Rh/WxC heterogeneous catalyst for preparing acetic acid by carbonylation reaction

Patent metadata

Field	Value
Publication number	US-10196339-B2
Application number	US-201515540857-A
Country	US
Kind code	B2
Filing date	Aug 24, 2015
Priority date	Dec 29, 2014
Publication date	Feb 5, 2019
Grant date	Feb 5, 2019

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

The invention claimed is:

1. 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).

2. The method of claim 1 , 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.

3. The method of claim 1 , wherein the silica molecular sieve is selected from a group consisting of SBA-15, MCM-41, and FSM-16.

4. The method of claim 1 , 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.

5. The method of claim 1 , wherein the rhodium compound used in (S2) is dichloro tetracarbonyl dirhodium (C 4 O 4 Cl 42 Rh 2 ).

6. The method of claim 1 , 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.

Assignees

• Korea Res Inst Chemical Tech

Inventors

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

Classifications

• B01J37/0203

  the impregnation liquid containing organic compounds · CPC title

• B01J35/1061

  Operations & Transport · mapped topic

• Y02P20/588

  Cross-Sectional Technologies · mapped topic

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• B01J2523/822

  Rhodium · CPC title