GB1572550A - Hydroalkylation of benzene and analogues - Google Patents

Description

(54)HYDROALKYLATIONOFBENZENEANDANALOGS (71) We, THESTANDARDOIL COMPANY, a corporation organised under the laws of the State of Ohio, United States of America of Midland Building, Cleveland, Ohio 44115, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to an improved process for the hydroalkylation of mononuclear aromatic hydrocarbons, namely benzene and analogs thereof, of form cycloalkylaromatics. Many patents have recently issued in the field of hydroalkylation of mononuclear aromatics. See, for example, U.S.3,760,019, U.S.3,784,617, U.S.3,784,618, U.S.3,829,514, U.S.3,829,515, U.S.3,829,516 and U.S.

3,829 517. In the processes disclosed in these patents, benzene or analog is contacted with a catalyst which is normally composed of a Group VIII transition metal supported on a suitable carrier, the catalyst optionally containing tungsten. Many different supports are disclosed as useful including silica-alumina, zeolite and alumina. Specific Group VIII transition metals disclosed to be useful are cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum.

Although processes disclosed in the foregoing patents are capable of effecting hydroalkylation of benzene and analogs to the corresponding cycloalkylaromatic compounds, they are disadvantageous in that they are unable to provide the desired cycloalkylaromatic product compounds with high yields and high selectivities. Moreover, in many processes it is necessary to subject the catalyst to be used to an activation pre-treatment by reducing the catalyst with H2 prior to beginning the hydroalkylation reaction. In still other processes, it is necessary to carry out the hydroalkylation reaction in stages, the total amount of hydrogen necessary to effect hydroalkylation being added to the reaction system in stepped additions.

Accordingly, it is an object of the present invention to provide an improved process for the catalytic hydroalkylation of benzene and analogs to the corresponding cycloalkylaromatic compounds which produces the desired product compounds in higher yield and with higher selectivities than processes known prior to the present invention.

It is a further object of the present invention to provide a hydroalkylation process of the type described above which can be carried out either in batch mode or continuously in a single stage operation, i.e. a process which does not require stepped addition of reactants.

It is still another object of the present invention to provide a hydrolkylation process in which the catalyst to be used can be employed directly after calcination, H2 reduction of the catalyst prior to use being unnecessary.

The present invention provides a process for the hydroalkylation of mononuclear aromatic hydrocarbons to give cyloalkyl aromatic hydrocarbons in which the mononuclear aromatic hydrocarbon together with hydrogen is contacted with a catalyst comprising a rare earth-exchanged Y-type zeolite support carrying a ruthenium, iriduim, rhodium and/or palladium promoter, the catalyst being calcined in an oxygen-containing atmosphere at a temperature of 250 to 600 C prior to the hydroalkylation reaction.

In a specific embodiment, the present invention provides a process for the hydroalkylation of mononuclear aromatic hydrocarbons which comprises contacting for a period of 10 minutes to 6 hours at a temperature of from room temperature to 400 C hydrogen and a mononuclear aromatic hydrocarbon selected from benzene and substituted benzene substituted benzene substituted with 1 to 4 alkyl groups each independently having 1 to 4 carbon atoms with a catalyst obtained by calcining in a molecular oxygen-containing atmosphere at a temperature of 250 to 6000C a composite comprising a rare earth-exchanged Y-type zeolite support impregnated with at least one compound decomposable to yield a promoter comprising at least one of ruthenium, iridium, rhodium and palladium, the amount of the decomposable compound on the support being such that the amount of promoter on the support after calcination is between 0.2 and 10 weight percent with the weight of the rare earth-exchanged Y-type zeolite plus the weight of the promoter being taken as 100%.

In accordance with the present invention it has been found that cycloalkylaromatics can be produced with higher yields and higher selectivities than previously known processes for hydroalkylation of benzene and analogs.

