High density fuels from renewable alcohols

Patent metadata

Field	Value
Publication number	US-9764997-B1
Application number	US-201615099214-A
Country	US
Kind code	B1
Filing date	Apr 14, 2016
Priority date	Apr 14, 2016
Publication date	Sep 19, 2017
Grant date	Sep 19, 2017

Abstract

A method for making hydrogenated cyclooctatetraene dimers including cyclo-dimerizing butadiene to form 1,5-cyclooctadiene in the presence of at least one first catalyst, dehydrogenating 1,5-cyclooctadiene to 1,3,5,7-cyclooctatetraene, dimerizing 1,3,5,7-cyclooctatetraene to a C 16 multicyclic hydrocarbon cyclooctatetraene dimer, and hydrogenating multicyclic hydrocarbon cyclooctatetraene dimer to form hydrogenated cyclooctatetraene dimers.

First claim

What is claimed is:

1. A method for making a high density fuel, comprising:
cyclo-dimerizing butadiene in the presence of at least one first catalyst to form 1,5-cyclooctadiene;
dehydrogenating said 1,5-cyclooctadiene to 1,3,5,7-cyclooctatetraene;
dimerizing said 1,3,5,7-cyclooctatetraene to a mixture of C 16 multicyclic cyclooctatetraene dimers;
hydrogenating said multicyclic hydrocarbon cyclooctatetraene dimers to form a reaction mixture comprising the at least one first catalyst and hydrogenated cyclooctatetraene dimers;
separating said hydrogenated cyclooctatetraene dimers from the reaction mixture; and
purifying said separated hydrogenated cyclooctatetraene dimers to generate a high density fuel comprising said hydrogenated cyclooctatetraene dimers, wherein said high density fuel has a density greater than 1.10 g/mL and a volumetric net heat of combustion greater than 165,000 btu/gal.

2. The method according to claim 1 , wherein said butadiene is derived from a renewable source.

3. The method according to claim 1 , further comprising dehydrating bio-derived n-butanol to 1-butene followed by dehydrogenation to yield said 1,3-butadiene.

4. The method according to claim 1 , wherein said dehydrogenating of said 1,5-cyclooctadiene is accomplished by forming a tetrahalide followed by dehydrohalogenation with a base to yield said 1,3,5,7-cyclooctadiene.

5. The method according to claim 1 , further comprising dehydrating ethanol to ethylene, followed by dimerizing said ethylene to 1-butene, and dehydrogenating said 1-butene to form said butadiene.

6. The method according to claim 1 , further comprising dehydrating bio-derived 2,3-butanediol or 1,4-butanediol to form said butadiene.

7. The method according to claim 1 , further comprising generating said butadiene from synthesis gas.

8. The method according to claim 1 , wherein said first catalyst includes a transition metal selected from the group consisting of Mn, Ni, Fe, Co, and Pd.

9. The method according to claim 1 , wherein said first catalyst includes nickel and electron withdrawing ligands are used to reduce Diels Alder products and improve the yield of 1,5-cyclooctadiene.

10. The method according to claim 1 , further comprising separating said 1,5-cyclooctadiene from the reaction mixture to provide a pure substrate.

11. The method according to claim 1 , wherein said dehydrogenating of said 1,5-cyclooctadiene to 1,3,5,7-cyclooctatetraene is accomplished by deprotonating 1,5-cyclooctadiene to generate a dianion C 8 H 8 ( 2− ).

12. The method according to claim 11 , further comprising treating said dianion with an oxidizing agent to form said 1,3,5,7-cyclooctatetraene.

13. The method according to claim 1 , wherein said dimerizing of said 1,3,5,7-cyclooctatetraene to a C 16 cyclooctatetraene dimer is conducted with at least one solvent.

14. The method according to claim 1 , wherein said dimerizing of said 1,3,5,7-cyclooctatetraene to C 16 cyclooctatetraene dimers is conducted with a second catalyst to increase the selectivity of the reaction to dimers and reduce the temperature of the reaction mixture.

15. The method according to claim 14 , wherein said second catalyst is a heterogeneous acid catalyst.

16. The method according to claim 14 , wherein said dimerizing of said 1,3,5,7-cyclooctatetraene is conducted between about 25° C. to about 200° C.

17. The method according to claim 1 , wherein said cyclooctatetraene dimers are hydrogenated with a heterogeneous or homogenous third catalyst based on metals selected from the consisting of Ni, Pd, Pt, Ru, Rh, Cu, and Cr under a hydrogen pressure.

18. The method according to claim 15 , wherein said third catalyst is selective for hydrogenation of alkenes present in the structure but not a cyclopropane ring which is present in one of the dimers.

19. The method according to claim 1 , wherein the high density fuel further comprises exo-tetrahydrodicyclopentadiene, and wherein said hydrogenated cyclooctatetraene dimers comprise about 10% to about 90% of the fuel by volume.

20. The method according to claim 1 , wherein the high density fuel further comprises dimethyltetrahydrodicyclopentadiene, and wherein said hydrogenated cyclooctatetraene dimers comprise about 10% to about 90% of the fuel by volume.

21. The method according to claim 1 , wherein the high density fuel further comprises hydrogenated norbornadiene dimers and exo-tetrahydrodicyclopentadiene, and wherein said hydrogenated cyclooctatetraene dimers comprise about 10% to about 90% of the fuel by volume.

22. High density fuels produced by the process of claim 1 .

23. Hydrogenated cyclooctatetraene dimers produced by the process of claim 1 .

Assignees

• Us Navy

Inventors

• Harvey Benjamin G

Classifications

• C10L1/04

  essentially based on blends of hydrocarbons · CPC title

• C07C2/403

  Catalytic processes · CPC title

• C10G2/32

  with the use of catalysts · CPC title

• C10G2400/08

  Jet fuel · CPC title

• C10L2290/42

  Fischer-Tropsch steps · CPC title