Methods for the production of renewable dimethyl JP10

Patent metadata

Field	Value
Publication number	US-9327279-B2
Application number	US-201213604115-A
Country	US
Kind code	B2
Filing date	Sep 5, 2012
Priority date	Jul 29, 2009
Publication date	May 3, 2016
Grant date	May 3, 2016

Abstract

A highly efficient method for the conversion of a natural product into the high density fuel RJ-4 with concomitant evolution of isobutylene for conversion to fuels and polymers, more specifically, embodiments of the invention relate to efficient methods for the conversion of the renewable, linear terpene alcohol, linalool into a drop-in, high density fuel suitable for ramjet or missile propulsion.

First claim

What is claimed is:

1. A method for manufacturing high density fuels, comprising:
reacting at least one terpene alcohol with at least one Ru-metathesis catalysts with a solvent or under solvent-free conditions to produce 1-methylcyclopent-2-enol and isobutylene;
continuously separating said isobutylene by distillation;
dehydrating said 1-methylcyclopent-2-enol with at least one heterogeneous dehydration catalyst to produce a mixture consisting of 2-methyl cyclopentadiene and 1-methyl cyclopentadiene;
thermal dimerizing said methylcyclopentadienes to produce a mixture of methylcyclopentadiene dimers comprising greater than 50% 3,9-dimethyl-endo-tricyclo[5.2.1.0 2,6 ]deca-3,8-diene and about 30% 4,9-dimethyl-endo-tricyclo [5.2.1.0 2,6 ]deca-3,8-diene;
hydrogenating said methylcyclopentadienes dimers with at least one hydrogenation catalyst to produce hydrogenated methylcyclopentadienes dimers; and
isomerizing said hydrogenated methylcyclopentadienes dimers with at least one Lewis acid catalyst to produce high density fuels.

2. The method according to claim 1 , wherein said at least one terpene alcohol is linalool.

3. The method according to claim 1 , wherein said at least one Ru-metathesis catalysts comprises of first generation Grubbs catalyst, second generation Grubbs, Grubbs-Hoveyda catalyst, catalysts with electron withdrawing alkoxides and labile pyridine ligands, heterogeneous metal oxides, and polymer supported catalysts.

4. The method according to claim 1 , wherein said at least one heterogeneous dehydration catalyst is selected from the group consisting of AlPO 4 , Al 2 O 3 , SiO 2 , MgSO 4 , and zeolites.

5. The method according to claim 1 , wherein said thermal dimerizing method comprises increasing the temperature to accelerate the dimerization of said methylcyclopentadienes to produce methylcyclopentadiene dimers.

6. The method according to claim 1 , wherein a Lewis acid catalyst is employed to increase the rate of dimerization of methylcyclopentadienes.

7. The method according to claim 1 , wherein said thermal dimerizing method comprises conducting the dimerization at room temperature.

8. The method according to claim 1 , wherein said at least one hydrogenation catalyst includes at least one of Ni, Pd, Pt, and Cu, either supported or unsupported.

9. The method according to claim 1 , wherein said at least one Lewis acid catalyst is selected from the group consisting of AICl 3 , ionic liquids or salts including AlCl 4 − as the anion.

10. The method according to claim 1 , wherein said high density fuels is tetrahydromethyl-cyclopentadiene dimmer(RJ-4).

11. A high density fuel produced by the methods of claim 1 .

Assignees

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

Inventors

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

Classifications

• C10G2300/1092

  C2-C4 olefins · CPC title

• C10G45/58

  to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins (C10G32/00 takes precedence; improving or increasing the octane number or aromatic content of naphtha C10G35/00) · CPC title

• B01J2531/48

  Zirconium · CPC title

• C10G2300/1011

  Biomass · CPC title

• C10G65/06

  at least one step being a selective hydrogenation of the diolefins · CPC title