Process for the preparation of p-ethylphenol

• US 4,927,979 A
• Filed: 12/06/1988
• Issued: 05/22/1990
• Est. Priority Date: 12/18/1987
• Status: Expired due to Fees

• Current Assignee: Maruzen Petrochemical Co., Ltd. (Cosmo Energy Holdings Co., Ltd.)
• Original Assignee: Maruzen Petrochemical Co., Ltd. (Cosmo Energy Holdings Co., Ltd.)
• Inventors: Idai, Tsutomu, Takahashi, Eiji, Yamagishi, Takanori
• Primary Examiner(s): Lone, Werren B.
• Application Number:
  US07/280,692
• Time in Patent Office: 532 Days
• Field of Search: 568/790, 568/791, 568/794
• US Class Current: 568/791
• CPC Class Codes: B01J 2229/26 to stabilize the total catalyst structure
• CPC Class Codes: B01J 2229/36 Steaming
• CPC Class Codes: B01J 2229/42 Addition of matrix or binder particles
• CPC Class Codes: B01J 29/40 of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
• CPC Class Codes: B01J 29/65 of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
• CPC Class Codes: B01J 29/70 of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• CPC Class Codes: C07C 37/14 by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
• CPC Class Codes: C07C 37/16 by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
• CPC Class Codes: C07C 39/06 Alkylated phenols

Abstract

A very simple process for preparing p-ethylphenol is disclosed. It is only necessary to contact phenol with an ethylating agent in vapor phase in the presence of a specific catalyst. The catalyst can be obtained by incorporating one or more alkoxysilanes to a crystalline aluminosilicte with a constraint index of 1-15 having a silica/alumina molar ratio of 20-400, wherein the amount of said alkoxysilanes to be incorporated is not less than 1.4 wt % calculated as silicon based on the amount of said crystalline aluminosilicate. Because the specific catalyst has the narrowed or restricted entrances of the micro pores of the crystalline aluminosilicate by the alkoxysilane treatment, it is possible to prepare p-ethylphenol in a high selectivity. The product contains only a very small amount of m-ethylphenol. The p-ethylphenol product obtained by the process of the present invention can be employed directly as raw materials for practical uses such as synthetic resins and antioxidants without m-ethylphenol elimination procedure.

Claims

1. In a process for the preparation of a mixture of ethylphenol isomers which comprises reacting phenol with an ethylating agent selected from the group consisting of ethylene and ethanol in the vapor phase in the presence of a catalyst at a temperature of 200°

-600°

C. under a pressure of not higher than 10 Kg/cm².G, the improvement which comprises that said mixture of ethylphenol isomers has a p-ethylphenol content of higher than about 80 wt. % and said catalyst comprises a crystalline aluminosilicate catalyst obtained by incorporating one or more alkoxysilanes represented by the formula R'"'"'_n Si(OR)_4-n wherein OR represents an alkoxy group having 1-6 carbon atoms, R'"'"' represents an alkyl group having 1-6 carbon atoms or a phenyl group and n represents an integer of 0-3, on a crystalline aluminosilicate having a constraint index of 1-15 and a silica/alumina molar ratio of 20-400, the amount of said incorporated alkoxysilanes being not less than 1.4 wt. % calculated as elemental silicon based on the amount of said crystalline aluminosilicate.

2. The process according to claim 1, wherein said crystalline aluminosilicate is a zeolite selected from the group consisting of ZSM-5, ZSM-11, ZSM-12, ZSM-35 and ZSM-38.

3. The process according to claim 1, wherein said crystalline aluminosilicate is a pentasil-type zeolite.

4. The process according to claim 3, wherein said pentasil-type zeolite is ZSM-5 or ZSM-11.

5. The process according to claim 1, wherein said crystalline aluminosilicate is an H-crystalline aluminosilicate.

6. The process according to claim 5, wherein said H-crystalline aluminosilicate is obtained by treating a crystalline aluminosilicate with an aqueous solution of one or more ammonium salts and then calcining thereby converting exchangeable cations positioned near the aluminum atoms into H⁺ ions.

7. The process according to claim 1, wherein said alkoxy group of said alkoxysilane is a methoxy group or an ethoxy group and said alkyl group of said alkoxysilane is a methyl group or an ethyl group.

8. The process according to claim 1, wherein the weight hourly space velocity (WHSV) calculated in the total of said phenol and said ethylating agent is 0.2-160 hr^-1.

9. The process according to claim 1, wherein said catalyst is prepared by calcining after the incorporation of said alkoxysilanes.

10. The process according to claim 1, wherein said catalyst is prepared without calcination after the incorporation of said alkoxysilanes.

11. The process according to claim 1, wherein the molar ratio of said phenol to said ethylating agent (phenol/ethylating agent) is 0.1-20.

12. The process according to claim 1, wherein said phenol and said ethylating agent are reacted in the presence of steam.

13. The process according to claim 12, wherein the molar ratio of said steam to said phenol (steam/phenol) is 0.05-50.

14. The process according to claim 13, wherein the ethylating agent is ethylene and the molar ratio of phenol to ethylene (phenol/ethylene) is 0.1-20.

15. The process according to claim 11, wherein said ethylating agent is ethanol.

16. The process according to claim 4, wherein said crystalline aluminosilicate is an H-crystalline alumino-silicate and in the ethylating reaction the weight hourly space velocity is 0.2-160 hr^-1 and a molar ratio of said phenol to said ethylating agent (phenol/ethylating agent) is 0.1-20.

17. The process according to claim 16, wherein said H-crystalline aluminosilicate is obtained by treating a crystalline aluminosilicate with an aqueous solution of one or more ammonium salts and then calcining thereby converting exchangeable cations positioned near the aluminum atoms into H⁺ ions.

18. The process according to claim 17, wherein said alkoxysilane is tetramethoxysilane or tetraethoxysilane.

19. The process according to claim 18, wherein said ethylating agent is ethylene and said ethylating reaction is conducted in the presence of steam in an amount of 0.05-50 moles per 1 mole of phenol.

20. The process according to claim 1, wherein the p-ethylphenol content of said mixture of ethylphenol isomers is in excess of 90%.