Efficient conversion of pure and mixed terpene feedstocks to high density fuels

Patent metadata

Field	Value
Publication number	US-9617488-B1
Application number	US-201514607346-A
Country	US
Kind code	B1
Filing date	Jan 28, 2015
Priority date	Aug 31, 2009
Publication date	Apr 11, 2017
Grant date	Apr 11, 2017

Abstract

A process for making high density fuels, pure terpene dimers, and byproducts from mixed terpene feedstocks and the resulting high density fuel products. The fuels produced by the process includes, dimerizing at least one terpene feedstock by mixing at least one terpene with at least one heterogeneous acidic catalyst and at least one solvent used to control the reaction temperature for a desired time and temperature to produce a crude terpene dimer (C 20 H 32 mixture) in about 65% to about 95% chemical yield, hydrogenating the crude terpene dimer (C 20 H 32 mixture) with at least one hydrogenation catalyst under a hydrogen atmosphere and removing the hydrogenating catalyst(s) to produce about 65% by weight to about 95% by weight of hydrogenated terpene dimer mixture, and utilizing a separation method against the hydrogenated terpene dimer mixture to produce byproducts, where the process generates a hydrocarbon mixture with a viscosity of between about 20 and 50 cSt at 40° C.

First claim

What is claimed is:

1. A fuel produced by the process for making terpene dimers, comprising:
dimerizing at least one terpene feedstock by mixing said at least one terpene with at least one heterogeneous acidic catalyst and at least one solvent used to control the reaction temperature for a desired time and temperature to produce a crude terpene dimer (C 20 H 32 mixture) in about 65% to about 95% chemical yield;
hydrogenating said crude terpene dimer (C 20 H 32 mixture) with at least one hydrogenation catalyst under a hydrogen atmosphere and removing said hydrogenating catalyst(s) to produce about 65% by weight to about 95% by weight of hydrogenated terpene dimer mixture; and
utilizing a separation method against said hydrogenated terpene dimer mixture to produce substantially pure terpene dimers and byproducts, wherein said process generates a hydrocarbon mixture with a viscosity of between about 20 and 50 cSt at 40° C.

2. The fuel of claim 1 , wherein said feedstock is selected from the group consisting of at least one of α-pinene, β-pinene, camphene, fenchene, carene, limonene, tricyclene, and turpentine, or any combination thereof.

3. The fuel of claim 1 , wherein said solvent is selected from the group consisting of at least one of n-heptane, n-octane, other linear alkanes, 2-ethylhexane, other branched alkanes, methylcyclohexane, cyclic alkanes with boiling points above 90° C., other non-aromatic liquid hydrocarbons, and any combination thereof; and removing said solvent by distillation after said hydrogenation process is complete.

4. The fuel of claim 1 , wherein said acid catalyst is selected from the group consisting of at least one of perfluorinated sulfonic acid resin, polyacidic clay, sulfonated polystyrene resin, mesoporous zeolites, Naflon, MMT-K10, and any combination thereof.

5. The fuel of claim 1 , further comprising said dimerizing step for a time period selected from the range of 0.5 to about 24 hours and at the temperature selected from the range of about 0° to about 160° C.

6. The fuel of claim 1 , wherein said separation method or said removal of said hydrogenating catalyst(s) is selected from at least one of filtration, decantation, distillation and centrifugation.

7. The fuel of claim 1 , wherein said hydrogenation catalyst having Ni, Pd, Pt, or Cu, including platinum oxide, palladium oxide, platinum supported on carbon, palladium supported on carbon, porous metallic nickel, and any combination thereof.

8. The fuel of claim 1 , wherein said hydrogen atmosphere is in the range of about 1 pound to about 750 pounds per square inch.

9. The fuel of claim 1 , wherein said byproducts comprise at least one of p-cymene and organic reaction products having greater than 20 carbon atoms.

10. The fuel of claim 1 , wherein said hydrogenated mixture comprises
about 65 to about 95% said hydrogenated terpene dimers; and
about 1 to about 15% said hydrogenated terpene trimers.

11. The fuel of claim 10 , wherein said high density fuel comprises >90% hydrogenated terpene dimers.

12. The fuel of claim 11 , wherein said fuel has a density in the range of 0.90 to about 0.95 grams per cubic centimeter and a NHOC (heat of combustion) in the range of 135,000 to about 145,000 btu/gallon measured at Standard Temperature and Pressure.

13. The fuel of claim 11 , further comprising adding to said fuel about 10 to about 90% (by volume) from the group consisting of at least one of JP-4, JP-5, JP-8, JP-10, F-76, RJ-4, hydrogenated pinene monomers, diesel fuels, fuels from renewable sources, and any combination thereof to produce a blended fuel, wherein said blended fuel generates a hydrocarbon mixture with a viscosity of between about 1 and 90 cP at 21° C.

14. The fuel of claim 1 , further comprising substantially isolating at least one of said byproducts including p-cymene, heavy oligomers (trimer, tetramer), and hydrogenated monomers.

15. The fuel of claim 1 , wherein said process is continuous.

16. A pure terpene dimer produced by the process, comprising:
dimerizing at least one terpene feedstock by mixing said at least one terpene with at least one heterogeneous acidic catalyst and at least one solvent used to control the reaction temperature for a desired time and temperature to produce a crude terpene dimer (C 20 H 32 mixture) in about 65% to about 95% chemical yield;
hydrogenating said crude terpene dimer (C 20 H 32 mixture) with at least one hydrogenation catalyst under a hydrogen atmosphere and removing said hydrogenating catalyst(s) to produce about 65% by weight to about 95% by weight of hydrogenated terpene dimer mixture; and
utilizing a separation method against said hydrogenated terpene dimer mixture to produce substantially pure terpene dimers, wherein said process generates a hydrocarbon mixture with a viscosity of between about 20 and 50 cSt at 40° C.

Assignees

• Us Navy
• Us Navy

Inventors

• Harvey Benjamin G
• Meylemans Heather A
• Quintana Roxanne L

Classifications

• C07C5/03

  of non-aromatic carbon-to-carbon double bonds · CPC title

• C10L2270/04

  for turbines, planes, power generation · CPC title

• C10L2270/026

  for diesel engines, e.g. automobiles, stationary, marine · CPC title

• C10L2290/547

  Filtration for separating fractions, components or impurities during preparation or upgrading of a fuel · CPC title

• C07C2/04

  by oligomerisation of well-defined unsaturated hydrocarbons without ring formation · CPC title