For example, it has been found that cyclohexylbenzene can be obtained with per pass conventions approaching 50% at selectivities close to 80%, which is significantly better than obtainable with the prior art processes disclosed in the above-noted patents. Moreover, the inventive process can be accomplished in a single stage operation, i.e., without the stepped addition of reactants and hence is easier to carry out than conventional processes carried out in multiple stages. Also, the catalyst employed in the inventive process can be used directly after calcination without H2 reduction, and hence practice of the inventive process is easier than conventional processes requiring H2 reduction as part of the catalyst preparation.

DETAILED DESCRIPTION Process Conditions The inventive hydroalkylation reaction is accomplished by contacting the mononuclear aromatic hydrocarbon to be reacted with a reaction catalyst in the presence of hydrogen.

The reaction can be accomplished both in batch mode and continuously with both fixed and fluid catalyst beds. The reaction is normally carried out in single stage operation, i.e., all of the reactants and the catalyst necessary for the reaction are brought together at the same time and not in stepped additions.

However, the reaction can be carried out in stages if desired.

The reaction temperature is normally maintained between room temperature and 400"C, preferably 100 to 3000C, more preferably 150 to 2500C and optionally 2000 C. The reaction pressure is normally maintained at 100 to 800 psig, preferably 200 to 500 psig and most preferably 300 to 400 psig. When the reaction is carried out in the batch mode, the reactants and catalysts are contacted with one another for a period of 10 minutes to 6 hours, preferably more than 1/2 to 3 hours, and optionally about 1.5 hours. A reaction time of less than 10 minutes or more than 6 hours can be used if desired although better results will be obtained if the reaction time is maintained within this range. When the process is carried out on a continuous basis, the reactant catalyst contact time is normally 10 seconds to 10 minutes, preferably 100 seconds to 5 minutes.

The amount of hydrogen in the reaction system is not critical, and the reaction will proceed so long as any amount of hydrogen is present. Preferably the amount of hydrogen correspond to the amount of hydrogen present when a 600 cc reactor containing 5 grams of catalyst and 2.0 moles of benzene is filled with hydrogen to the pressures indicated above. If desired, a carrier gas which is inert to the reactants, product and catalyst can be included in the reaction system.

The present invention finds wide applicability in the hydroalkylation of all types of mononuclear aromatic hydrocarbons. Benzene (unsubstituted) and substituted benzene substituted with 1 to 4 alkyl groups each independently having 1 to 4 carbon atoms can be readily converted to the corresponding cycloalkylaromatics in accordance with the present invention. Specific examples of compounds which can be processed by the present invention include benzene, ethylbenzene, cumene (isopropyl benzene), toluene, xylene, and durene (tetramethylbenzene).

In order to recover the product compound from the reaction mixture when the reaction is completed, the liquid reaction product is separated from any unreacted hydrogen and carrier gas that may be present in the system.

The liquid reaction product is then filtered to remove catalysts therefrom and the filtrate is subjected to distillation or other suitable separation technique to recover the product compound from unreacted starting material.

CA TAL YST The catalyst employed in the invention process comprises a rare earth-exchanged Y-type zeolite impregnated with a small but suitable amount of a Group VIII transition metal promoter selected from ruthenium, iridium, rhodium and palladium. Y-type zeolite is a well-known material in the art and described in detail in Chapters 18-20 of Meier and Uytterhoeven, MOLECULAR SEIVES, American Chemical Society, Washington, D.C., copyright 1973. See also U.S. 3,130,007. As well-known in the art, Y-type zeolite can be treated to accept various types of ions by impregnating the Y-type zeolite with a solution of the ions to be accepted. Such a procedure causes an exchange reaction to occur, cations in the aqueous solution being exchanged for cations originally in the zeolite. See column 18 of U.S. 3,130,007. The catalyst support useful in the inventive process is a rare earthexchanged Y-type zeolite which is produced by exchanging rare earth ions from an aqueous solution thereof with the ions originally in Y-type zeolite. This material is well-known as pointed out in columns 7 and 8 of U.S.

