Rh/WxC Heterogeneous Catalyst for Preparing Acetic Acid by Carbonylation Reaction

Patent metadata

Field	Value
Publication number	US-2017342012-A1
Application number	US-201515540857-A
Country	US
Kind code	A1
Filing date	Aug 24, 2015
Priority date	Dec 29, 2014
Publication date	Nov 30, 2017
Grant date	—

Abstract

This invention relates to a catalyst used in a carbonylation of methanol using carbon monoxide to acetic acid, and more particularly to a heterogeneous catalyst represented by Rh/WxC (where x is an integer of 1 or 2) in which a complex of a rhodium compound and 3-benzoylpyridine is fixed on a support of tungsten carbide.

First claim

1 . A heterogeneous catalyst represented by Rh/WxC (where x is an integer of 1 or 2), used for preparing an acetic acid by a carbonylation of methanol using carbon monoxide in which a complex of a rhodium compound and 3-benzoylpyridine is fixed as an active material on a support of tungsten carbide.

2 . The heterogeneous catalyst of claim 1 , wherein the tungsten carbide support has a pore structure having an average pore size of 3 to 10 nm, with a specific surface area of 10 to 200 m 2 /g.

3 . The heterogeneous catalyst of claim 1 , wherein the complex is fixed in an amount of 3 to 30 wt % based on a total weight of the tungsten carbide support.

4 . A method of preparing a heterogeneous catalyst, comprising:
(S1) preparing a tungsten carbide support powder by thermally treating a tungsten carbide gel including a tungsten precursor, a carbon precursor and a silica molecular sieve template to a temperature of 800 to 1000° C. in presence of a gas mixture comprising hydrogen gas and nitrogen gas so as to harden a surface thereof and then by extracting and removing the silica molecular sieve template; (S2) preparing a complex by reacting a rhodium compound with 3-benzoylpyridine; and (S3) preparing a heterogeneous catalyst represented by Rh/WxC (wherein x is an integer of 1 or 2) by, fixing the complex prepared in (S2) on the tungsten carbide support prepared in (S1) complex.

5 . The method of claim 4 , wherein the thermally treating in (S1) is performed in the presence of the gas mixture including hydrogen gas and nitrogen gas through gradual heating under temperature gradient conditions in a manner in which a reaction temperature is increased to 250 to 300° C. from room temperature at a heating rate of 1 to 3° C./min, maintained for 3 to 7 hr, further increased to 550 to 650° C. at a heating rate of 1 to 3° C./min, maintained for 3 to 7 hr, additionally increased to 800 to 1000° C. at a heating rate of 1 to 3° C./min, and maintained for 3 to 7 hr.

6 . The method of claim 4 , wherein the silica molecular sieve is selected from a group consisting of SBA-15, MCM-41, and FSM-16.

7 . The method of claim 4 , wherein the tungsten carbide support prepared in (S1) has a pore structure having an average pore size of 3 to 10 nm, with a specific surface area of 10 to 200 m 2 /g.

8 . The method of claim 4 , wherein the rhodium compound used in (S2) is dichloro tetracarbonyl dirhodium (C 4 O 4 Cl 4 Rh 2 ).

9 . The method of claim 4 , wherein in (S3), the complex is fixed in an amount of 3 to 30 wt % based on a total weight of the tungsten carbide support.

10 . A method of preparing acetic acid, including carbonylation of methanol using carbon monoxide in presence of the heterogeneous catalyst of any one of claims 1 to 3 .

11 . The method of claim 10 , wherein a carbonylation of the methanol is performed at a reaction temperature of 50 to 200° C. under a reaction pressure of 10 to 70 bar.

12 . The method of claim 10 , wherein a [CO]/[CH 3 OH] molar ratio of methanol and carbon monoxide falls in a range from 0.5 to 10.

13 . The method of claim 10 , wherein the carbonylation of methanol is performed using, as an activity promoter, iodomethane (CH 3 I) and deionized water.

14 . The method of claim 13 , wherein a molar ratio of methanol/iodomethane/deionized water falls in a range of (10 to 80)/(10 to 60)/(10 to 30).

Assignees

• Korea Res Inst Chemical Tech
• Reserch Business Foundation Sungkyunkwan Univ

Inventors

• Park Jae Hyun
• Bae Jong Wook
• Chang Tae Sun
• Kim Beom Sik

Classifications

• B01J31/4046

  containing rhodium · CPC title

• C07C51/12 Primary

  on an oxygen-containing group in organic compounds, e.g. alcohols · CPC title

• B01J31/18

  containing nitrogen, phosphorus, arsenic or antimony {as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms (double metal cyanides B01J27/26; N-heterocyclic carbenes B01J31/2265)} · CPC title

• B01J35/10

  Operations & Transport · mapped topic

• B01J31/20

  Carbonyls · CPC title