High density fuels from oxygenated terpenoids

Patent metadata

Field	Value
Publication number	US-9682897-B1
Application number	US-201615142871-A
Country	US
Kind code	B1
Filing date	Apr 29, 2016
Priority date	Apr 30, 2015
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

A method for the efficient synthesis of useful deoxygenated terpenoids from an abundant renewable source, using catalytic conversion of oxygenated terpenoids. Oxygenated terpenoids such as 1,4-cineole and 1,8-cineole are, for example, major components of turpentine and essential oils. These oxygenated terpenoids can also be produced from sugars via a biosynthetic approach. Catalytic deoxygenation of these substrates can be used to efficiently generate commercially important chemicals and high density fuels for turbine or diesel propulsion.

First claim

The invention claimed is:

1. A low temperature process for producing deoxygenated terpenoids comprising: providing a renewable feedstock comprised of at least one oxygenated cyclic terpene;
wherein said at least one oxygenated cyclic terpene is comprised of a terpenoid ether, a terpenoid alcohol, or combinations thereof;
deoxygenating said at least one oxygenated cyclic terpene with a catalyst at a temperature up to about 170° C. to produce said deoxygenated terpenoids;
isolating said deoxygenated terpenoids; wherein said deoxygenated terpenoids comprise one or more terpene dimers;
hydrogenating said deoxygenated terpenoids to generate hydrogenated deoxygenated terpenoids comprising hydrogenated terpene dimers; and
wherein said hydrogenated terpene dimers have net heats of combustion ranging from about 135,000 Btu/gal up to about 145,000 Btu/gal and densities ranging from about 0.90 g/mL up to about 0.95 g/mL.

2. The process of claim 1 wherein said deoxygenated terpenoids further comprise one or more cyclic terpenes.

3. The process of claim 1 wherein said renewable feedstock comprises 1,4-cineole, 1,8-cineole, eucalyptus oil, hydrodistilled pine oil, gum spirit turpentine, crude sulfate turpentine, red oils or combinations thereof.

4. The process of claim 1 wherein said catalyst is a heterogeneous acid catalyst.

5. The process of claim 4 wherein said catalyst is selected from the group consisting of zeolites, aluminosilicates, clays, cation exchange resins, sulfated zirconia, sulfated titania, metal oxides, and combinations thereof.

6. The process of claim 1 wherein the process is performed at a temperature ranging from about 20° C. to about 100° C.

7. The process of claim 1 wherein said deoxygenated terpenoids are isolated using fractional distillation.

8. The process of claim 1 wherein the process is performed in a continuous fashion using a flow reactor.

9. The process of claim 1 wherein the process is performed in the gas phase.

10. The process of claim 1 wherein said deoxygenated terpenoids further comprise p-cymene, α-terpinene, γ-terpinene, or combinations thereof.

11. The process of claim 1 wherein said process utilizes a solvent comprising aprotic hydrocarbon solvents, aromatic solvents, ethers, cyclic ethers, and combinations thereof.

12. The process of claim 11 wherein said solvent has a boiling point in the range of about 80° C. to about 150° C.

13. The process of claim 11 wherein said solvent comprises heptane, octane, nonane, other acyclic alkanes, cyclohexane, methylcyclohexane, other alkyl cyclohexanes, benzene, toluene, xylenes, ethers, cyclic ethers or combinations thereof.

14. The process of claim 1 wherein said process is conducted without a solvent.

Assignees

• Us Navy
• Us Navy

Inventors

• Harvey Benjamin G
• Meylemans Heather A

Classifications

• C10L1/04

  essentially based on blends of hydrocarbons · CPC title

• C10L2290/06

  Heat exchange, direct or indirect · CPC title

• C07C2531/10

  sulfonated · CPC title

• C07C1/24 Primary

  by elimination of water · CPC title

• C07C13/21

  Menthadienes · CPC title