butyric acid, [0040] The production of cyclohexanone from cyctohexylbenzene (with phenol as a co- product) is an emerging technology. The production of cyclohexanone from cyclohexylbenzene also produces various contaminants that are difficult to separate from the desired products. However, the nature of those contaminants and the separations involved are significantly different than those involved in the conventional production of cyclohexanone from cyclohexane or phenol. For example, hydrosikylation of benzene produces significant amounts of, inter alia, cyclohexane and lesser amounts of methyleyelopentane, cyclohexene, phenyleyclohexene, and phenyleyelohexyldiene. ‘Similarly, the oxidation of cyclohexylbenzene typically produces peroxide species alien to conventional processes for making cyclohexanone, such as the desired cyclohesyl-t-pheayl-I hydroperoxide (CHBHP), and undesired byproduct hydroperoxides. such as _eyclohexyl-1-phenyl-2-hydroperoxide, cyclohexy!-1-pheny!-3-hydroperoxide and cyclohexyl-t-phenyl-4-hydroperoxide, Finally, the cleavage of these various hydroperoxides produces, as both the product of the undesired hydroperoxides and the undesired byproducts of the desired CHBHP, a wide variety of contaminant species are not produced by the chemistry and technology of the cyclohexane oxidation or phenol hydrogenation processes, such as cyclohexanedione and hydroxyeyclohexanone. SUMMARY [0011] In one aspect, the invention resides in @ process for producing phenol, the process comprising: (a) cleaving cyclohexylbenvene hydroperoxide to produce a cleavage efMluent stream comprising phenol and cyclohexanone; (b) _ fractionating at least a portion of the cleavage effluent stream to produce a first fraction richer in cyclohexanone than said portion of the cleavage effluent stream and a second fraction richer in phenol and depleted in cyclohexanone as compared with said portion of the cleavage effluent stream: and (© contacting at least @ portion of the second fraction with « dehydrogenation catalyst in a dehydrogenation reaction zone under dehydrogenation conditions effective to convert at least a portion of the cyclohexanone in said portion of the second fraction into phenol and eyclohexanol10 20 25 WO 2013/052216 PCT/US2012/052876 10012} Conveniently, the first fraction comprises no more than 1000 ppm of phenol, based upon the total weight of the first fraction, 10013] Conveniently, the weight ratio of phenol to cyclohexanone in said portion of the cleavage effluent stream is less than or equal to 2.57, such as about 0.7 to about 1.5, and the fractionating (b) is effected by simple distillation [0014] Conveniently, the weight ratio of phenol to cyclohexanone in said second fraction is about 2.0 to about 2.5, 10015] Conveniently, the contacting (c) produces (i) @ product stream comprising phenol, cyclohexanol and eyclohexanone; and (ii) a hydrogen stream, 10016] Conveniently, the provess further comprises: (@) recovering a phenol-containing stream from said product stream to leave a residual stream comprising cyclohexanol and cyetohexanone; and (e) contacting at least a portion of the residual stream with a dehydrogenation catalyst in a dehydrogenation reaction zone under dehydrogenation conditions effective to convert at least a portion of the cyclohexanol and cyclohexanone in said portion of the residual stream into phenol and produce (i) a product stream comprising phenol, cyclohexanol and cyclohexanone; and (ii) « hydrogen stream. [0017] In one embodiment, the phenol-containing stream recovered in (d) contains less than 1 wi% of cyclohexanone and cyclohexanol combined, Generally, the weight ratio of phenol to cyclohexanone in said product stream is greater than 2.57 and said phenol-containing stream is recovered from said product stream in (d) by simple distillation. [0018] Conveniently, said portion of the residual stream and said portion of the second fraction are contacted with a dehydrogenation catalyst in the same dehydrogenation reaction zone. [0019] Conveniently, the process further comprises: (£) recycling at least a portion of said further product stream to said recovering (@); and (g) repeating said recovering (d), said contacting (e) and said recycling (f) to convert at least 90 wi% of the cyclohexanone in the second fraction to phenol [0020] In a further aspect, the invention resides in a process for producing phenol from benzene, the process comprising {@) contacting benzene and hydrogen with @ catalyst under hydroalkylation conditions to produce eyclohexylbenzene;WO 