3,786,106 United States Patent Office Patented Jan. 15, 1974 1. 2 3,786,106 aromatics are produced by the reaction of aromatics with CYCLOALKYLAROMATIC PRODUCTION cycloolefins over an active clay catalyst such as Filtrol Ernest A. Zuech and Donald L. Crain, Bartlesville, Okla., assignors to Phillips Petroleum Company grade 71, Filtrol grade 62 and Filtrol grade 49. No Drawing. Filed Oct. 4, 1972, Ser. No. 294,989 In a specific embodiment of the invention, cyclohexyl Int, C. C07c5/I2 5 benzene is produced by the alkylation of benzene with U.S. C. 260-668 R 7 Claims cyclohexene over an active clay catalyst. The aromatic feedstocks which are suitable for use in the present invention are aromatic hydrocarbons, i.e., ABSTRACT OF THE DISCLOSURE monocyclic aromatic hydrocarbons and alkyl-substituted Cycloalkylaromatics are produced by the reaction of 10 monocyclic aromatic hydrocarbons. The alkyl substituents aromatics with cycloolefins over an active clay catalyst. preferred normally contain from 1 to 5 carbon atoms per In one embodiment cyclohexylbenzene is produced by the substituent. Some specific examples of suitable aromatic alkylation of benzene with cyclohexene over active clay compounds are benzene, toluene, the xylenes, ethylben catalysts such as Filtrol grade 71, Filtrol grade 62 and Zene, and the like, and mixtures thereof. Benzene is a Filtrol grade 49 catalysts. 15 presently preferred aromatic reactant. The olefinic portion of the feedstocks which are suit able for use in the present invention are cycloolefins hav This invention relates to a novel process for the prepa ing from, say, 5 to 10 carbon atoms per molecule. Some ration of alkylated aromatics. In accordance with another specific examples of these are cyclopentene, cyclohexene, aspect, this invention relates to the production of cyclo 20 cycloheptene, cyclooctene, cyclodecene, and the like, and alkylaromatics from aromatics and cycloolefins over an mixtures thereof. active clay catalyst. In accordance with a further aspect, Diluents suitable for use in the present process include this invention relates to the production of cyclohexylben both straight and branched chain paraffinic hydrocarbons zene by the alkylation of benzene with cyclohexene over containing 5 to 10 carbon atoms such as pentane, hexane, an active clay catalyst. In accordance with a further as 25 heptane, octane, nonane, and decane, and mixtures there pect, this invention relates to the production of cyclo of. Cyclic paraffinic hydrocarbons such as cyclohexane alkylaromatics from aromatics and cycloolefins over an can also be used. active clay catalyst wherein the reaction is carried out at The invention is catalyzed by active clay catalysts. Cat temperatures below about 400 F. alysts which have been found suitable in the practice of Methods are available in the art for the production of 30 the present invention include the so-called Filtrol clay aryl naphthene. One method for producing aryl naph materials. Other similar clays can also be used if desired. thene comprises the coupling of aromatic nuclei in the Presently preferred active clay catalysts include Filtrol presence of molecular hydrogen to produce partially hy grade 71, Filtrol grade 62, and Filtrol grade 49. A typical drogenated dimer derivatives of the aromatic reactants. analysis of the preferred Filtrol grade 71 clay catalyst is For example, benzene is hydrodimerized at elevated tem 35 as follows: 71.2% SiO2, 16.5% Al-O, 3.6% Fe.O.s, peratures to a mixture containing cyclohexylbenzene in 3.2% MgO, 2.6% CaO, 1.3% SO, 1.0% (KO--NaO) the presence of various catalysts. Also, it is known to and 0.6% TiO2 (analysis on a volatile free basis). The partially hydrogenate polycyclic aromatics such as bi catalyst can be employed as pills in a fixed bed or can be phenyl to cyclohexylbenzene. None of the prior art meth used as a slurry or suspension. In the preparation of ods of producing cyclohexylbenzene, for example, have 40 tablets it is advantageous to incorporate a small amount, yet been proved for a stable continuous operation neces preferably about 3 weight percent, graphite as a processing sary for commercial exploitation. Problems therewith in aid. It is desirable that the tablets have a crushing strength clude high catalyst cost, catalyst stability and regen of 5 to 10 pounds. eration. The process is advantageously practiced under substan Cyclohexylbenzene is a compound of commercial im 45 tially anhydrous conditions in an inert atmosphere pro portance and has principal utility as a solvent and plas vided by nitrogen, hydrogen, methane, and the Group