3,784,617. In the preferred embodiment of the invention, the rare earth-exchanged Y-type zeolite employed in Linde's SK-500 (Registered Trade Mark), which is a well-known commercially available catalyst support. Linde's SK-500 is composed of 65.0 weight percent Six2, 22.7 weight percent Awl203, 1.6 weight percent Na2O and 10.7 weight percent various rare earth metals. Rare earth-exchanged Y-type zeolites other than Linde's SK-500 can be employed in the present invention, the specific rare earth impregnating the Y-type zeolite being unimportant. In this connection, since it is expensive to separate one rare earth from another, commercially available rare earthexchanged Y-type zeolites are made with mixtures of different rare earths rather than a single rare earth.

In accordance with the present invention, the rare earth-exchanged Y-type zeolite employed as the catalyst additionally contains a promoter metal selected from the group consisting of ruthenium, iridium, rhodium and palladium. The preferred promoter is ruthenium. The amount of promoter metal in the catalyst can vary between relatively broad proportions. If the amount of promoter metal is 0.1 weight percent, no significant promoting effect will be obtained. Moreover, although amounts of promoter metal above 10% will provide effective catalysts, the cost of using such large amounts of promoter metal is prohibitively expensive. Threfore, the amount of promoter metal in the catalyst is greater than 0.1 weight percent and usually between 0.2 and 10 weight percent based on the weight of promoter metal in the catalyst with the weight of the rare earth-exchanged Y-type zeolite plus the weight of the promoter metal being taken as 100 percent. Preferably the catalyst contains 0.5 to 2 weight percent promoter metal, while the most preferred amount is about one percent by weight.

In order to deposit the promoter metal on the rare earth-exchange Y-type zeolite support of the present invention, any convenient technique can be employed. For example, the promoter metal in the form of a decomposable salt or other compound can be dissolved in a solvent therefore and the solution so obtained used to impregnate the rare earth-exchanged Y-type zeolite material. Chloride salts (i.e.

RuCl3 .3H2O, IrCI3 .4H2O, RhC13 .3H2O and PdC12) dissolved in ethanol or isopropanol as the solvent have been found especially suitable for this purpose. Any other compound (e.g.

nitrates, acetates, etc.) which yield catalytically active ruthenium, rhodium, iridium or palladium when heated in the presence of oxygen under the calcining conditions discussed below can be employed in place of chloride. Processes for depositing transition metals including ruthenium, iridium, rhodium and palladium, on Y-type zeolite supports are well-known as taught in U.S. 3,784,617. This patent further teaches that it is well-known to deposit other types of Group VIII metals on rare earth-exchanged Y-type zeolites. Therefore, those skilled in the art should have no difficulty in producing catalysts including ruthenium, iridium, rhodium and/or palladium on a rare earth-exchanged Y-type zeolite as used in the present invention.

Once the promoter metal in chloride or other decomposable compound form is deposited on the rare earth-exchanged Y-type zeolite, the composite so formed is activated by calcination.

In accordance with the present invention, calcination is accomplished in a molecular oxygen-containing atmosphere at a temperature of 250 to 6000 C, preferably 350 to 5000 C, most preferably 4270 C. Temperatures below 250"C can be employed but activation is so slow that such temperatures are impractical.

At temperatures above 6000 C, the zeolite support will begin to decompose hence reducing the catalytic activity of the catalyst produced. Calcination has the effect of expelling water from the zeolite support, which in turn causes the calcined catalyst obtained to exhibit a superior catalytic activity. Therefore, calcination should be carried out for a time sufficient to drive off water from the zeolite support and hence improve the catalytic activity of the catalyst obtained. Those skilled in the art can determine the optimum calcination time by simple routine experimentation. In this connection, it has been found that at the preferred calcination temperature of 427" C, the calcination time is approximately two hours, whereas at the maximum calcination temperature of 600"C calcination should last no more than about eight hours while at the minimum calcination temperature of 250"C calcination should be accomplished for at least about 24 hours.

Once the promoter metal-containing zeolite composite of the present invention has been subjected to calcination, it can be directly used as the catalyst to effect the hydroalkyl ation reaction, reduction with hydrogen gas being unnecessary.

