Supported rhodium catalyst, method of preparing same and process of producing acetic acid by methanol carbonylation using same

• US 5,364,963 A
• Filed: 12/20/1993
• Issued: 11/15/1994
• Est. Priority Date: 04/30/1993
• Status: Expired due to Term

• Current Assignee: Chiyoda Corporation (Mitsubishi Corporation)
• Original Assignee: Chiyoda Corporation (Mitsubishi Corporation)
• Inventors: Shimokawa, Kenji, Minami, Takeshi, Yoneda, Noriyuki, Shiroto, Yoshimi, Hamato, Kazuhiko
• Primary Examiner(s): PRESCOTT, ARTHUR
• Application Number:
  US08/169,639
• Time in Patent Office: 330 Days
• Field of Search: 562/519, 562/522, 562/607, 502/326, 502/402, 502/439, 502/507
• US Class Current: 562/519
• CPC Class Codes: B01J 2531/822 Rhodium
• CPC Class Codes: B01J 31/1658 immobilised by covalent linkages, i.e. pendant complexes with optional linking groups, e.g. on Wang or Merrifield resins
• CPC Class Codes: B01J 31/181 Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
• CPC Class Codes: C07C 51/12 on an oxygen-containing group in organic compounds, e.g. alcohols
• CPC Class Codes: C07C 53/08 Acetic acid pyroligneous acid C10C; preparation of vinegar C12J
• CPC Class Codes: Y10S 502/507 Synthetic resin, natural resin, polysaccaride, or polypeptide

Abstract

A methanol carbonylation catalyst includes a rhodium complex supported on a porous, cross-linked vinylpyridine resin, wherein the vinylpyridine resin has a cross-linking degree of 30-60%, a pore volume of 0.1-0.4 ml/g and an average pore diameter of 20-100 nm. The catalyst may be prepared by contacting the pyridine ring-containing resin with an aqueous solution containing rhodium ion and then contacting the resulting rhodium ion-carrying resin with carbon monoxide and an alkyl iodide in an organic solvent to convert the rhodium ion to a rhodium complex bound to the resin. Acetic acid is produced by reacting carbon monoxide with methanol at a temperature of 140°-250° C. and a partial pressure of carbon monoxide of 7-30 kg/cm² in the presence of an alkyl iodide and the above catalyst.

Claims

1. A catalyst for the production of acetic acid from methanol and carbon monoxide, comprising a rhodium complex supported on a porous, cross-linked vinylpyridine resin, wherein said vinylpyridine resin has a cross-linking degree of 30-60%, a pore volume of 0.2-0.4 cc/g and an average pore diameter of 20-100 nm.

2. A catalyst as claimed in claim 1, wherein said vinylpyridine resin is a copolymer of vinylpyridine and styrene.

3. A catalyst as claimed in to claim 1, wherein said vinylpyridine resin contains divinylbenzene as a cross-linking agent.

4. A catalyst as claimed in claim 1, wherein the amount of said rhodium complex is 0.2-2% by weight in terms of elemental rhodium based on the weight of said vinylpyridine resin.

11. A process for the production of acetic acid, comprising reacting carbon monoxide with methanol at a temperature of 140°

-250°

C. and a partial pressure of carbon monoxide of 7-30 kg/cm² in the presence of an alkyl iodide and a catalyst according to claim 1.

5. A method of preparing a supported rhodium catalyst, comprising the steps of:

(a) contacting a solid, pyridine ring-containing resin with an aqueous solution containing rhodium ion so that the rhodium ion is bound to said resin; and

(b) contacting said rhodium ion-carrying resin with carbon monoxide and an alkyl iodide in an organic solvent so that said rhodium ion is converted to a rhodium complex bound to said resin.

6. A method as claimed in claim 5, wherein said organic solvent includes a mixture of methanol with acetic acid.

7. A method as claimed in claim 5, wherein step (a) is performed at a temperature of 20°

-70°

C.

8. A method as claimed in claim 5, wherein step (b) is performed at a temperature of 50°

-250°

C. under a carbon monoxide partial pressure of 5-30 kg/cm².

9. A method as claimed in claim 5, wherein said pyridine ring-containing resin has a cross-linking degree of 30-60%, a pore volume of 0.1-0.4 cc/g and an average pore diameter of 20-100 nm.

10. A catalyst obtained by a method according to claim 9.