2013/052216 PCT/US2012/052876 {b) oxidizing at least @ portion of the eyclohexylbenzene from (a) to produce an oxidation effluent stream — comprising eyelohexylbenzene hydroperoxide and cyelohexylbenzene; (©) cleaving cyclohexybenzene hydroperoxide in at least a portion of said oxidation effluent stream to produce a cleavage effluent steam comprising phenol, cyclohexanone and cyclohexyibenzene; (d) fractionating at feast a portion of the cleavage effluent stream to produce a first, fraction richer in cyclohexanone than said portion of the cleavage effluent stream and a second fraction richer in phenol and depleted in cyclohexanone as compared with said portion of the 10 cleavage efffuont stream; and (©) contacting at feast a portion of the second fraction with a dehydrogenation catalyst ina dehydrogenation reaction zone under dehydrogenation conditions effective to convert at Jeast 4 portion of the cyclohexanone in said portion of the second fraction into phenol and cyclohexanol and produce a product stream comprising phenol, cyctohexano! and 18 cyclohexanone and a hydrogen stream [0021] Conveniently. the process further comprises: (8) removing a third fraction comprising eyclohexylbenzene from at least a portion of the cleavage effluent stream so that said second fraction contains less than 2 wt% cyclohexylbenzene. 20 (0022) Im yet a further aspect, the invention resides in a composition comprising: (a) at least 99 wi% cyclohexanone; (b) 0.1 wppm to 400 wppm of cyclohexanol and (c) 0.1 wppm to 100 wppin of at least one of methyleyctopentenone, eyclohexenol, cyctohexanedione and hydroxyeyciohexanone, wh in the wi% and wppm are based upon the total weight of the composition. Conveniently, the composition comprises less than 1 wppm of one oF more of 25. methyleyclopentenone, methyleyclopentenal, cyclohexenone, cyclohexenol, phenol, butyleyclohexylether, pentyleyclohexane, eycloitexy! acetate, pentanal, valerie acid, and butyric acid. In another embodiment, the composition comprises 0.1 wppm to 1000 ppm of water as determined according to DIN 51777 / Part I, based upon the total weight of the composition.10 20 25 WO 2013/052216 PCT/US2012/052876 BRIEF DESCRIPTION OF THE DRAWINGS [0023] Figure 1 is @ schematic jew of @ simplified process for producing phenol and cyclohexanone from eyclohexylbenzene in accordance with first example of the present invention, [0024] Figure 2 is a schematic view of a more detailed process for producing phenol and cyclohexanone from cyclohexylbenzene in accordance with a second example of the present invention and including additional intermediate purification steps. 10025] Figure 3 is a schematic view of a modified version of the process shown in Figure 2 DETAILED DESCRIPTH 10026] Des of ¢ OF THE EMBODIMENTS ribed herein is a process for produeing phenol and cyclohexanone by eleavage Johexylbenzene hydroperoxide, In the present process, the production of phenol is enhanced by separating cyclohexanone from the cleavage effluent, typically by conventional distillation, to leave an effluent fraction with reduced cyclohexanone content typically approaching the azeotropic amount of 28 wi%, This effluent fraction is then subjected to dehydrogenation to convert at least a portion of the cyclohexanone into phenol and cyclohexanol and produce @ product stream comprising phenol, cyclohexanol and cyclohexanone and a hydrogen stream. Phenol is recovered from this product stream to leave a residual stream which comprises cyclohexanol and cyclohexanone and which can be recycled to the debydrogenation process, By repeating the phenot recovery and dehydrogenation processes, it is possible to convert at least 90 wi% of the cyclohexanone produced in the effluent fraction to phenol. [0027] The cyclohexanone product of the present proces after separation from the cleavage effluent, is of exceptional quality for further processing, in say, caprolactam production, relative to both the conventional cyclohexane oxidation and phenol hydrogenation processes, containing far fewer impurities, with those impurities having @ significantly lower impact on the downstream process steps and the product. [0028] In one preferred embodiment, the present process forms part of an integrated process for producing cyclohexanone and phenol from benzene in which the benzene is initially converted 10 eyclohexylbenzene, conveniently by hydroalkylation, The cyclohexylbenzene is then oxidized to produce eyclohexylbenzene hydroperoxide, which is then subjected to the cleavage, separation and dehydrogenation operations