Methods of higher alcohol synthesis

• US 8,785,699 B2
• Filed: 04/19/2013
• Issued: 07/22/2014
• Est. Priority Date: 07/17/2008
• Status: Expired due to Fees

• Current Assignee: Pioneer Energy, Inc.
• Original Assignee: Pioneer Energy, Inc.
• Inventors: White, Emily Bostwick, Wilson, Cherie, Berggren, Mark, Zubrin, Robert M.
• Primary Examiner(s): WITHERSPOON, SIKARL A
• Application Number:
  US13/866,948
• Publication Number:
  US 20130232861A1
• Time in Patent Office: 459 Days
• Field of Search: 568/905, 502/184, 502/324, 502/343, 502/346
• US Class Current: 568/905
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 21/185 Carbon nanotubes carbon nanotubes per se C01B32/15
• CPC Class Codes: B01J 23/007 Mixed salts
• CPC Class Codes: B01J 23/34 Manganese
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/80 with zinc, cadmium or mercury
• CPC Class Codes: B01J 23/8892 Manganese
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C07C 2523/04 Alkali metals
• CPC Class Codes: C07C 29/154 containing copper, silver, gold, or compounds thereof
• CPC Class Codes: C07C 29/34 by condensation involving hydroxy groups or the mineral ester groups derived therefrom, e.g. Guerbet reaction
• 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 31/12 containing four carbon atoms
• CPC Class Codes: C10G 2/33 characterised by the catalyst used
• CPC Class Codes: C10L 1/1824 mono-hydroxy
• CPC Class Codes: Y02P 20/52 using catalysts, e.g. selective catalysts

Abstract

Systems, catalysts, and methods are provided for transforming carbon based material into synthetic mixed alcohol fuel.

Claims

1. A method of producing liquid fuel from synthesis gas, the method comprising reacting the gas at pressures between about 500 and about 3000 psi and temperatures between about 200°

C. and about 400°

C. over a catalyst, wherein the catalyst consists essentially of copper, zinc, and potassium on a substrate.

2. The method of claim 1, wherein the catalyst further comprises cobalt, manganese, or both cobalt and manganese.

3. The method of claim 1, wherein the substrate is selected from the group consisting of silica, carbon nanotubes, and aluminum oxide.

4. The method of claim 1, wherein the liquid fuel produced comprises methanol, ethanol, propanol, butanol, hydrocarbons, and/or mixtures thereof.

5. The method of claim 4, wherein the methanol component of the product is removed via distillation to increase the energy content of the remaining fuel.

6. The method of claim 1, wherein the synthesis gas is produced by steam reforming of biomass, corn stover, lignin, hemicellulose, coal, natural gas, landfill gas, and/or trash.

7. The method of claim 1, wherein the synthesis gas is produced using the reverse water gas shift to convert CO₂ to CO.

8. The method of claim 1, wherein waste CO₂ and hydrogen are converted into CO using reverse water gas shift, and wherein the CO is used as synthesis gas.

9. A method of producing butanol, the method comprising reacting methanol with ethanol, propanol, or mixtures thereof at pressures under 3000 psi and temperatures between about 200°

C. and about 400°

C. using a catalyst, wherein the catalyst consists essentially of copper on hydrotalcite.

10. The method of claim 9, wherein the hydrotalcite is a strongly basic variety and has a MgO to Al₂O₃ ratio greater than 1:

1.

11. The method of claim 9, wherein the methanol is produced on site by reacting synthesis gas on a copper and zinc catalyst at pressures between about 100 psi and about 3000 psi and temperatures between about 200°

C. and about 400°

C.

12. The method of claim 9, wherein the methanol, ethanol, and/or propanol is produced from synthesis gas derived from of biomass, corn stover, lignin, hemicellulose, coal, natural gas, landfill gas, and/or trash.

13. A method of producing a mixture of butanol, higher alcohols, and hydrocarbons from synthesis gas, the method comprising:

(a) reacting the gas at pressures between about 500 and about 3000 psi and temperatures between about 200°

C. and about 400°

C. over a catalyst, wherein the catalyst consists essentially of copper, zinc, and potassium on a substrate, to yield a mixture of alcohols and hydrocarbons comprising methanol, ethanol, propanol and butanol, as well as other alcohols and hydrocarbons; and

(b) reacting the methanol with the ethanol and/or propanol to produce butanol at pressures under 3000 psi and temperatures between about 200°

C. and about 400°

C. using a catalyst comprising copper on hydrotalcite.

14. The method of claim 13, wherein the catalyst of step (a) further comprises cobalt, manganese, or both cobalt and manganese.

15. The method of claim 13, wherein the hydrotalcite catalyst employed in step (b) is a basic variety and has a MgO to Al₂O₃ ratio greater than 1:

1.

16. The method of claim 13, wherein the synthesis gas is produced by steam reformation of biomass, corn stover, lignin, hemicellulose, coal, natural gas, landfill gas, and/or trash.

17. The method of claim 13, wherein the synthesis gas is produced using the reverse water gas shift to convert CO₂ to CO.

18. A catalyst consisting essentially of copper, zinc, and potassium deposited on a substrate.

19. A catalyst consisting essentially of copper, zinc, and potassium and at least one of cobalt and/or manganese deposited on a substrate.

20. A catalyst consisting essentially of copper on hydrotalcite, wherein the hydrotalcite is a strongly basic variety with a MgO to Al₂O₃ ratio greater than 1:

1.

21. The catalyst of claim 20, wherein the hydrotalcite comprises carbon nanotubes.

22. The catalyst of claim 20, wherein the source for Al and/or Cu are nanomaterials.

23. The catalyst of claim 20, wherein a molecular template for ethanol is created by evaporating ethanol from the catalyst suspension.

24. The catalyst of claim 20, wherein the catalyst is calcined in flowing air or a mixture of gases containing oxygen for about 2 to about 10 hours at a temperature between about 200°

C. and about 1000°

C.