Efficient and selective chemical recycling of carbon dioxide to methanol, dimethyl ether and derived products

• US 8,212,088 B2
• Filed: 08/07/2009
• Issued: 07/03/2012
• Est. Priority Date: 04/15/2005
• Status: Active Grant

• Current Assignee: University of Southern California
• Original Assignee: University of Southern California
• Inventors: Olah, George A., Prakash, G. K. Surya
• Primary Examiner(s): Price, Elvis O
• Application Number:
  US12/537,647
• Publication Number:
  US 20090293348A1
• Time in Patent Office: 1,061 Days
• Field of Search: 568/884, 568/885
• US Class Current: 568/884
• CPC Class Codes: C07C 1/20 starting from organic compounds containing only oxygen atoms as heteroatoms
• CPC Class Codes: C07C 11/02 Alkenes
• CPC Class Codes: C07C 29/04 by hydration of carbon-to-carbon double bonds
• CPC Class Codes: C07C 29/136 of >C=O containing groups, e.g. —COOH
• CPC Class Codes: C07C 29/14 of a —CHO group
• CPC Class Codes: C07C 29/141 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 29/149 with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/04 Methanol
• CPC Class Codes: C07C 31/08 Ethanol
• CPC Class Codes: C07C 31/10 containing three carbon atoms
• CPC Class Codes: C07C 41/09 by dehydration of compounds containing hydroxy groups
• CPC Class Codes: C07C 43/043 Dimethyl ether
• CPC Class Codes: C07C 51/15 by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
• CPC Class Codes: C07C 53/02 Formic acid
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 67/38 by addition to an unsaturated carbon-to-carbon bond
• CPC Class Codes: C07C 68/01 from carbon monoxide and oxygen
• CPC Class Codes: C07C 68/02 from phosgene or haloformates
• CPC Class Codes: C07C 69/06 of monohydroxylic compounds
• CPC Class Codes: C07C 69/96 Esters of carbonic or haloformic acids
• CPC Class Codes: C25B 3/25 : Reduction

Abstract

An efficient and environmentally beneficial method of recycling and producing methanol from varied sources of carbon dioxide including flue gases of fossil fuel burning powerplants, industrial exhaust gases or the atmosphere itself. Converting carbon dioxide by chemical or electrochemical reduction seconardy treatment to produce essentially methanol, dimethyl ether and derived products.

Claims

1. An environmentally beneficial method of preparing a renewable fuel, which method comprises:

obtaining carbon dioxide from a natural or chemical source that would otherwise be present in or discharged into the atmosphere; and

producing an energy storage and transportation material or a fuel sufficient to generate energy by hydrogenatively converting the carbon dioxide thus obtained under conditions sufficient to produce methanol as the material or fuel.

2. The method of claim 1, wherein the methanol is produced by reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde to formic acid and methanol.

3. The method of claim 2, wherein the methanol is produced by generating carbon monoxide from the carbon dioxide through a high temperature reaction with carbon, reacting the carbon monoxide with the previously produced methanol under conditions sufficient to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form additional methanol.

4. The method of claim 1, wherein the methanol is produced by reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, augmenting the reaction mixture by reacting, without separation of the reaction mixture, the formaldehyde into methanol with some of the formic acid used as a hydrogen source, and reacting some of the formic acid with methanol to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form methanol.

5. The method of claim 1, which further comprises transporting the thus produced methanol fuel to a facility where the fuel is to be combusted to generate energy.

6. The method of claim 5, which further comprises combusting the methanol fuel in a power plant to form an exhaust stream that contains carbon dioxide, and recovering the carbon dioxide of the exhaust stream for use as the chemically recyclable source of carbon dioxide for preparing additional fuel.

7. The method of claim 1 wherein the methanol is produced by hydrogenatively converting the carbon dioxide to form a reaction mixture that contains methanol, formic acid and formaldehyde, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde and formic acid to methanol.

8. The method of claim 7, which comprises reacting the formaldehyde with the co-formed formic acid as a hydrogen source, without separation of the reaction mixture, into methanol, including reacting of the formic acid with methanol to form methyl formate, followed by hydrogenating the methyl formate under conditions sufficient to form double the starting amount of methanol.

9. The method of claim 8, wherein the hydrogen needed for the hydrogenation of methyl formate is obtained at least in part from cleavage of the formic acid from the reaction mixture.

10. The method of claim 1, wherein the hydrogen needed for the hydrogenative conversion of carbon dioxide is obtained by the reforming of methane or natural gas or by electrolysis of water using an available energy source.

11. The method of claim 1, which further comprises combusting the fuel to form an exhaust stream that contains carbon dioxide and in a manner that allows collection of the exhaust stream, and recovering the carbon dioxide of the exhaust stream for use as the chemically recyclable source of carbon dioxide for preparing additional fuel.

12. The method of claim 10, wherein the exhaust stream is obtained by combusting the fuel in a fossil fuel burning power or industrial plant.

13. The method of claim 1, which further comprises dehydrating the methanol under conditions sufficient to produce dimethyl ether;

using the dimethyl ether as the fuel or as a component of the fuel.

14. The method of claim 13, which further comprises utilizing. as the convenient energy storage and transportation materials, the methanol or dimethyl ether in order to minimize or eliminate the disadvantages or dangers inherent in the use and transportation of hydrogen, LNG or LPG.

15. An environmentally beneficial method of preparing a renewable fuel, which method comprises:

obtaining carbon dioxide from a natural or chemical source; and

producing an energy storage and transportation material or a fuel sufficient to generate energy by hydrogenatively converting the carbon dioxide thus obtained under conditions sufficient to produce methanol as the material or fuel.

16. The method of claim 15, wherein the chemical source is an exhaust stream collected from the burning or combustion of a fossil fuel.

17. The method of claim 15, wherein the natural or chemical source of carbon dioxide is the atmosphere, an exhaust stream from a power or industrial plant, or a source accompanying natural gas.

18. The method of claim 15, wherein the carbon dioxide is captured and obtained from the source and is converted under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde to formic acid and methanol.

19. The method of claim 15, wherein the carbon dioxide is captured and obtained from the source and is reduced under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, augmenting the reaction mixture by reacting, without separation of the reaction mixture, the formaldehyde into methanol with some of the formic acid used as a hydrogen source, and reacting some of the formic acid with methanol to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form methanol.

20. An environmentally beneficial method of reducing the carbon dioxide content of the atmosphere by recycling carbon dioxide and producing methanol using a reductive conversion of an available source of carbon dioxide from a natural or chemical source, which method comprises:

(A) reducing the carbon dioxide under conditions sufficient to produce a reaction mixture containing formic acid with concomittant formation of formaldehyde and small amounts of methanol and methane, followed, without separation of the reaction mixture, by a treatment step conducted under conditions sufficient to convert the formaldehyde to formic acid and methanol;

or

(B) augmenting the reaction mixture of (A) by reacting the formaldehyde with some of the formic acid as a hydrogen source, without separation of the reaction mixture, into methanol, and by reacting some of the formic acid with methanol to form methyl formate, followed by catalytically hydrogenating the methyl formate under conditions sufficient to form methanol;

or

(C) generating carbon monoxide from the carbon dioxide through a high temperature reaction with carbon, reacting the carbon monoxide with methanol produced in (A) under conditions sufficient to form methyl formate, followed by catalytic hydrogenation of the methyl formate under conditions sufficient to form methanol.