discussed above. ‘The ensuing description will therefore focus on this integrated process,10 15 20 WO 2013/052216 PCT/US2012/052876 Produ in of the Cyclohexyibenzen: [0029] One step of the integrated process starting from benzene, eyclohexylbenzene is produced by reacting the benzene with cyclohexene in the presence of @ catalyst having an alkylation function and under conditions to promote the following reaction CO O-X 10030] The cyclohexene can be supplied to the reaction zone as a separate feed from the benzene, but normally is produced i situ by selective hydrogenation of the benzene in the presence of a hydrogenation component provided on the catalyst having the alkylation function, The bifunctional catalyst is therefore referred to herein as a hydroalkylation catalyst and overall the hydroatkylation reaction proceeds as follows to produce cyclohexytbenzene [0031] Any commercially available benzene feed can be used in the hydroalkylation step, but preferably the benzene has a purity level of at least 99 wt%, Similarly, although the source of hydrogen is not critical, it is generally desirable that the hydrogen is at least 99 wt% pure. 10032} In one embodiment, the total feed to the hydroalkytation step contains less than 1000 ppm, such as less than S00 ppm, for example tess than 100 ppm, water. In various embodiments, the total feed typically contains less than 100 ppm, such as less than 30 ppm, for example less than 3 ppm, sulfisr and less than 10 ppm, such as less than 1 ppm, for example less than 0.1 ppm, nitrogen. [0033] Hydrogen can be supplied to the hydroalkylation step over a wide range of values, but typically is arranged such that the molar ratio of hydrogen to benzene in the hhydroalkylation feed is between about 0.15:1 and about 15:1, such as between about 0.4:1 and about 4:1, for example between about 0.4 and about 0.9:110 15 20 30 WO 2013/052216 PCT/US2012/052876 [0034] in addition to the benzene and hydrogen, a diluent, which is substantially inert under hydroalkylation conditions, may be supplied to the bydroalkylation reaction. Typically the diluent is « hydrocarbon, in which the desired cyctoalkylaromatic product, in this case cyclohexylbenzene, is soluble, such as a straight chain paraffinic hydrocarbon, a branched chain paraffinic hydrocarbon, and/or @ cyclic paraffinic hydrocarbon, Examples of suitable diluents are decane and cyclohexane, Cyclohexane is a particularly attractive dituent since itis ‘an unwanted by-product of the hydroalkylation reaction, 10035] Although the amount of diluent is not narrowly defined, generally the diluent is added in an amount such that the weight ratio of the diluent to the aromatie compound is at least 1:100; for example at least 1: 10, but nu more than 10:1, typically no more than 4:1 10036} The hydroaikylation reaction can be conducted in a wide range of reactor configurations including fixed bed, slurry reactors, and/or catalytic distillation towers. In addition, the hydroalkylation reaction can be conducted in @ single reaction zone or in a plurality of reaction zones, in which at least the hydrogen is introduced to the reaction in stages. Suitable reaction temperatures are between about 100°C and about 400°C, such as between about 125°C and about 250°C, white suitable reaction pressures are between about 100 and about 7,000 kPa, such as between about 500 and about 5,000 kPa, [0037] The catalyst employed in the hydroalkylation seaction is a bifunctional catalyst comprising @ molecular sieve of the MCM-22 family and a hydrogenation metal. The term or “molecular sieve of the 1CM-22 family material” (or “material of the MCM-22 family” MCM-22 family”), as used herein, includes one or more of * molecular sieves made from @ common first degree crystalline building block unit cell, ‘which unit cell has the MWW framework topology. (A unit cell is @ spatial arrangement of atoms which if tied in three-dimensional space describes the crystal structure, Such crystal structures are discussed in the "Atlas of Zeolite Framework Types", Fifth edition, 2001, the entire content of which is incorporated as reference}; + molecular sieves made from a common second degree building block, being a 2- dimensional tiling of such MWW framework topology unit cells, forming a monolayer of cone unit cell thickness, preferably one c-unit cell thickness; ‘+ molecular sieves made from common second degree building blocks, being layers of one ot more than one unit cell thickness, wherein the layer of more than one unit cell thickness is made from stacking, packing, or binding at least two monolayers of one unit cell thickness.15 0 WO 2013/052216 PCT/US2012/052876 ‘The stacking of such second degree building blocks ean be in a regular fashion, an irregular nd fashion, a random fashion, of any combination thereof: © molecular sieves made by any regular or random 2-dimensional or 3-dimensional combination of unit cells having the MWW framework topotogy. 