As indicated above, the products of the inventive process, namely cycloalkylaromatic hydrocarbons, are produced in accordance with the present invention with high per pass conversions and high selectivities. Thus the present invention marks a significant advance over prior art processes since it is possible to pro duce more end product with a given amount of feed. Moreover, with superior selectivities, recycle requirements are reduced, thereby decreasing energy costs. Also, because hydrogen reduction of the catalyst prior to use is unnecessary, and because the inventive process can be carried out in single stage oper ation the inventive process is simpler to accomplish than many analogous prior art processes.

The end products of the inventive process, namely cycloalkylaromatic hydrocarbons, have many significant uses. For example, these compounds can be converted to phenol and/or cyclohexanone in the case of benzene and analogous products in the case of benzene analogs, which compounds have known utilities.

Working Examples In order to more thoroughly illustrate the present invention, the following working examples are presented. In these examples "% ppc" means percent per pass conversion and is defined as moles carbon in reactant ppc = converted to product x 100 moles carbon in reactant fed EXAMPLE 1 0.193 gram Irk13 4H2O was dissolved in 200 cc distilled water to form a green solution.

9.9 grams Linde's SK-500 ( < 50 mesh powder) was added, and the water was evaporated from the composition so obtained to form a light brown paste which was dried overnight at 1100 C to form an essentially white material.

This material was then calcined in air at 427"C for 2'% hours to produce a grayishwhite catalyst containing 1% Ir and 99% SK-500.

5 grams of the catalyst so obtained were charged into a 600 cc PARR autoclave.

156.22 grams (2.0 moles) benzene was also fed into the reactor. The autoclave was then pressurized with hydrogen to a pressure 400 psig. The reaction progressed for approximately 35 minutes over which time the pressure in the reactor decreased from 400 to 180 psig and the reaction temperature increased from an initial value of 22"C to 1850 C. After the 35 minute reaction period, the reaction product was recovered from the reactor and subjected to analysis by gas chromotography. The following results were obtained: % pope cyclohexane 8.36 bicyclohexane 0.10 cyclohexylbenzene 43.94 dicyclohexylbenzene 0.52 unreacted benzene 47.09 selectivity 83.00 EXAMPLE 2 The procedure of Example 1 was repeated except that catalyst employed was composed of 1% Rh and 99% SK-500. This catalyst was prepared in the same way as the catalyst employed in Example 1 except that 0.256 grams RhCl3 3H2O was employed rather than 0.193 grams IrCI3 .4H2O. Also, in Example 2, the reaction time was 1 IA hours rather than IA hour. The following results were obtained: %ppc cyclohexane 32.51 bicyclohexane 1.80 cyclohexylbenzene 35.78 dicyclohexylbenzene 0.52 unreacted benzene 11.40 selectivity 40.4 EXAMPLE 3 Example 2 was repeated except that the catalyst employed contained 1% Pd and 99% SK-500. The catalyst of Example 3 was prepared as the catalyst of Example 1 was prepared except that 0.167 grams PdC12 was employed. The following results were obtained: %ppc cyclohexane 10.74 bicyclohexane 0.10 cyclohexylbenzene 50.44 dicyclohexylbenzene 4.43 unreacted benzene 33.46 selectivity 75.80 EXAMPLE 4 U.S. Patent 3,784,617 to Suggitt discloses a process for the catalytic hydroalkylation of mononuclear hydrocarbons in which the catalyst may be ruthenium supported on NH4-exchanged Y-zeolite. This Example 4 as well as the following Comparative Examples A, B and C are presented to show the improved results realized in accordance with the present invention when the catalyst is composed of ruthenium supported on rare earth-exchanged Y-zeolite.

1.056 grams RuCl3 3H2O was dissolved in 200 cc of isopropanol to form a red-brown solution. 39.6 grams Linde's SK-500 was added to this red-brown solution, and the solvent was then evaporated with constant stirring at low heat. The green paste formed thereby was dried overnight at 110"C in an oven to produce a gray powder. A portion of this gray powder was calcined at 4270 C for 2 hours in the presence of air to provide the Example 4 catalyst having 1% Ru and 99% SK-500.

