Processes for producing aromatic hydrocarbon, p-xylene and terephthalic acid

Patent metadata

Field	Value
Publication number	US-10604455-B2
Application number	US-201615291989-A
Country	US
Kind code	B2
Filing date	Oct 12, 2016
Priority date	Oct 12, 2015
Publication date	Mar 31, 2020
Grant date	Mar 31, 2020

Abstract

The present invention relates to a process for preparing an aromatic hydrocarbon, and processes for producing p-xylene and terephthalic acid. The process for producing said aromatic hydrocarbon comprises a step of contacting an olefin with a diene in the presence of a catalyst to produce an aromatic hydrocarbon, which is characterized in that, at least a part of said olefin is substituted with dienophile. The reaction pressure can be reduced and the xylene selectivity can be increased with the improvement of the present invention.

First claim

The invention claimed is:

1. A process for preparing an aromatic hydrocarbon, comprising a step of reacting a reaction mixture comprising a diene, an alcohol, and optionally an olefin in the presence of a catalyst to produce a product mixture comprising aromatic hydrocarbons,
wherein a molar percentage of said alcohol is 5-100 mol % of a total amount of said olefin and said alcohol,
wherein said diene is of formula (I):

wherein R 1 and R 2 are identical or different, and are selected from a group consisting of hydrogen, an optionally substituted C1-20 linear or branched alkyl, an optionally substituted C2-20 linear or branched alkenyl, an optionally substituted C2-20 linear or branched alkynyl, an optionally substituted C3-20 cycloalkyl and an optionally substituted C6-20 aryl respectively and independently,
said olefin is selected from C2-C10 olefins and mixtures thereof, and
said alcohol is selected from C2-C10 alcohols and mixtures thereof, and
wherein said catalyst comprises 20 to 80 weight parts of a molecular sieve, 20 to 80 weight parts of a binder, and 0 to 10 weight parts of an adjuvant, wherein the molecular sieve is selected from the group consisting of ZSM-type molecular sieve, Y-type molecular sieve, beta-type molecular sieve, MCM-type molecular sieve, and combinations thereof, the binder is selected from the group consisting of silica sol, pseudo-boehmite, alumina, acid-treated clay, kaolin, montmorillonite, bentonite, combinations thereof, and the adjuvant comprises Na, Ca, K, Be, Ba, V, Nb, Mo, W, Mn, Re, Ga, Ru, Pd, Pt, Ag, B, Sn, P, Sb, Ce or a combination of two or more thereof.

2. The process according to claim 1 , wherein said ZSM-type molecular sieve has a SiO 2 /Al 2 O 3 molar ratio of 10-500, said Y-type molecular sieve has a SiO 2 /Al 2 O 3 molar ratio of 2-80, said beta-type molecular sieve has a SiO 2 /Al 2 O 3 molar ratio of 10-150, said MCM-type molecular sieve has a SiO 2 /Al 2 O 3 molar ratio of 20-250.

3. The process according to claim 1 , wherein a molar ratio of said diene to the total of said alcohol and said olefin is 0.1-10.

4. The process according to claim 1 , wherein said reacting step is conducted at a reaction temperature of 80 to 400° C. and under a reaction pressure of 0.5 to 10 MPa.

5. The process according to claim 1 , wherein said reacting step is conducted at a predetermined reaction pressure, and said reaction pressure decreases as the molar percentage of said alcohol in the total amount of said olefin and said alcohol increases.

6. The process according to claim 1 , wherein said diene and/or said alcohol is derived from a biomass material selected from the group consisting of xylitol, glucose, cellobiose, cellulose, hemicellulose, lignin, paper sludge, waste paper, sugar cane bagasse, glucose, wood, corn cobs, corn stalks, rice straw, and mixtures thereof.

7. The process according to claim 1 , further comprising catalytically converting and optionally catalytically hydrogenating the biomass material to produce said diene and/or said alcohol.

8. A process for producing p-xylene, comprising:
producing aromatic hydrocarbons according to the process of claim 1 ; and
separating p-xylene from said aromatic hydrocarbons.

9. A process for producing terephthalic acid, comprising:
producing p-xylene according to the process of claim 8 ; and
converting p-xylene to terephthalic acid.

10. The process according to claim 3 , wherein the molar percentage of said alcohol is 50 mol % or more of the total amount of said olefin and said alcohol.

11. The process according to claim 3 , wherein the molar percentage of said alcohol is 90 mol % or more of the total amount of said olefin and said alcohol.

12. The process according to claim 1 , wherein R 1 and R 2 are identical or different, and are selected from a group consisting of hydrogen, an optionally substituted C1-5 linear or branched alkyl, and an optionally substituted C2-10 linear or branched alkenyl.

13. The process according to claim 1 , wherein R 1 and R 2 are both methyl.

14. The process according to claim 1 , wherein said olefin is selected from the group consisting of C2-C10 α-olefins and mixtures thereof.

15. The process according to claim 1 , wherein said olefin is ethylene, propene, or a mixture thereof.

16. The process according to claim 1 , wherein said alcohol is selected from the group consisting of C2-C4 alcohols and mixtures thereof.

17. The process according to claim 1 , wherein said alcohol is selected from the group consisting of ethanol, n-propanol, isopropanol, sec-butanol, and mixtures thereof.

18. The process according to claim 1 , wherein said catalyst comprises 20 to 80 weight parts of the molecular sieve, and 20 to 80 weight parts of the binder.

19. The process according to claim 1 , wherein the molar percentage of said alcohol is 100 mol % of the total amount of said olefin and said alcohol.

Assignees

• China Petroleum & Chem Corp
• Shanghai Res Inst Petrochemical Tech Sinopec

Inventors

• Kong Dejin
• Tsang Sc Edman
• Teixeria Ivo
• Song Qi

Classifications

• C07C2521/12

  Silica and alumina · CPC title

• C07C2529/80

  Mixtures of different zeolites · CPC title

• C07C2529/40

  of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 · CPC title

• C07C1/2072 Primary

  by condensation (C07C2/86 takes precedence) · CPC title

• C07C15/04

  Benzene · CPC title