High density renewable fuels based on barbatene and thujopsene

Patent metadata

Field	Value
Publication number	US-10246654-B1
Application number	US-201514919446-A
Country	US
Kind code	B1
Filing date	Oct 21, 2015
Priority date	Nov 22, 2011
Publication date	Apr 2, 2019
Grant date	Apr 2, 2019

Abstract

A process for making high density fuels having the potential to increase the range and/or loiter time of Navy platforms. Derivation of these fuels from a sustainable source will decrease the carbon footprint of the Department of Defense (DoD) and reduce reliance on nonsustainable petroleum sources. Fuels based on barbatene and thujopsene have volumetric energy densities comparable to JP-10 and can be produced from biomass sugars.

First claim

What is claimed is:

1. A method for manufacturing turbine and diesel fuels, comprising:
providing a sesquiterpene mixture consisting of barbatene, thujopsene, alpha-barbatene, beta-chamigrene, beta-acoradiene, cuparene, and combinations thereof, wherein the sesquiterpene mixture is generated by metabolically engineered organisms from substrates including glucose, sucrose, fructose, other reducing sugars, cellobiose, cellulose, hemicellulose, lignocellulose, lignin, methane, and CO 2 , or by isolating the sesquiterpene mixture from plant material by solvent extraction or steam distillation;
purifying said sesquiterpene mixture, thereby forming a purified sesquiterpene mixture;
isomerizing said purified sesquiterpene mixture with at least one heterogeneous or homogenous acid catalyst to produce isomers; and
hydrogenating said isomers with at least one hydrogenation catalyst under hydrogen pressure to generate hydrogenated isomers; and distilling said hydrogenated isomers to produce a first high density fuel and a higher molecular weight residue.

2. The method according to claim 1 , wherein said sesquiterpene mixture has thujopsene present in an amount greater than 12 weight % and barbatene present in an amount greater than 25 weight %.

3. The method according to claim 1 wherein said hydrogenating catalyst has at least one metal selected from the group consisting of Ni, Cu, Pd, Pt, and Ru.

4. The method according to claim 1 , wherein said heterogeneous or homogenous acid catalyst is selected from the group consisting of at least one of perfluorinated sulfonic acid resins, cross-linked sulfonic acid resins, acid clays, zeolites, polyphosphoric acid, cation exchange resins, Lewis acid catalysts, supported Brønsted acid catalysts, mineral acids including H 2 SO 4 and H 3 PO 4 , and any mixtures thereof.

5. A method for manufacturing turbine and diesel fuels, comprising:
providing a sesquiterpene mixture consisting of barbatenes, thujopsene, alpha-barbatene, beta-chamigrene, beta-acoradiene, cuparenes, and combinations thereof, wherein the sesquiterpene mixture is generated by metabolically engineered organisms from substrates including glucose, sucrose, fructose, other reducing sugars, cellobiose, cellulose, hemicellulose, lignocellulose, lignin, methane, and CO 2 , or by isolating the sesquiterpene mixture from plant material by solvent extraction or steam distillation;
purifying said sesquiterpene mixture, thereby forming a purified sesquiterpene mixture;
isomerizing said purified sesquiterpene mixture with at least one heterogeneous or homogenous acid catalyst to produce isomers;
hydrogenating said isomers with at least one hydrogenation catalyst under hydrogen pressure to generate hydrogenated isomers; and distilling said hydrogenated isomers to produce a first high density fuel and a higher molecular weight residue; and
further isomerizing said hydrogenated isomers with at least one Lewis acid catalyst to generate a hydrocarbon mixture including adamantanes and distilling the hydrocarbon mixture including adamantane to produce a second high density fuel mixture and a higher molecular weight residue.

6. The method according to claim 5 wherein said residue obtained after distillation of said first or said second high density fuel is purified by vacuum distillation to yield a lubricant composed primarily of C30 hydrocarbons.

7. The method according to claim 5 , wherein said Lewis acid catalyst is selected from AlCl 3 , AlBr 3 , AlI 3 , Lewis acidic ionic liquids, BF 3 , gallium triflate, indium triflate, and other strong Lewis acids, and any combinations thereof.

8. The method according to claim 5 , wherein said first or second high density fuel has a density between 0.88 and 0.93 g/mL and a volumetric net heat of combustion >138,000 btu/gal.

9. The method according to claim 5 , wherein said first high density fuel or said second high density fuel mixture is blended with cetane enhancers including alkyl nitrates to generate fuels with cetane numbers >40.

10. The method according to claim 5 , wherein said first high density fuel or said second high density fuel mixture has a dynamic viscosity between about 30 and 50 cP at −20° C.

11. The method according to claim 5 , wherein said first high density fuel or said second high density fuel mixture has a dynamic viscosity <5 cP at 40° C.

12. The method according to claim 5 , wherein said first high density fuel or said second high density fuel mixture is blended with petroleum-based fuels including JP-10, RJ-4, JP-8, JP-5, F-76, Diesel #2, and Jet A.

13. The method according to claim 5 , wherein said first high density fuel or said second high density fuel mixture is blended with a high cetane blendstock including fuels generated via a Fischer-Tropsch process, ethylene oligomerization, butene oligomerization, or hexene oligomerization, to generate fuels with cetane numbers >40.

14. The method according to claim 6 , wherein said lubricant has a dynamic viscosity >20 cP at 40° C.

Assignees

• Us Navy

Inventors

• Harvey Benjamin G

Classifications

• C10G2300/307

  Cetane number, cetane index · CPC title

• C10L1/1608

  Well defined compounds, e.g. hexane, benzene · CPC title

• C10G3/50

  in the presence of hydrogen, hydrogen donors or hydrogen generating compounds · CPC title

• C10G2400/04

  Diesel oil · CPC title

• C10N2020/02

  Viscosity; Viscosity index · CPC title