ticizer in the plastics, coatings and adhesives fields. It is VIII-A elements (helium, neon, etc.). also utilized as a penetrating agent. The high boiling point The reaction can be carried out either batchwise or of cyclohexylbenzene together with a freezing point well continuously and any convenient contacting mode can be below normal or room temperature render it highly suited 50 for the purposes stated. It is also useful as an intermedi used. Continuous operation using a fixed catalyst bed re ate in the production of cyclohexene which in turn can be actor is presently preferred. utilized for the production of adipic acid and capro Suitable parameters for the practice of the present in lactam. It can also be converted in high yield to phenol vention are as follows: and cyclohexanone by air oxidation or auto-oxidation with 55 subsequent acid treatment. This invention relates to a novel process for the produc Suitable Preferred tion of cycloalkylaromatics from aromatics and cycloole (a) Molar ratio of aromatic/cyclo alkene---------------------------- 1:1-30:1 3:1-5: fins over an active clay catalyst. (b) Temperature, C.J. F.------- 100-180/212-356 115-160/239-320 Accordingly, an object of this invention is to provide 60 (c) Pressure, p.S.i.g---------- -- a- 0-2,000 100-1,000 an efficient and economical process for the production of (d) LHSV-------------------------- 0-20 -10 cycloalkylaromatics. Another object of this invention is to provide a novel process for the preparation of higher alkylaromatic com After leaving the reaction zone the effluent can be col pounds in improved yields. 65 lected and separated using any conventional and suitable A further object of this invention is to provide an im CaS proved process for the production of cyclohexylbenzene. EXAMPLE I Other objects and aspects as well as the several advan A charge of 19.2 g (30 ml.) of Filtrol Grade 62 tages of the invention will be apparent to one skilled in extrudate was placed in a /2-inch pipe reactor and covered the art upon reading the specification and the appended 70 with 10 ml. of 4 mm. glass beads. The system was pres claims. sure checked and heated to 150° C. under 200 p.si.g. In accordance with the present invention, cycloalkyl nitrogen with nitrogen purge. A total feed of 210 g. (2.7 3,786,106 3. 4. moles) benzene and 22 g (0.27 mole) cyclohexene was the top of the catalyst bed and at the middle of the cata pumped into the reactor at a rate of 1 ml/min. Samples lyst bed were, respectively, 154 C. and 162 C. TABLE I Cyclohexybenzene over Filtrol 71 powder Reactor effluent composition, wt. percent 1 Cs s / Time on Lighter Cyclo stream than hexyl (min.) CEI CE. Unknown benzene Run number: -- 88 1.0 0.3 , 4 0.9 96.4 48 1, 3 Trace 2.8 1.3 94.7 28 3.6 0.0 4.2 3. 89.2 1. Excluding benzene and heavies. of reactor effluent were taken for glo analysis at time At the end of 281 minutes the reactor was drained, and intervals shown in Table I. During the reaction period of the catalyst bed was left under 200 p.s.i.g. N. 448 minutes, the average temperatures near the top of the catalyst bed and at the middle of the catalyst bed EXAMPLE III were, respectively, 154 C. and 172 C. 25 This run was carried out over the same catalyst bed as TABLE Cyclohexylbenzene process over Filtrol 62 Reactor effluent composition, wt. percent 1 C e Time on Lighter Cyclo stream than hexyl (min.) CoHo CE10 Unknown benzene 60 Trace 4.2 3. O, 55.0 20 Trace 13, 2 2.5 ... 3 83.0 216 0.4 6.2 1.6 1, 6 90.2 268 0.6 4.2 ... 6 1.3 92, 3 328 0.6 3.4 2.2 1, 6 92.0 448 0, 6 5.5 2.. O 1. 90.8 EXAMPLE II in Example II. The procedure of this run differed from 45 that used in Example II in the following respects: (a) dur A charge of 18.8 g. (30 ml.) of Filtrol Grade 71 ing the reaction period of 450 minutes, the average tem powder was placed in a /2-inch pipe reactor and covered peratures near the top of the catalyst bed and at the with 10 ml. of 4 mm. glass beads. The system was pres middle of the catalyst bed were, respectively, 130 C, and sure checked and heated to above 150° C. under 200 141 C., (b) after 206 minutes on stream the initial p.s. i.g. nitrogen with nitrogen purge. A total feed of 210 50 charge of 210 g. (2.7 moles) benzene and 22 g (0.27 g. (2.7 moles) benzene and 22 g. (0.27 mole) cyclo mole) cyclohexene had been added and the feed rate was hexene was pumped into the reactor at a rate of 1 ml./ increased from 1 ml./min. to 2 ml/min. and an additional min. Samples of reactor effluent were taken for glo anal charge of benzene/cyclohexene (210 g./22 g.) was passed ysis at time intervals shown in Table II.