Hydroalkylation of benzene was carried out in the same way as in Example 1 except that the reaction pressure was maintained at about 300 psig and the reaction temperature was maintained at about 200"C. Also, a portion of the liquid reaction medium was withdrawn at IA hour intervals and the composition of each withdrawn portion determined. The following results were obtained, as shown overleaf.

Comparative Example A Example 4 was repeated except that the catalyst employed was composed of 1% Ru and 99% NH4-exchanged Y-zeolite which was calcined at 4270 C for 2 hours. The following results were obtained, as shown overleaf.

Comparative Example B A portion of the gray powder produced during catalyst preparation in Example 4 was prepared for use in accordance with the technique disclosed in U.S. Patent 3,829,517.

Namely, the gray powder was calcined at 800"C for 2 hours in the presence of air and then reduced with H2 at 4800 C at atmospheric pressure for 2 hours. Example 4 was then repeated using this catalyst. The following results were obtained: EXAMPLE 4 Catalyst: 1% Ru & 99% SK-500 Calcined in Air at 4270C for 2 Hours % pope Time Unreacted Experiment No. (in hrs.) CHXN BiCHXN CHB DiCHB Benzene Selectivity 41 1/2 OA9 ~0 13.91 0.92 84.68 90.8 42 1 2.75 ~0 31.67 2.72 62.86 85.3 43 11/2 5.05 0.24 46.57 7.02 41.12 79.1 44 after cooling 6.74 0.24 46.06 6.94 40.02 76.8 in autoclave COMPARATIVE EXAMPLE A Catalyst: 1% Ru & 99% NH4-Exchanged Y-Zeolite Calcined in Air at 4270C for 2 Hours % pope Time Unreacted Experiment No. (in hrs.) CHXN BiCHXN CHB DiCIIB Benzene Selectivity A1 1/2 1.78 ~0 20.64 1.17 76.41 87.5 A2 1 4.06 ~0 34.56 4.08 57.31 89.9 A3 11/2 7,88 0.25 40.64 7A6 43.77 72.3 A4 after cooling 9.32 0.25 40.51 8.09 41.83 69.6 in autoclave COMPARATIVE EXAMPLE B Catalyst: 1% Ru & 99% SK-500 Calcined in Air at 8000C For 2 Hours and Then Reduced in H2 at 480"C for 2 Hours % ppc Time Unreacted Experiment No. (in hrs.) CHXN BiCHXN CHB DiCHB Benzene Selectivity B1 1/2 0.56 ~0 11.36 0.23 87.85 93.5 B2 1 0.99 trace 15.64 0.63 82.74 90.6 B3 11/2 1.60 trace 20.19 1.25 76.96 87.6 B4 after cooling 2.78 trace 20.97 1.63 74.61 82.6 in autoclave Comparative Example C Example 4 was repeated except that the catalyst employed was composed of 1% Ru.

and 99% NH4-exchanged Y-zeolite, the catalyst having been calcined at 8000 C for 2 hours in the presence of air and thereafter reduced at 4800C in the presence of 112 for 2 hours in accordance with the technique taught in U.S. Patent 3,829,517. The following results were obtained: COMPARATIVE EXAMPLE C Catalyst: 1% Ru & 99% NH4-Exchange Y-Zeolite Calcined In Air at 8000C for 2 Hours and Then Reduced in 112 for 2 Hours at 480"C % pope Time Unreacted Experiment No. (in hrs.) CHXN BiCHXN CHB DiCHB Benzene Selectivity C1 1/2 2.60 ~0 26.25 1.53 69.62 86.4 C2 1 5.11 0.27 33.79 4.46 56.38 77.5 C3 11/2 7.34 0.27 38.24 8.02 46.13 71.0 C4 after cooling 8.16 0.24 35.29 7.09 49.21 69.5 in autoclave Comparatrve Example D U.S. Patent 3,829,517 to Zuech discloses a catalytic hydroalkylation process employing a ruthenium halide-active clay catalyst which has not been heated under calcination conditions prior to use. This Comparative Example D as well as the following Comparative Example E and F are presented to show the superiority of the inventive process as illustrated in Example 4 with respect to the process shown in U.S. 3,829,517.