10038} Molecular sieves of MCM-22 family generally have an X-ray diffraction pattern including d-spacing maxima at 12.430.25, 6.90.15, 3.5710.07 and 3.4240.07 Angstrom. The X-ray diffraction data used to characterize the material (b) are obtained by standard techniques using the K-alpha doublet of copper as the incident radiation and a diffractometer equipped with a scintillation counter and associated computer as the collection system, Molecular sieves of MCM-22 family include MCM-22 (described in U.S. Patent No. 4,954,325), PSH-3 (described in U.S. Patent No. 4,439,409), SS: ERB-I (described in European Patent No. 0293032), ITQ-1 (described in U.S. Patent No 6,077,498), 1TQ-2 (deseribed in International Patent Publication No. WO97/17290), MCM-36 (described in U.S. Patent No, 5,250,277), MCM-49 (described in U.S. Patent No, 5,236,575), MCM-S6 (described in U.S. Patent No. 5,362,697}, UZM-8 (described in U.S. Patent No. 6,756,030), and mixtures thereof. Preferably, the molecular sieve is selected from (2) MCM- 49, (b) MCM-56 and (¢) isotypes of MCM-49 and MCM-56, such as ITQ-2. 10039} Any known hydrogenation metal can be employed in the hydroalkylation catalyst, 5 (described in U.S, Patent No. 4,826,667), although suitable metals include palladium, ruthenium, nickel, zinc, tin, and cobalt, with palladium being particularly advantageous, Generally, the amount of hydrogenation metal present in the catalyst is between about 0.05 and about 10 wt %, such as between about 0.1 and about $ wt %, of the catalyst, In one embodiment, where the MCM.-22 family molecular sieve is an aluminosilicate, the amount of hydrogenation metal present is such that the molar ratio of the aluminum in the molecular si 1500, for example from about 75 to about 750, such as from about 100 to about 300. [0040] The hydrogenation metal may be directly supported on the MCM-22 family we to the hydrogenation metal is from about 1.5 to about molecular sieve by, for example, impregnation or ion exchange. However, in a more preferred embodiment, at feast 50 wi%, for example at least 75wi%, and generally substantially all of the hydrogenation metal is supported on an inorganic oxide separate from but composited with the molecular sieve. In particular, itis found that by supporting the hydrogenation metal on the inorganic oxide, the activity of the catalyst and its selectivity to cyclohexylbenzene and dieyclohexylbenzene are increased as compared with an equivalent catalyst in which the hydrogenation metal is supported on the molecular sieve,10 20 25 WO 2013/052216 PCT/US2012/052876 10041] The inorganic oxide employed in such a composite hydroalkylation catalyst is not narrowly defined provided it is stable and inert under the conditions of the hydroalkylation reaction, Suitable inorganic oxides include oxides of Groups 2, 4, 13 and 14 of the Periodic ‘Table of Elements, such as alumina, titania, and/or zirconia, As used herein, the numbering heme for the Periodic Table Groups is as disclosed in Chemical and Engineering News, 63(5), 27 (1985), [0042] ‘The hydrogenation metal is deposited on the inorganic oxide, conveniently by impregnation, before the metal-containing inorganic oxide is composited with said molecular sieve, Typically, the catalyst composite is produced by co-pelletization, in which « mixture of the molecular sieve and the metal-containing inorganic oxide are formed into pellets at high pre re (generally about 350 to about 350,000 kPa), or by co-extrusion, in which a slurry of the molecular sieve and the metal-containing inorganic oxide, optionally together with separate binder, are forced through a die. If necessary, additional hydrogenation metal can subsequently be deposited on the resultant catalyst composite [0043] Suitable binder materials include as inorganic materials such as clay, silica and/or metal oxides. The latter may be cither thetic or naturally occurring substances as well naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Naturally occurring clays which can be used as a binder include those of the montmorillonite and kaolin families, which families include the subbentonites and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite