Method for producing aromatic compound from biomass-derived acetic acid

Patent metadata

Field	Value
Publication number	US-9714207-B2
Application number	US-201414896141-A
Country	US
Kind code	B2
Filing date	Jun 3, 2014
Priority date	Jun 5, 2013
Publication date	Jul 25, 2017
Grant date	Jul 25, 2017

Abstract

In a specific example according to the present invention, a method is disclosed in which a catalytic reaction is used in order to convert acetic acid, which has been produced by the biological processing or physicochemical processing of biomass, into an aromatic compound constituting a raw material for a high-added-value product such as BTX and, more particularly, p-xylene.

First claim

The invention claimed is:

1. A method for producing an aromatic compound from acetic acid, comprising:
a1) providing acetic acid;
b1) converting said acetic acid into an acetate salt; pyrolyzing the acetate salt to an acetone; and
c1) converting the acetone into an aromatic compound in the presence of a ruthenium-supported niobia catalyst (Ru/Nb);
wherein the ruthenium-supported niobia catalyst (Ru/Nb) contains ruthenium in an amount of 0.3 to 2.5% by weight on an elemental basis.

2. The method of claim 1 , wherein the acetic acid is biomass-derived acetic acid.

3. The method of claim 1 , wherein the ruthenium of the ruthenium-supported niobia catalyst has a particle size or crystal size of 1 to 20 nm.

4. The method of claim 1 , wherein the niobia of the ruthenium-supported niobia catalyst is thermally treated at 300 to 1000° C.

5. The method of claim 1 , wherein step c1) is conducted at a temperature of 250 to 400° C., a hydrogen pressure of 5 to 100 bar, and a hydrogen (H 2 )/acetone molar ratio of 0.5 to 50.

6. The method of claim 5 , wherein step c1) is conducted at a space velocity (WHSV) of 0.1 to 10 h −1 in a continuous mode, or is conducted in the presence of 0.1 to 10 g the ruthenium-supported niobia catalyst based on 100 cc of acetone in a batch mode.

7. The method of claim 6 , wherein the acetone is converted into acetone at a rate of at least 50% with a selectivity for aromatic compounds of at least 50% in step c1).

8. The method of claim 7 , wherein the aromatic compound further comprises naphthenic compound and olefinic compound and wherein overall selectivity for aromatic and naphthenic compounds is at least 60% in step c1), with an olefinic content of 3 wt % or less in the product of step c1).

9. The method of claim 1 , wherein the aromatic compound is a monocyclic aromatic compound having 6 to 15 carbon atoms.

10. The method of claim 9 , wherein the aromatic compound is an unsubstituted, mono- or polysubstituted monocyclic aromatic compound, the substituent being —CH 3 , —C 2 H 5 , —C 3 H 7 , or —C 4 H 9 .

11. The method of claim 10 , wherein the aromatic compound is selected from the group consisting of xylene, trimethyl benzene, tetramethyl benzene, pentamethyl benzene, dimethylethyl benzene, dimethylpropyl benzene, dimethylbutyl benzene, trimethylpropyl benzene, and trimethylbutyl benzene.

12. The method of claim 1 , further subjecting the recovered aromatic compound to trans-alkylation to obtain an aromatic product selected from the group consisting of benzene, toluene, and xylene.

13. The method of claim 12 , wherein the xylene is divided into para-xylene and other xylenes, followed by isomerizing the other xylenes into para-xylene.

14. The method of claim 1 , wherein the acetate is calcium acetate.

15. A method for producing an aromatic compound from biomass-derived acetic acid, comprising:
a2) providing an aqueous solution containing the biomass-derived acetic acid;
b2) reacting the aqueous solution containing the biomass-derived acetic acid in presence of a catalyst selected from the group consisting of zirconia, titania, alumina, silica, silica-alumina to give an acetone-containing aqueous solution; and
c2) converting the acetone of the acetone-containing aqueous solution into an aromatic compound in presence of a ruthenium-supported niobia catalyst (Ru/Nb); and
d2) separating water from the product of step c2) to recover the aromatic compound,
wherein the ruthenium-supported niobia catalyst (Ru/Nb) contains ruthenium in an amount of 0.3 to 2.5% by weight on an elemental basis.

16. The method of claim 15 , wherein the acetic acid-containing aqueous solution of step a2) has an acetic acid concentration of 1 to 90 wt %, and the acetone-containing aqueous solution of step b2) has an acetone concentration of 1 to 90 wt %.

17. The method of claim 15 , wherein step c2) is carried out at a temperature of 250 to 400° C., a hydrogen pressure of 5 to 100 bar, and a hydrogen (H 2 )/acetone molar ratio of 0.5 to 50.

18. The method of claim 17 , wherein step c2) is conducted at a space velocity (WHSV) of 0.1 to 10 h −1 in a continuous mode, or is conducted in the presence of 0.1 to 10 g of the ruthenium-supported niobia catalyst based on 100 cc of acetone in a batch mode.

19. The method of claim 18 , wherein the acetone is converted into acetone at a rate of at least 50% with a selectivity for aromatic compounds of at least 50% in step c2).

20. The method of claim 19 , wherein the aromatic compound further comprises naphthenic compound and olefinic compound and wherein overall selectivity for aromatic compound and naphthenic compounds is at least 60% in step c2), with an olefinic content of 3 wt % or less in the product of step c2).

21. The method claim 15 , wherein an aromatic compound is recovered from the product of step c2) by phase separation in step d2).

22. The method of claim 15 , wherein steps b2) to d2) are carried out consecutively in a single reactor.

23. The method of claim 15 , wherein the ruthenium of the ruthenium-supported niobia catalyst has a particle size or crystal size of 1 to 20 nm.

24. The method of claim 15 , wherein the niobia of the ruthenium-supported niobia catalyst is thermally treated at 300 to 1000° C.

25. The method of claim 15 , wherein thee aromatic compound is a monocyclic aromatic compound having 6 to 15 carbon atoms.

26. The method of claim 15 , further subjecting the recovered aromatic compound to trans-alkylation to obtain an aromatic product selected from the group consisting of benzene, toluene, and xylene.

Assignees

• Sk Innovation Co Ltd

Inventors

• Kim Hee Soo
• Lee Ho Won
• Lim Seon Ju
• Park Dong Ryul

Classifications

• Y02P20/52

  using catalysts, e.g. selective catalysts · CPC title

• C07C6/126

  of more than one hydrocarbon · CPC title

• C07C1/2076

  by a transformation in which at least one -C(=O)- moiety is eliminated · CPC title

• C07C45/66

  by dehydration · CPC title

• C07C45/74 Primary

  combined with dehydration · CPC title