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(12) United States Patent (10) Patent No.: US 7,579,511 B1 Dakka Et Al

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(12) United States Patent (10) Patent No.: US 7,579,511 B1 Dakka Et Al US007579511B1 (12) United States Patent (10) Patent No.: US 7,579,511 B1 Dakka et al. (45) Date of Patent: Aug. 25, 2009 (54) PROCESS FOR MAKING 6,489.529 B1 12/2002 Cheng et al. CYCLOHEXYLBENZENE FOREIGN PATENT DOCUMENTS (75) Inventors: Jihad Mohammed Dakka, Whitehouse CS 177505 7/1977 Station, NJ (US); Lorenzo Cophard DeCaul, Langhorne, PA (US); Teng Xu, OTHER PUBLICATIONS Hampton, NJ (US) U.S. Appl. No. 61/047,821, filed Apr. 25, 2008, ExxonMobil Chemi cal Patents, Inc. (73) Assignee: Exxonmobil Research and Neftekhimiya, V17. N. 5705-9, Sep.-Oct. 1977, “A Commercial Syn Engineering Company, Annadale, NJ thesis of Phenylcyclohexane ((PHCH)) by the Hydrodimerization of (US) Benzene. (*) Notice: Subject to any disclaimer, the term of this Primary Examiner Thuan Dinh Dang - patent is extended or adjusted under 35 (74) Attorney, Agent, or Firm Robert A. Migliorini U.S.C. 154(b) by 0 days. (57) ABSTRACT (21) Appl. No.: 12/287.655 Provided is a process for making cyclohexylbenzene. The (22) Filed: Oct. 10, 2008 process includes the following steps: (a) contacting benzene and hydrogen in the presence of a first catalyst under (51) Int. Cl hydroalkylatirOakVat1On COnd1t1OnSditi SullC1entffici to fOrm a first effeffluent CD7C 2/64 (2006.01) stream having cyclohexylbenzene, cyclohexane, methyl CD7C 2/66 (2006.01) cyclopentane, and unreacted benzene; (b) Supplying at least (52) U.S. Cl. ....................... 585/316; 585/314:585/318; part of said first effluent stream to a first separation system to 585/319; 585/320:585/323 divide said first effluent stream part into a cyclohexane/me (58) Field of Classification Search ................. 585/316, thylcyclopentane-rich stream, a cyclohexane-rich stream, a 585/314, 315, 318,319, 320, 323 benzene-rich stream, and a dicyclohexyl benzene-rich See application file for complete search history. stream; (c) recycling at least part of the benzene-rich stream to the contacting step (a); (d) contacting the cyclohexane/ (56) References Cited methylcyclopentane-rich stream with a second catalyst that U.S. PATENT DOCUMENTS catalyzes dehydrogenation and exhibits low acidity under conditions sufficient to convert at least a portion of the cyclo 3,962,362 A 6/1976 Suggitt hexane to benzene and at least a portion of the methylcyclo 4,094.918 A 6, 1978 Murtha et al. pentane to linear and/or branched paraffins to form a second 4,122,125 A 10, 1978 Murtha et al. 4,177,165 A 12/1979 Murtha et al. effluent stream; and (e) recycling at least part of the second 4,206,082 A 6, 1980 Murtha et al. effluent stream to the contacting step (a). 5,053,571 A 10, 1991 Makkee 6,037,513 A 3/2000 Chang et al. 9 Claims, 2 Drawing Sheets U.S. Patent Aug. 25, 2009 Sheet 1 of 2 US 7,579,511 B1 FIGURE 1 Cyclohexane/Methylcyclopentane (9575%) dehydrogenation Over 0.3% Pt/Akzo CK300 Cyclohexane con -H-MCP Conv. T.O.S (hrs) U.S. Patent Aug. 25, 2009 Sheet 2 of 2 US 7,579,511 B1 FIGURE 2 -- CH ConV 0.3%PAKZO --MCP conv., O.3%PIAKZO -A-CH Conv KL ...-e-MCP conv KL US 7,579,511 B1 1. 2 PROCESS FOR MAKING methylcyclopentane) therefore the invention concept could CYCLOHEXYLBENZENE be used to solve the problems associated with the benzene hydrogenation. FIELD Unless removed, cyclohexane and methyl cyclopentane build up in recycle streams, thereby displacing benzene and increasing the production of undesirable by-products. How The present disclosure relates to a process for making ever, the similar boiling points of benzene, cyclohexane and cyclohexylbenzene. methyl cyclopentane render separation difficult with conven tional distillation. The hydroalkylation process and the vari BACKGROUND 10 ous end products (and unreacted benzene) are shown in the following: Cyclohexylbenzene can be produced from benzene by the process of hydroalkylation or reductive alkylation. Benzene is heated with hydrogen in the presence of a catalyst Such that the benzene undergoes partial hydrogenation to produce 15 cyclohexene, which then alkylates the benzene to form cyclo H hexylbenzene. 2 -- + Dialkyl benzene + U.S. Pat. Nos. 4,094,918 and 4,177,165 disclose Cat hydroalkylation of aromatic hydrocarbons over catalysts of nickel- and rare earth-treated Zeolites and a palladium pro moter. Similarly, U.S. Pat. Nos. 4,122,125 and 4,206,082 disclose the use of ruthenium and nickel compounds Sup ported on rare earth-treated Zeolites as aromatic hydroalky lation catalysts. The Zeolites employed are zeolites X and Y. In addition, U.S. Pat. No. 5,053,571 proposes the use of 25 -- -- ruthenium and nickel Supported on Zeolite beta as anaromatic hydroalkylation catalyst. These processes have disadvan Bp 80. C. Bp 80.7° C. Bp. 72° C. tages of low selectivity to cyclohexylbenzene, particularly at economically viable benzene conversion rates, and large 30 Moreover, during dehydrogenation of the recycle stream quantities of unwanted by-products, particularly cyclohexane (dehydrogenation of cyclohexane by-product to benzene), and methylcyclopentane. methyl cyclopentane by-product forms methyl cyclopentadi U.S. Pat. No. 6,037,513 discloses that cyclohexylbenzene ene, a very reactive precursor for coke formation and an selectivity in the hydroalkylation of benzene can be improved accelerator of catalyst deactivation. by contacting benzene and hydrogen with a bifunctional cata lyst having at least one hydrogenation metal and a molecular 35 sieve of the MCM-22 family. The hydrogenation metal is CH3 preferably selected from among palladium, ruthenium, nickel, cobalt and mixtures thereof, and the contacting step is conducted at a temperature of about 50° C. to 350° C., a pressure of about 100 to 7000 kPa, benzene to hydrogen 40 all- O -- molar ratio of about 0.01 to 100 and a WHSV of about 0.01 to 100. The 513 patent discloses that the cyclohexylbenzene CH3 can then be oxidized to the corresponding hydroperoxide and the peroxide cleaved to the desired phenol and cyclohex 45 aOC. Although the use of MCM-22 family catalysts has afforded an increase in cyclohexylbenzene selectivity, significant COKE amounts of cyclohexane and methyl cyclopentane are none theless produced. The conditions of low temperature (less 50 It would be desirable to have a process for hydroalkylating than 200° C.) and high pressure (greater than 790 kPa) typi benzene affording enhanced conversion rates to cyclohexyl cally employed in hydroalkylation processes also favor the benzene. It would be further desirable to have a process competing reaction of benzene reduction to cyclohexane. As wherein the buildup of cyclohexane and methylcyclopentane a result, cyclohexane and methylcyclopentane selectivities of in recycle streams is reduced and the proportion of benzene 5 to 20 wt % are commonly observed. The production of 55 therein is increased. cyclohexane and methyl cyclopentane results in the loss of valuable benzene feed and reduces the level of benzene con SUMMARY version (typically 40 to 60 wt %), which necessitate recycle of unreacted benzene. According to the present disclosure, provided is a process Cyclohexylbenzene can be formed by benzene alkylation 60 for making cyclohexylbenzene. The process includes the fol with cyclohexene using MCM-22 family catalyst. Cyclohex lowing steps: (a) contacting benzene and hydrogen in the ene can be produced by selective partial benzene hydrogena presence of a first catalyst under hydroalkylation conditions tion using homogenous and heterogeneous catalyst as sufficient to form a first effluent stream having cyclohexyl described in many patents and articles (EP 323192, JP benzene, cyclohexane, methyl cyclopentane, and unreacted 85-204370, U.S. Pat. No. 4,055,512, DE 2520430). The 65 benzene; (b) Supplying at least part of said first effluent stream major by products formed in the benzene hydrogenation are to a first separation system to divide said first effluent stream similar to the hydroalkylation process (cyclohexane and part into a cyclohexylbenzene-rich stream, a cyclohexane/ US 7,579,511 B1 3 4 methylcyclopentane-rich stream, a benzene-rich stream, and cyclohexane and unreacted benzene. At least part of the first a dicyclohexyl benzene-rich stream (the dicyclohexyl ben effluent stream comprising cyclohexane and unreacted ben Zene-rich stream also having other heavy products); (c) recy Zene is then contacted with a second catalyst under dehydro cling at least part of the benzene-rich stream to the contacting genation conditions to convert at least part of the cyclohexane step (a); (d) contacting the cyclohexane/methylcyclopentane to benzene and/or bisphenyl and produce a second effluent rich stream with a second catalyst that catalyzes dehydroge stream containing less cyclohexane than the first effluent nation and exhibits low acidity under conditions sufficient to stream. At least part of the second effluent stream is recycled convert at least a portion of the cyclohexane to benzene and at back to the first contacting (hydroalkylation) step. least a portion of the methylcyclopentane to linear and/or In the present process, cyclohexylbenzene is produced by branched paraffins to form a second effluent stream; and (e) 10 contacting benzene with hydrogen under hydroalkylation recycling at least part of the second effluent stream to the conditions in the presence of a hydroalkylation catalyst contacting step (a). whereby the benzene undergoes the following reaction (1) to These and other features and attributes of the disclosed produce cyclohexylbenzene (CHB): processes for making cyclohexylbenzene of the present dis closure and their advantageous applications and/or uses will 15 be apparent from the detailed description which follows, par (1) ticularly when read in conjunction with the figures appended hereto. BRIEF DESCRIPTION OF THE DRAWINGS He To assist those of ordinary skill in the relevant artin making and using the Subject matter hereof, reference is made to the appended drawings, wherein: FIG. 1 is a plot showing cyclohexane and methyl cyclo 25 pentane conversion vs.
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