or anauxite, Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid weatment or chemical modification. Suitable metal oxide binders include silica, alumina, zirconia, titania, silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silic titania as well as temary compositions such as silica-alumina-thoria, silica-alumina-zirconia, alumina-magnesia and silica-magnesia-zitconia, [0044] Although the hydroalkylation reaction using an MCM-22 family zeolite catalyst activated by the process described herein is high! effluent from the hydroalkyls by-product. Depending on the amount of this dicyelohexytbenzene, it may be desirable to elective towards cyclohexylbenzene, the jon reaction will inevitably contain some dicyclohexylbenzene either (a) transalkylate the dicyciohexylbenzene with additional benzene or (b) dealkylate the dicyclohexylbenzene to maximize the production of the desired monoalkylated species. -10-WO 2013/052216 PCT/US2012/052876 10045] Transatkylation with additional benzene is typically effected in @ transalkylation reactor, separate from the hydroalkylation reactor, over a suitable transalkylation catalyst, such as a molecular sieve of the MCM-22 family, zeolite beta, MCA -68 (see U.S. Patent No. 6,014,018), zeolite Y and mordenite, The transalkylation reaction is typically conducted under at least partial Liquid phase conditions, which suitably include a temperature of about 100 to about 300°C, a pressure of about $00 to about 3500 kPa, a weight hourly space velocity of about 1 to about 10 hr on total feed, and a benzene/dieyelohexylbenzene weight ratio about of 1:1 to about 5:1 10046] —_Dealkylation or cracking is also typically effected in @ reactor separate from the hydroalkylation reactor, such as a reactive distillation unit, at a temperature of about 150°C to about 5( and a pressure of 15 to 500 psig (200 to 3550 kPa) over an acid catalyst such as an aluminosilicate, an aluminophosphate, a silicoaluminphosphate, amorphous silica-alumina, an acidic clay, a mixed metal oxide, such as WO/ZrO>, phosphoric acid, sulfated zirconia and mixtures thereof. Generally, the acid catalyst includes at least one aluminosilicate, ‘alominophosphate or silicoaluminphosphate of the FAU, AEL, AFT and MWW family. Unlike transalkylation, dealkylation can be conducted in the absence of added benzene, although it may be desirable to add benzene to the dealkylation reaction to reduce coke formation, In this case, the weight ratio of benzene to poly-alkylated aromatic compounds in the feed to the deaikylation reaction is typically is from 0 to about 0.9, such as from about 0.01 to about 0.5 Similarly, although the dealkylation reaction can be conducted in the absence of added hydrogen, hydrogen is generally introduced into the dealkylation reactor to assist in coke reduction. Suitable hydrogen addition rates are such that the molar ratio of hydrogen to poly- alkylated aromatic compound in the total feed to the dealkylation reactor is from about 0.01 to about 10, [0047 Another significant by-product of the hydroalkylation reaction is cyclohexane. Although a Cetich stream comprising eyctohesane and unreacted benzene can be readily removed from the hydroalkylation reaction effluent by distillation, owing to the similarity in the boiling points of benzene and cyclohexane, the Co-tich stream is difficult to further separate by simple distillation, However, some or alf of the Cs-rich stream can be recyeled to the hydroalkylation reactor to provide not only part of the benzene feed but also part of the diluents mentioned above: (0048), In some cases, it may be desirable to supply some of the Cerich stream to a dehydrogenation reaction zone, where the Cy-rich stream is contacted with a dehydrogenation ) fructionating at least @ portion of the cleavage effluent stream to produce (i) a first fraction richer in cyclohexanone than said portion of the cleavage effluent stream; and (ii) a second fraction richer in phenol and depleted in cyclohexanone than said portion of the cleavage effluent stream; and 10 (©) contacting at least @ portion of the second fraction with » dehydrogenation catalyst in a dehydrogenation reaction zone under dehydrogenation conditions effective to convert at least a portion of the cyclohexanone in said portion of the second fraction into phenol and eyclohexanol, 2, ‘The process of claim 1, wherein the first fraction comprises no more than 1000 ppm of 15 phenol, based upon the total weight of the first fraction, 3. The process of claim 1 or claim 2, wherein the weight ratio of phenol to cyclohexanone in said portion of the cleavage effluent stream in (b) is tess than or equal to 2.57. 