Rendering petroleum oil as an environmentally carbon dioxide neutral source material for fuels, derived products and as a regenerative carbon source

• US 8,461,218 B2
• Filed: 04/07/2010
• Issued: 06/11/2013
• Est. Priority Date: 04/10/2009
• 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): PARSA, JAFAR F
• Application Number:
  US12/755,975
• Publication Number:
  US 20100261937A1
• Time in Patent Office: 1,161 Days
• Field of Search: 518/700, 518/703, 518/704
• US Class Current: 518/703
• CPC Class Codes: C07C 29/1518 one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
• CPC Class Codes: C07C 31/04 Methanol
• CPC Class Codes: C07C 41/09 by dehydration of compounds containing hydroxy groups
• CPC Class Codes: C07C 43/043 Dimethyl ether
• CPC Class Codes: C10L 1/02 essentially based on components consisting of carbon, hydrogen, and oxygen only

Abstract

The invention provides a method for rendering petroleum oil as an essentially environmentally carbon dioxide-neutral fuel and source material. Carbon dioxide produced from petroleum oil combustion is captured, purified, combined with steam and light hydrocarbon fractions, or with hydrogen, and reacted under reaction conditions sufficient to form methanol and/or dimethyl ether, which can be used as fuel or feedstock for derived synthetic hydrocarbons and products.

Claims

1. A method for rendering petroleum oil as an essentially environmentally carbon dioxide-neutral fuel and regenerative carbon source for producing methanol or dimethyl ether, which comprises:

subjecting petroleum oil to refining or combustion conditions sufficient to produce carbon dioxide;

capturing and purifying the produced carbon dioxide; and

combining the purified carbon dioxide with water and a suitable light hydrocarbon fraction having the formulation of C_nH_(2n+2), wherein n=1-4, in a molar ratio of 3;

(3n−

1);

1 as 3C_nH_(2n+2)+(3n−

1)H₂O+CO₂ to conduct a bi-reforming reaction by;

conducting steam reforming of the light hydrocarbon fraction with water to form carbon monoxide and hydrogen as follows;

(3−

1/n)[C_nH_(2n+2)+2nH₂O→

nCO+(2n+1)H₂];

conducting dry reforming of the light hydrocarbon fraction with carbon dioxide to form carbon monoxide and hydrogen as follows;

1/n[C_nH_(2n+2)+nCO₂→

2nCO+(n+1)H₂];

combining effluents including carbon monoxide and hydrogen from the steam and dry reforming reactions without separation of components of the reforming reactions or their effluents to produce a mixture of hydrogen and carbon monoxide having a molar ratio of hydrogen to carbon monoxide that is about 2;

1 to 2.1;

1; and

converting the molar mixture of hydrogen and carbon monoxide under conditions sufficient to exclusively form methanol, as follows;

(3n+1)CO +(6n+2)H₂→

(3n+1)CH₃OH,

so that the carbon dioxide generated from the petroleum oil is not introduced into the atmosphere, thus rendering the petroleum oil as an essentially environmentally carbon dioxide-neutral fuel and regenerative carbon source.

2. The method of claim 1 which further comprises:

recycling the methanol or dimethyl ether for use as a fuel or feedstock;

subjecting the methanol or dimethyl ether fuels or products made from the feedstock to further use to generate carbon dioxide; and

repeating the capturing, combining, recycling and conversion steps of the generated carbon dioxide so that the carbon dioxide produced from the methanol fuels or products made from the methanol feedstock also is not released into the atmosphere.

3. The method of claim 1, wherein the combustion of petroleum oil in a power plant generates energy.

4. The method of claim 1, wherein the carbon dioxide, suitable light hydrocarbon fraction, and water are combined in suitable molar ratios and are reacted in separate steps or in a single step to produce methanol.

5. The method of claim 1, wherein the suitable hydrocarbon fractions are saturated hydrocarbons including methane, ethane, propane and butanes.

6. The method of claim 1, which further comprises:

combusting the petroleum oil while producing carbon dioxide;

capturing the produced carbon dioxide on an adsorbent; and

treating the adsorbent to release the captured carbon dioxide therefrom for use in producing methanol or dimethyl ether.

7. The method of claim 6, wherein the adsorbent is treated with sufficient heating, reduced pressure, vacuum, gas purge, or a combination thereof to release the captured carbon dioxide.

8. The method of claim 6, wherein the absorbent is a polyamino-containing polymer deposited on a nano-structured supporting having a high surface area.

9. The method of claim 8, wherein the polyamino-containing polymer is polyethyleneimine and the support is nano-structured fused silica or alumina.

10. The method of claim 1, wherein the steam reforming and the dry reforming are performed simultaneously in a single bi-reforming step.

11. The method of claim 10, wherein the light hydrocarbon fraction, steam and carbon dioxide are reacted in a single step in a suitable molar ratio to form a mixture of hydrogen and carbon dioxide in a molar ratio of about 2:

1.

12. The method of claim 1, wherein the bi-reforming is carried out over a catalyst at a temperature between about 800°

C. and 1100°

C.

13. The method of claim 12, wherein the catalyst is provided on a support of a high surface area nano-structured fumed alumina or fumed silica.

14. The method of claim 12, wherein the catalyst comprises V, Ti, Ga, Mg, Cu, Ni, Mo, Bi, Fe, Mn, Co, Nb, Zr, La or Sn, or an oxide thereof.

15. The method of claim 12, wherein the catalyst comprises a single metal catalyst, a single metal oxide catalyst, a mixed catalyst of a metal and a metal oxide, or a mixed catalyst of at least one metal oxide and another metal oxide, the catalyst optionally being provided on an oxide support.

16. The method of claim 15, wherein the catalyst is NiO or a mixed catalyst of NiO, V₂O₅:

Ni₂O₃, Ni₂V₂O₇ and Ni₃V₂O₅.

17. The method of claim 15, wherein the catalyst is NiO supported on fumed alumina or NiO/V₂O₅ supported on fumed silica.

18. The method of claim 1 , which further comprises dehydrating methanol by removing water under conditions sufficient to produce dimethyl ether and recycling the water from dehydration during subsequent reforming.

19. The method of claim 18, which further comprises reacting the dimethyl ether in the presence of an acidic-basic or zeolitic catalyst under conditions sufficient to form ethylene or propylene.

20. The method of claim 19, which further comprises converting ethylene or propylene under conditions sufficient to produce synthetic hydrocarbons, chemicals, or polymers.

21. The method of claim 1, which further comprises combusting the produced methanol, optionally in a mixture that includes gasoline, in a power plant that produces energy with the combusted methanol while also generating carbon dioxide and recycling the generated carbon dioxide for producing methanol.

22. The method of claim 18, which further comprises combusting the produced dimethyl ether, as diesel oil substitute, optionally in a mixture that includes natural and light petroleum gas, in a power plant that produces energy while also generating carbon dioxide and recycling the generated carbon dioxide for producing methanol which in turn produces additional dimethyl ether.