Process for the production of ethylene glycol

• US 4,087,470 A
• Filed: 06/23/1976
• Issued: 05/02/1978
• Est. Priority Date: 06/23/1976
• Status: Expired due to Term

• Current Assignee: Chevron Research Company (Chevron Corp.)
• Original Assignee: Chevron Research Company (Chevron Corp.)
• Inventors: Suzuki, Shigeto
• Primary Examiner(s): Thomas, Jr., James O.
• Assistant Examiner(s): Breitenstein, G. T.
• Application Number:
  US05/699,099
• Time in Patent Office: 678 Days
• Field of Search: 260/635 D, 260/449 M
• US Class Current: 568/864
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/08 Ethanol
• CPC Class Codes: C07C 31/202 Ethylene glycol
• CPC Class Codes: C07C 51/10 by reaction with carbon monoxide
• CPC Class Codes: C07C 51/12 on an oxygen-containing group in organic compounds, e.g. alcohols
• CPC Class Codes: C07C 59/06 Glycolic acid
• CPC Class Codes: C07C 59/305 containing ether groups, groups, groups, or groups

Abstract

A cyclic process for producing ethylene glycol comprising the steps of:

(1) contacting formaldehyde with a synthesis gas comprising carbon monoxide and hydrogen in the presence of a catalytic amount of hydrogen fluoride under conditions effective to deplete carbon monoxide from the synthesis gas and produce glycolic acid and diglycolic acid;

(2) contacting the acid product of step (1) with ethylene glycol, diethylene glycol, or mixtures thereof under conditions effective to produce ethylene glycol glycolate and diglycolate, diethylene glycol glycolate and diglycolate, or mixtures thereof;

(3) removing residual carbon monoxide from the carbon monoxide depleted synthesis gas of step (1) thereby producing a hydrogen rich gas;

(4) contacting the glycolate and diglycolate product of step (2) with the hydrogen-rich gas mixture of step (3) under conditions effective to produce ethylene glycol, diethylene glycol, or mixtures thereof; and

(5) recycling from step (4) to step (2) an amount of the glycol product effective to esterify substantially all the acid product present in the reaction zone of step (2).

Claims

1. A process for producing ethylene glycol which comprises the steps of:

(1) contacting formaldehyde with a synthesis gas comprising carbon monoxide and hydrogen in the presence of hydrogen fluoride under conditions effective to deplete carbon monoxide from the synthesis gas and produce glycolic acid and diglycolic acid;

(2) contacting the acid product of step (1) with ethylene glycol, diethylene glycol or mixtures thereof under conditions effective to produce ethylene glycol glycolates, diethylene glycol glycolates or mixtures thereof;

(3) removing residual carbon monoxide and hydrogen fluoride from the carbon monoxide depleted synthesis gas of step (1) to produce a hydrogen-rich gas stream;

(4) contacting the glycolate product of step (2) with the hydrogen-rich gas stream of step (3) under conditions effective to produce ethylene glycol or diethylene glycol; and

(5) recycling sufficient glycol product from the product of step (4) to the esterification zone of step (2) so as to maintain a molar excess of glycol during esterification.

2. A process according to claim 1 wherein the source of hydrogen in hydrogenation step (4) is the carbon monoxide depleted hydrogen stream of step (1) which has been hydrogenated to form a hydrogen and methane mixture.

3. A process according to claim 1 wherein the formaldehyde and synthesis gas are contacted at a temperature between 0°

and about 100°

C and a carbon monoxide partial pressure between 10 psig and 4000 psig.

4. A process according to claim 1 wherein the formaldehyde and synthesis gas are contacted at a temperature between 20°

and about 60°

C and a carbon monoxide partial pressure between 10 psig and 3000 psig.

5. A process according to claim 1 wherein step (1) is carried out in the presence of water.

6. A process according to claim 1 wherein the acid product formed in step (1) is dehydrated prior to step (2) to form various anhydrous forms of glycolic acid.

7. A process according to claim 1 wherein the glycolic acid is contacted with ethylene glycol or diethylene glycol at a temperature of from about 150°

to about 250°

C and a pressure of from about 0 psig to about 100 psig.

8. A process according to claim 1 wherein the glycolate product is contacted with hydrogen at a temperature of from about 150°

to about 300°

C and a pressure of from about 500 psig to about 5000 psig, in the presence of a hydrogenation catalyst.