0.7895 grams RuC13 3H30 was dissolved in 200 cc ethanol to produce a dark red-brown solution. 29.7 grams Filtrol Grade-71 (Registered Trade Mark) powder was suspended in the solution and impregnated at low heat with constant stirring. The solvent was then removed and the wet powder obtained dried in an oven at 1100C for 3 hours to produce a gray powder. A portion of the gray powder was calcined at 427"C in the presence bf air for 2 hours in the manner of Example 4 to yield a catalyst containing 1% Ru and 99% Filtrol Grade-71, which was employed as the catalyst in Comparative Example D.

Example 4 was repeated using as the catalyst the catalyst obtained above. The following results were obtained: COMPARATIVE EXAMPLE D Catalyst: 1% Ru & 99% Filtrol Grade - 71 Calcined in Air for 2 Hours at 427"C % pope Time Unreacted Experiment No. (in hrs.) CHXN BiCHXN CHB DiCHB Benzene Selectivity D1 1/2 1.02 8.48 0.30 90.20 86.5 D2 1 2.40 trace 19.73 0.73 77.14 86.3 D3 11/2 4.03 0.13 25.43 1.38 69.02 82.1 D4 after cooling 5.23 0.12 21.49 1.51 71.66 75.8 in autoclave Comparative Example E Example 4 was repeated using as the catalyst a portion of the gray powder produced during catalyst preparation in Comparative Example D. It will be noted that this catalyst was composed of 1% Ru and 99% SK-500 and was not calcined prior to use. The following results were obtained ,as shown overleaf.

Comparative Example F Comparative Example D was repeated except that the catalyst was not calcined prior to use. It will thus be appreciated that the catalyst employed in this comparative example was composed of 1% Ru and 99% Filtrol Grade-7 1, the catalyst being uncalcined as taught in U.S. 3,829,517. The following results were obtained: COMPARA HVE EXAMPLE E Catalyst: 1% Ru & 95% SK-500 Uncalcined % pope Time Unreacted Experiment No. (in hrs.) CHXN BiCHXN CHB DiCHB Benzene Selectivity E1 1/2 0.0 ~0 1.72 97.68 74.1 E2 1 1.33 ~0 7.32 0.11 91.25 83.6 E3 11/2 3.38 ~0 12.98 0.32 83.32 77.8 E4 after cooling 5.68 trace 12.73 0.40 81.18 67.7 in autoclave COMPARATIVE EXAMPLE F Catalyst: 1% Ru & 99% Filtrol Grade-71 Uncalcined % pope Time Unreacted Experiment No. (in hrs.) CHXN BiCHXN CHB DiCHB Benzene Selectivity Fl 1/2 0.26 0 0.62 0 99.12 70.5 F2 1 0.21 0 1.01 0 98.78 82.8 F3 11/2 0.29 0 1.30 0 98.42 81.8 F4 after cooling 0.35 0 1.34 0 98.31 79.3 in autoclave WHAT WE CLAIM IS:- 1. A process for the hydroalkylation of mononuclear aromatic hydrocarbons to give cycloalkyl aromatic hydrocarbons comprising contacting a mononuclear aromatic hydrocarbon and hydrogen with a catalyst comprising a rare earth-exchanged Y-type zeolite support carrying a promoter comprising at least one of ruthenium, iridium, rhodium and palladium, said catalyst having been calcined in a molecular oxygen-containing atmosphere at a temperature of 250a to 6000C prior to use.

2. The process of claim 1 wherein calcination is accomplished for a time sufficient to activate said zeolite support.

3. The process of claim 1 wherein said mononuclear aromatic hydrocarbon is benzene or a substituted benzene substituted with 1 to 4 alkyl groups each independently having 1 to 4 carbon atoms.

4. The process of claim 3 wherein said mononuclear aromatic compound is benzene.

5. The process of claim 3 wherein said catalyst contains greater than 0.1 weight percent promoter with the weight of said rare earth-exchanged Y-type zeolite plus the weight of said promoter being taken as 100%.

