Renewable diesel and jet fuel from microbial sources

• US 9,434,909 B2
• Filed: 02/19/2014
• Issued: 09/06/2016
• Est. Priority Date: 06/01/2007
• Status: Expired due to Fees

• Current Assignee: Corbion Biotech, Inc. (Corbion NV)
• Original Assignee: Solazyme Inc.
• Inventors: Trimbur, Donald E., Im, Chung-Soon, Dillon, Harrison F., Day, Anthony G., Franklin, Scott, Coragliotti, Anna
• Primary Examiner(s): Chen, Shin Lin
• Application Number:
  US14/184,288
• Publication Number:
  US 20140170716A1
• Time in Patent Office: 930 Days
• Field of Search: 435/159, 435/195, 435/257.2, 424/93.21, 536/23.2
• US Class Current: 1/1
• CPC Class Codes: C07H 21/04 with deoxyribosyl as saccharide radical
• CPC Class Codes: C10L 1/026 for compression ignition
• CPC Class Codes: C10L 1/06 for spark ignition
• CPC Class Codes: C10L 2200/0484 Vegetable or animal oils
• CPC Class Codes: C10L 2270/026 for diesel engines, e.g. automobiles, stationary, marine
• CPC Class Codes: C10L 2270/04 for turbines, planes, power generation
• CPC Class Codes: C11C 3/00 Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom sulfonated fats or oils C07C309/62; factice C08H; drying oils C09F
• CPC Class Codes: C12N 1/12 Unicellular algae; Culture media therefor as new plants A01H13/00
• CPC Class Codes: C12N 1/32 Processes using, or culture media containing, lower alkanols, i.e. C1 to C6
• CPC Class Codes: C12N 15/79 Vectors or expression systems specially adapted for eukaryotic hosts
• CPC Class Codes: C12N 9/0006 acting on CH-OH groups as donors (1.1)
• CPC Class Codes: C12N 9/0008 acting on the aldehyde or oxo group of donors (1.2)
• CPC Class Codes: C12N 9/1205 Phosphotransferases with an alcohol group as acceptor (2.7.1), e.g. protein kinases
• CPC Class Codes: C12N 9/14 Hydrolases (3)
• CPC Class Codes: C12N 9/16 acting on ester bonds (3.1)
• CPC Class Codes: C12N 9/20 Triglyceride splitting, e.g. by means of lipase
• CPC Class Codes: C12N 9/2408 acting on alpha -1,4-glucosidic bonds
• CPC Class Codes: C12N 9/2431 Beta-fructofuranosidase (3.2.1.26), i.e. invertase
• CPC Class Codes: C12N 9/88 Lyases (4.)
• CPC Class Codes: C12P 21/06 produced by the hydrolysis of a peptide bond, e.g. hydrolysate products preparing foodstuffs by protein hydrolysis A23J3/00
• CPC Class Codes: C12P 5/02 : acyclic C12P5/007 takes precedence
• CPC Class Codes: C12P 7/6409 : Fatty acids
• CPC Class Codes: C12P 7/6458 : by transesterification, e.g. interesterification, ester interchange, alcoholysis or acidolysis
• CPC Class Codes: C12P 7/6463 : obtained from glyceride producing microorganisms, e.g. single cell oil
• CPC Class Codes: C12P 7/649 : Biodiesel, i.e. fatty acid alkyl esters
• CPC Class Codes: C12Y 302/01026 : Beta-fructofuranosidase (3.2.1.26), i.e. invertase
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02E 50/30 : Fuel from waste, e.g. synthetic alcohol or diesel
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02T 50/678 : Aviation using fuels of non-fossil origin

Abstract

The invention provides methods of manufacturing alkanes from triglyceride oils produced through fermentation of oil-bearing microbes. The processes provided herein can utilize a variety of carbohydrate feedstocks including cane bagasse, sugar beet pulp, corn stover, glycerol, corn starch, sorghum, molasses, waste glycerol, and other renewable materials. These processes further comprise hydrotreating, hydrocracking, isomerization, distillation, and other petrochemical processes for use with oil-bearing microbes and products derived therefrom to manufacture fuels. Particular embodiments include the manufacture of ASTM D975 and ASTM D1655 compliant fuels. Genetically engineered microbes provided herein can be used in the manufacture of renewable diesel and renewable jet fuel.

Claims

1. A method for producing renewable diesel, comprising:

(a) providing glycerolipid isolated from a population of microalgae of the genus Prototheca, the population of microalgae heterotrophically cultivated in the presence of sucrose, wherein the microalgae are genetically engineered to express sucrose invertase; and

(b) subjecting the isolated glycerolipid to chemical reactions to generate alkanes, wherein the chemical reactions are selected from the group consisting of hydrodeoxygenation, isomerization, and distillation to remove naptha,

whereby renewable diesel is produced.