4, The process of any one of the preceding claims, wherein the weight ratio of phenol to cyclohexanone in seid portion of the cleavage effluent stream in (b) is about 0.7 to about 1.5, 205, The process of claim 3, wherein said fractionating (b) is effected by distillation, 6, The process of any one of the preceding claims, wherein the weight ratio of phenol to cyclohexanone in said second fraction is about 2.0 to about 2, 7. ‘The process of any one of the preceding claims, wherein the contacting (¢) produces (i) 4 product stream comprising phenol, cyclohexanol, and cyclohexanone; and (ii) # hydrogen 25 stream. 8. The process of claim 7, and further comprising: (@) recovering @ phenol-containing stream from said product stream to leave residual stream comprising cyclohexanol and cyclohexanone; and (©) contacting at least « portion of the residual stream with a dehydrogenation 30, catalyst in a dehydrogenation reaction zone under dehydrogenation conditions effective 10 convert at least a portion of the cyclohexanol and cyclohexanone in said portion of the residual stream into phenol and produce (j) a further product stream comprising phenol, cyclohexanone, and cyclohexanol; (ii) and a further hydrogen stream, -39-WO 2013/052216 PCT/US2012/052876 9. The process of claim 8, wherein said phenol-containing stream recovered in (d) contains no more than 1 wt% of cyclohexanone and cyclohexanol combined, the wt% based upon the total weight of the phenol-containing stream, 10. ‘The process of claim 9, wherein the weight ratio of phenol t cyclohexanone in s product s product stream by simple distillation, id ream is greater than 2.57 and said phenol-containing stream is recovered from said 11 The process of claim 8, wherein said portion of the residual stream in (c) and said portion of the second fraction in (b) are contacted with a dehydrogenation catalyst in the same dehydrogenation reaction zone. 10 12. The process of claim 8, and further comprising: (1) recycling at least a portion of said further product stream to said recovering (d); and (e) repeating said recovering (d), said contacting (e) and said recycling (0 to convert at feast 90 wt of the cyclohexanone in said second fraction to phenol, the wi% based 15 upon the total weight of said second fraction. 12. At least one of a phenolic resin, bisphenol A, s-caprolactam, an adipic acid, or a plasticizer produced trom the phenol in the product stream of any one of claims 7-12. 14, At least one of adipic acid, a cyclohexanone resin, a cyclohexanone oxime, caprolactam, or nylon produced trom the cyclohexanone in the first fraction of any one of the 20 preceding claims. 15, The process of any one of the preceding claims, wherein the dehydrogenation catalyst comprises (3) 4 support; (ii) a dehydrogenation component comprising at least one metal or compound thereof selected from Groups 6 to 10 of the Periodic Table of Elements; and (ii) tin or a tin compound, wherein the tin is present in an amount of 0.01 wt% to about 0.25 wt%, the 25 wi% based upon the total weight of the dehydrogenation catalyst. 16, The process of any one of the preceding claims, wherein the dehydrogenation conditi ions comprise a temperature of about 250°C to about S00°C and a pressure of about 100 kPa to about 3550 kPa. 17. A process for producing phenol from benzene, the process comprising 30 (contacting benzene and hydrogen with a hydroalkylation catalyst under bydrosikyletion conditions to produce eyctohexyibenzene; -40-10 20 25 WO 2013/052216 PCT/US2012/052876 (b) oxidizing at least a portion of the eyclohexylbenzene from (a) to produce an oxidation effluent stream — comprising eyelohexylbenzene hydroperoxide and cyelohexylbenzene; {e) cleaving the eyclohexylbenzene hydroperoxide in at least a portion of said oxidation effluent stream to produce a cleavage effluent stream comprising phenol, cyclohexanone, and eyclohexylbenzene; (@)__ fractionating at feast a portion of the cleavage effluent stream to produce a first fraction richer in cyclohexanone than said portion of the cleavage effluent stream and a second fraction richer in phenot and depleted in cyclohexanone as compared with said portion of the cleavage effluent stream; and (©) contacting at feast a portion of the second fraction with a dehydrogenation catalyst in a dehydrogenation reaction zone under dehydrogenation conditions effective to convert at least portion of the cyclohexanone in said portion of the second fraction into phenol and eyclohexenol. 