# US 10,246,655 B1 · High density renewable fuels from santalenes

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- Number: US 10,246,655 B1
- Document ID: US10246655B1
- Status: Granted
- Kind: B1
- Application number: 14/919,503
- Filed: 2015-10-21
- Granted: 2019-04-02
- Earliest claimed: 2011-11-22
- Assignees: The United States of America as represented by the Secretary of the Navy
- Applicants: The United States of America, as Represented by the Secretary of the Navy
- Inventors: Benjamin G Harvey
- Web page: https://patentgrep.com/patent/US10246655B1

## CPC

- C10L 1/04: essentially based on blends of hydrocarbons
- C10G 3/47: {containing platinum group metals or compounds thereof}
- C10G 3/50: {in the presence of hydrogen, hydrogen donors or hydrogen generating compounds}
- C10L 1/08: for compression ignition
- C10L 1/1608: {Well defined compounds, e.g. hexane, benzene}
- C10L 1/231: {nitro compounds; nitrates; nitrites (C10L1/221 takes precedence)}
- C10M 105/04: aliphatic
- C10M 177/00: Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
- C10G 2300/1014: of vegetal origin
- C10G 2300/307: Cetane number, cetane index
- C10G 2300/4043: Limiting CO2 emissions
- C10G 2400/04: Diesel oil
- C10L 2200/0484: Vegetable or animal oils
- C10L 2270/026: for diesel engines, e.g. automobiles, stationary, marine
- C10L 2270/04: for turbines, planes, power generation
- C10L 2290/543: Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel
- C10M 2203/04: Well-defined cycloaliphatic compounds
- C10M 2203/045: used as base material
- C10N 2020/02: Viscosity; Viscosity index
- C10N 2060/02: Reduction, e.g. hydrogenation
- Y02E 50/10: Biofuels, e.g. bio-diesel
- Y02P 30/20: using bio-feedstock
- Y02T 50/678: Aviation using fuels of non-fossil origin
- C10L: FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10M: LUBRICATING COMPOSITIONS (well drilling compositions C09K8/02); USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION (mould release, i.e. separating, agents for metals B22C3/00, for plastics or substances in a plastic state, in general B29C33/56, for glass C03B40/02; textile lubricating compositions D06M11/00, D06M13/00, D06M15/00; immersion oils for microscopy G02B21/33)
- C10N: INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION

## 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 santalenes have volumetric energy densities greater than JP-5 and F-76 and can be produced from biomass sugars.

## Claims

### Claim 1

A method for manufacturing turbine and diesel fuels, comprising:
providing a sesquiterpene mixture consisting of santalene, alpha-santalene, beta-santalene, alpha-bergamotene, farnesene, 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, natural gas, and CO2, or by isolating 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.

### Claim 2 (depends on 1)

The method according to claim 1, wherein said sesquiterpene mixture has santalene present in an amount greater than 60 weight %.

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

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 H2SO4 and H3PO4, and any mixtures thereof.

### Claim 5

A method for manufacturing turbine and diesel fuels, comprising:
providing a sesquiterpene mixture consisting of santalene, alpha-santalene, beta-santalene, alpha-bergamotene, farnesene, 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, natural gas, and CO2, or by isolating 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 having adamantanes and distilling the adamantane mixture to produce a second high density fuel mixture and a higher molecular weight residue.

### Claim 6 (depends on 5)

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.

### Claim 7 (depends on 5)

The method according to claim 5, wherein said Lewis acid catalyst is selected from AlCl3, AlBr3, AlI3, Lewis acidic ionic liquids, BF3, gallium triflate, indium triflate, other strong Lewis acids, and any combination thereof.

### Claim 8 (depends on 5)

The method according to claim 5, wherein said first or second high density fuel has a density between 0.86 and 0.92 g/mL and a volumetric net heat of combustion>130,000 btu/gal.

### Claim 9 (depends on 5)

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.

### Claim 10 (depends on 5)

The method according to claim 5, wherein said first high density fuel or said second high density fuel mixture has a viscosity between about 15 and 60 cP at −20° C.

### Claim 11 (depends on 5)

The method according to claim 5, wherein said first high density fuel or said second high density fuel mixture has a viscosity<4 cP at 40° C.

### Claim 12 (depends on 5)

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.

### Claim 13 (depends on 5)

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.

### Claim 14 (depends on 6)

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