6. The process of claim 5 wherein said catalyst contains 0.2 to 10 weight percent promoter.

7. The process of claim 5 wherein said mononuclear aromatic compound is contacted with said catalyst at a temperature between room temperature and 400" C.

8. The process of claim 7 wherein said process is carried out in the batch mode, said mononuclear aromatic hydrocarbon and hydrogen contacting said catalyst for a period of 10 minutes to 6 hours.

9. The process of claim 8 wherein said mononuclear aromatic hydrocarbon and said hydrogen contact said catalyst for a period of more than IA to three hours.

10. The process of claim 8 wherein said promoter is ruthenium.

11. A process for the hydroalkylation of mononuclear aromatic hydrocarbons as claimed in claim 1 substantially as herein described with reference to the Examples.

12. Hydroalkylation products of mononuclear hydrocarbons when made by a process

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (12)

**WARNING** start of CLMS field may overlap end of DESC **. results were obtained: COMPARA HVE EXAMPLE E Catalyst: 1% Ru & 95% SK-500 Uncalcined % pope Time Unreacted Experiment No. (in hrs.) CHXN BiCHXN CHB DiCHB Benzene Selectivity E1 1/2 0.0 ~0 1.72 97.68 74.1 E2 1 1.33 ~0 7.32 0.11 91.25 83.6 E3 11/2 3.38 ~0 12.98 0.32 83.32 77.8 E4 after cooling 5.68 trace 12.73 0.40 81.18 67.7 in autoclave COMPARATIVE EXAMPLE F Catalyst: 1% Ru & 99% Filtrol Grade-71 Uncalcined % pope Time Unreacted Experiment No. (in hrs.) CHXN BiCHXN CHB DiCHB Benzene Selectivity Fl 1/2 0.26 0 0.62 0 99.12 70.5 F2 1 0.21 0 1.01 0 98.78 82.8 F3 11/2 0.29 0 1.30 0 98.42 81.8 F4 after cooling 0.35 0 1.34 0 98.31 79.3 in autoclave WHAT WE CLAIM IS:-

1. A process for the hydroalkylation of mononuclear aromatic hydrocarbons to give cycloalkyl aromatic hydrocarbons comprising contacting a mononuclear aromatic hydrocarbon and hydrogen with a catalyst comprising a rare earth-exchanged Y-type zeolite support carrying a promoter comprising at least one of ruthenium, iridium, rhodium and palladium, said catalyst having been calcined in a molecular oxygen-containing atmosphere at a temperature of 250a to 6000C prior to use.

2. The process of claim 1 wherein calcination is accomplished for a time sufficient to activate said zeolite support.

3. The process of claim 1 wherein said mononuclear aromatic hydrocarbon is benzene or a substituted benzene substituted with 1 to 4 alkyl groups each independently having 1 to 4 carbon atoms.

4. The process of claim 3 wherein said mononuclear aromatic compound is benzene.

5. The process of claim 3 wherein said catalyst contains greater than 0.1 weight percent promoter with the weight of said rare earth-exchanged Y-type zeolite plus the weight of said promoter being taken as 100%.

6. The process of claim 5 wherein said catalyst contains 0.2 to 10 weight percent promoter.

7. The process of claim 5 wherein said mononuclear aromatic compound is contacted with said catalyst at a temperature between room temperature and 400" C.

8. The process of claim 7 wherein said process is carried out in the batch mode, said mononuclear aromatic hydrocarbon and hydrogen contacting said catalyst for a period of 10 minutes to 6 hours.

9. The process of claim 8 wherein said mononuclear aromatic hydrocarbon and said hydrogen contact said catalyst for a period of more than IA to three hours.

10. The process of claim 8 wherein said promoter is ruthenium.

11. A process for the hydroalkylation of mononuclear aromatic hydrocarbons as claimed in claim 1 substantially as herein described with reference to the Examples.

12. Hydroalkylation products of mononuclear hydrocarbons when made by a process

as claimed in any of claims 1 to 11.