18 The process of claim 17, wherein the weight ratio of phenol to cyclohexanone in said portion of the cleavage effluent stream is less than or equal to 2.57. 19. The process of claim 17 or claim 18, wherein the weight ratio of phenol to cyclohexanone in said second fraction is about 2.0 to about 2.5, 20. The process of any one of claims 17-19, wherein the contacting (c) produces (i) a product stream comprising phenol, cyclohexanol, and cyclohexanone; and (ii) a hydrogen stream. 21. ‘The process of any one of claims 17-20, and further comprising: {0 removing a third fraction comprising eyclohexylbenzene from at least a portion of the cleavage effluent stream so that said second fraction contains less than 2 wi% cyclohexylbenzene, based upon the total weight of the second fraction. 22. The process of claim 20, and further comprising; (g) recovering @ phenol-containing stream from said product stream to leave residual stream depleted in phenol relative to the product stream and comprising cyclohexanol and cyclohexanone; and (h) contacting at feast a portion of the residual stream with a dehydrogenation catalyst in a dehydrogenation reaction zone under dehydrogenation conditions effective to convert at least a portion of the cyclohexanone and cyclohexanol in said portion of the residual -41-10 WO 2013/052216 PCT/US2012/052876 stream into phenol and produce a further product stream comprising phenol, eyclohexanone, and cyclohexanol, and a further hydrogen stream, 23. A cyclohexanone composition compris (A) at least 99.1% of cyclohexanone: {B) 0.1 wppm to 400 wppm of cyclohexanol; and (C) 0.1 wppm to 100 wppm of at least one of methyleyclopentanone, cyctohexenol, cyclohexanedione, and hydroxyeyclohexanone, wherein the wt% and wppm values are based upon the total weight of the composition, 24. The cyclohexanone composition of claim 23, and further comprising 0.1 wppm to 1000 wppm of water as determined according to DIN 51777 / Part 1, based upon the total weight of the composition. 25. The cyclohexanone composition of claim 23 or claim 24, and comprising less than 1 wppm of one or more of methyleyelopentenone, methylcyclopentensl, cyclobexenone, cyclohexenol, phenol, butyleyclohexylether, pentyleyclohexane, cyclohexyl acetate, pentanal, valeric acid, and butyric acid,WO 2013/052216 PCT/US2012/052876 Figure 4 100 410 116 122 128 106 ] 112. ] 134 |WO 2013/052216 PCT/US2012/052876 2/3 200 2 gerade! oe 228 . 2g 216 220 240 an 4 208 bate >| 222 228 234 a2 202 | ae cole aoe pay 82. ea . 240 26 258 262 I 250 284 - . 280 254 248 et J 252WO 2013/052216 PCT/US2012/052876 3/3 Figure 3 8 338 24 58-4 332 220 522) 328 338 386 226 306 Me 380 a 2 364 352 suo + t 342 350 ous be tase 362 Jmened PS aaa . 34 “370 adINTERNATIONAL SEARCH REPORT Trternationel apptoaton Ne PCT/us2012/052876 7 GEASSIIOATON OF SUBVEST WATER. TW. CO7C37/08 -CO/C37/74 —CO7C37/07 —CO7C39/E4 —«CO7C45/53 co7cas/e2 —co7c4g/403 © Co7c4ag/14 —co7C2/74 c07¢13/28 ADD. According to eration Patent Casleaten (PC) otoboth nana claseaton and PC Tin dboureriaton seated (lesoTauton ayer Towed by dasToatono7RBOR) core’ Ear data bane Sons ng is WaT Fea a Tea EPO-Internal, CHEN ABS Data, WPI Data ‘aiegon” | Otatonofdourent wih ndoaten, where appropiate a he eleven passes Rebvart tala Ne x Us 2011/105805 A1 (BUCHANAN JOHN S [US] ET 14 AL) 5 May 2011 (2011-05-05) cited in the application Paragraphs [0006], [0058]; claims 1,4,5 x US 4 621.490 A_(HUDSON PAUL S) 23-25 3. May 1977 (1977-05-03) claim 1; table 1 X,P WO 2012/036818 Al (EXXONMOBIL CHEM PATENTS 23-25 INC [US]; KUECHLER KEITH H [US]; BENITEZ FRANC) 22 March 2012 (2012-03-22) claims 1,8 Farmer document rte nthe sonthuston ot 8%, XX] see pater taney anne. a “ltr decuent publishes ate the rtratona fing date of priy : sitet cerca ecient ct ourentrng tee tel atichinnstindens Gusta cay conse tr “courtier wieh speteegcieer esc SSrosirmen(orsected) ona Ssionsiaher om aecunentt parol meee he tied perio sno “Frommers datecamed © ne emONa rae hulle Fors ascent aber of he same plenty 29 November 2012 07/12/2012 (NE Z2a0 Hen = BL Gsing bho, Steinreiber, JINTERNATIONAL SEARCH REPORT Information on patent family members us 4021490 A WO 2012036818 AL 03-05-1977 22-03-2012 NONE NONE PCT/US2012/052876 Patent document Pubieation Patent family Pubieaton| cotedin seat report ‘ate member) ate US 2011105805 Al 05-05-2011 EP 2346803 Al 27-07-2011 JP 2011525196 A 15-09-2011 KR 20110014240 A 10-02-2011 US 2011105805 Al 05-05-2011 i) 2010024975 Al 04-03-2010 Fan pRT y a ROTH