2. The method of claim 1, wherein the microalgae are of the species Prototheca moriformis.

3. The method of claim 1, wherein the chemical reactions are performed in the presence of a catalyst.

4. The method of claim 3, wherein the catalyst in the hydrodeoxygenation step contains metals selected from the group consisting of Pd, Pt, Ni, NiMo and CoMo.

5. The method of claim 3, wherein the catalyst in the hydrodeoxygenation step contains metals selected from the group consisting of NiMo/Al₂O₃ and CoMo/Al₂O₃.

6. The method of claim 3, wherein the catalyst in the isomerization step contains metals selected from the group consisting of SAPO-11, SAPO41, ZSM-22, ZSM-23, ferrierite, Pt, Pd, Ni, Al₂O₃ and SiO₂.

7. The method of claim 3, wherein the catalyst in the isomerization step contains metals selected from the group consisting of Pt/SAPO-11/ Al₂O₃, Pt/ZSM-22/ Al₂O₃, Pt/ZSM-23/ Al₂O₃, and Pt/SAPO-11/SiO₂.

8. The method of claim 1, wherein the hydrodeoxygenation step is performed at temperatures between 200°

C. and 500°

C.

9. The method of claim 1 , wherein the hydrodeoxygenation step is performed at pressures between 20 and 150 bar.

10. The method of claim 1, wherein the isomerization step is performed at pressures between 20 and 150 bar.

11. A method for producing jet fuel, comprising:

(a) providing glycerolipid isolated from a population of cells of the genus Prototheca, the cells heterotrophically cultivated in the presence of sucrose, wherein the cells are genetically engineered to express sucrose invertase; and

(b) subjecting the isolated glycerolipid to one or more chemical reactions selected from the group consisting of cracking, hydrodeoxygenation, isomerization, and distillation to remove naptha, to generate alkanes having a carbon number distribution between about 8 and 16 carbon numbers,

whereby jet fuel is produced.

12. The method of claim 11, wherein the cells are of the species Prototheca moriformis.

13. The method of claim 11, wherein the chemical reactions are performed in the presence of a catalyst.

14. The method of claim 13, wherein the catalyst in the hydrodeoxygenation step contains metals selected from the group consisting of Pd, Pt, Ni, NiMo and CoMo.

15. The method of claim 13, wherein the catalyst in the hydrodeoxygenation step contains metals selected from the group consisting of NiMo/Al₂O₃ and CoMo/Al₂O₃.

16. The method of claim 13, wherein the catalyst in the isomerization step contains metals selected from the group consisting of SAPO-11, SAPO41, ZSM-22, ZSM-23, ferrierite, Pt, Pd, Ni, Al₂O₃ and SiO₂.

17. The method of claim 13, wherein the catalyst in the isomerization step contains metals selected from the group consisting of Pt/SAPO-11/ Al₂O₃, Pt/ZSM-22/ Al₂O₃, Pt/ZSM-23/ Al₂O₃, and Pt/SAPO-11/SiO₂.

18. The method of claim 11, wherein the hydrodeoxygenation step is performed at temperatures between 200°

C. and 500°

C.

19. The method of claim 11, wherein the hydrodeoxygenation step is performed at pressures between 50 and 100 bar.

20. The method of claim 11, wherein the isomerization step is performed at pressures between 20 and 100 bar.

21. A method for producing jet fuel, comprising:

(a) providing glycerolipid isolated from a population of cells of the genus Prototheca, the cells heterotrophically cultivated in the presence of sucrose, wherein the cells are genetically engineered to express sucrose invertase; and

(b) subjecting the isolated glycerolipid to one or more chemical reactions selected from the group consisting of fluid catalytic cracking, hydrodeoxygenation, isomerization, and distillation to remove naptha, to generate alkanes having a carbon number distribution between about 5 and 15 carbon numbers,

whereby jet fuel is produced.

22. The method of claim 21, wherein the fluid catalytic cracking occurs in steps selected from the group consisting of:

(a) flowing the glycerolipid through a fluid catalytic cracking reactor zone;

(b) vaporization of the glycerolipid;

(c) contacting the glycerolipid with a cracking catalyst;

(d) discharging the catalyst and glycerolipid vapors;

(e) collecting a product vapor stream comprised of hydrocarbons and catalyst particles; and

(f) separating the catalyst from the product vapor stream.

23. The method of claim 21, wherein the cells are of the species Prototheca moriformis.

24. The method of claim 21, wherein the glycerolipid is contacted with a catalyst in a catalyst to lipid ratio of about 5 to about 20.

25. The method of claim 24, wherein the glycerolipid is contacted with a catalyst in a catalyst to lipid ratio of about 10 to about 15.