# US 9,040,757 B2 · Synthesis of high caloric fuels and chemicals

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- Number: US 9,040,757 B2
- Document ID: US9040757B2
- Status: Granted
- Kind: B2
- Application number: 13/789,952
- Filed: 2013-03-08
- Published: 2014-09-11
- Granted: 2015-05-26
- Earliest claimed: 2011-11-10
- Assignees: Pioneer Energy, Inc.
- Applicants: John Henri; Jan Zygmunt; Mark Bergren; Robert Zubrin
- Inventors: John Henri; Jan Zygmunt; Mark Bergren; Robert Zubrin
- Web page: https://patentgrep.com/patent/US9040757B2

## CPC

- C07C 29/175: {with simultaneous reduction of an oxo group}
- C07C 1/207: from carbonyl compounds
- C07C 1/2076: {by a transformation in which at least one -C(=O)- moiety is eliminated}
- C07C 29/145: with hydrogen or hydrogen-containing gases
- C07C 29/149: with hydrogen or hydrogen-containing gases
- C07C 29/153: characterised by the catalyst used
- C07C 29/154: containing copper, silver, gold, or compounds thereof
- C07C 31/08: Ethanol
- C07C 31/12: containing four carbon atoms
- C07C 31/125: containing five to twenty-two carbon atoms
- C07C 45/455: {with carboxylic acids or their derivatives}
- C07C 45/89: from carboxylic acids, their anhydrides, esters or halides
- C07C 51/09: from carboxylic acid esters or lactones
- C07C 67/46: from ketenes or polyketenes
- C07D 305/12: Beta-lactones
- C10L 1/18: containing oxygen
- C10L 10/10: for improving the octane number
- C07C 2523/06: of zinc, cadmium or mercury
- C07C 2523/26: Chromium
- C07C 2523/72: Copper
- C07C 2523/80: with zinc, cadmium or mercury
- C07C 2523/86: Chromium
- C10L 1/1824: {mono-hydroxy}
- C10L 2270/02: for internal combustion engines
- C10L 2270/023: for gasoline engines
- C10L 2290/24: Mixing, stirring of fuel components
- Y02E 50/10: Biofuels, e.g. bio-diesel
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- 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
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

In one embodiment, the present application discloses methods to selectively synthesize higher alcohols and hydrocarbons useful as fuels and industrial chemicals from syngas and biomass. Ketene and ketonization chemistry along with hydrogenation reactions are used to synthesize fuels and chemicals. In another embodiment, ketene used to form fuels and chemicals may be manufactured from acetic acid which in turn can be synthesized from synthesis gas which is produced from coal, biomass, natural gas, etc.

## Claims

### Claim 1

A method for the preparation of an alkyl compound or a mixture of alkyl compounds, the method comprising:
a) preparing a compound of the formula I:
where:
R1 is H or C1-6 alkyl; and
R2 is H or C1-6 alkyl;
b) reacting the compound of the formula I to form a self-addition product; and
c) hydrogenating the self-addition product in the presence of a metal catalyst to form the alkyl compound or mixtures of alkyl compounds.

### Claim 2 (depends on 1)

The method of claim 1 where R1 and R2 are hydrogen and the formula I is ketene, and the ketene is prepared from acetic acid.

### Claim 3 (depends on 2)

The method of claim 2 where the ketene self-addition product is diketene.

### Claim 4 (depends on 3)

The method of claim 3 where the alkyl compound or mixture of alkyl compounds comprises butanol.

### Claim 5 (depends on 2)

The method of claim 2 where the acetic acid is prepared by the carbonylation of methanol and the methanol prepared from synthesis gas.

### Claim 6

A method for the preparation of an alkyl compound or mixture of alkyl compounds, comprising:
a) preparing a compound of the formula I:
where:
R1 is H; and
R2 is H;
b) reacting the compound of the formula I to form a diketene self-addition product;
c) reacting the diketene self-addition product with a C1-6 alcohol to form an acetoacetate ester; and
d) the acetoacetate ester is hydrogenated to from 1-butanol, 2-butanol or a mixture thereof.

### Claim 7 (depends on 6)

The method of claim 6 wherein the C1-6 alcohol is methanol.

### Claim 8 (depends on 6)

The method of claim 6 where the C1-6 alcohol is butanol.

### Claim 9 (depends on 1)

The method of claim 1 where the metal catalyst is a transition metal.

### Claim 10 (depends on 9)

The method of claim 9 where the transition metal catalyst contains a main group metal.

### Claim 11 (depends on 10)

The method of claim 10 where the transition metal catalyst is a copper-zinc based catalyst.

### Claim 12

A method for the preparation of an alkyl compound or mixture of alkyl compounds, comprising:
a) preparing a ketene of the formula I:
where:
R1 is H; and
R2 is H;
b) dimerizing the ketene to diketene;
c) dimerizing the diketene to dehydroacetic acid; and
d) hydrogenating the dehydroacetic acid to the alkyl compound or mixture of alkyl compounds.

### Claim 13 (depends on 12)

The method of claim 12 where the alkyl compound or mixture of alkyl compounds is a mixture of alcohols, alkanes and ketones.

### Claim 14 (depends on 12)

The method of claim 12 where the alkyl compound or mixture of alkyl compounds comprises 4-heptanol and 2-heptanol.

### Claim 15 (depends on 14)

The method of claim 14, further comprising dehydrating and hydrogenating the 4-heptanol and 2-heptanol to an alkane product.

### Claim 16 (depends on 12)

The method of claim 12 where the alkyl compound or mixture of alkyl compounds is selected from C7, C8, C9, C10, C11, C12, C13 and C14 alkanes or alkyl compounds.

### Claim 17 (depends on 12)

The method of claim 12 where step (d) is performed in the presence of a transition metal catalyst.

### Claim 18 (depends on 17)

The method of claim 17 where the transition metal catalyst contains a main group metal.

### Claim 19 (depends on 18)

The method of claim 18 where the transition metal catalyst is a copper-zinc based catalyst.

### Claim 20 (depends on 12)

The method of claim 12 where the ketene is prepared by the carbonylation of methanol to acetic acid and the acetic acid is dehydrated to the ketene.

### Claim 21 (depends on 13)

The method of claim 13 where the alcohols are converted to alkanes by:
a) dehydrating the alcohols to alkenes; and
b) hydrogenating the alkenes to the alkanes.

### Claim 22

A method for preparing an alkyl compound or mixture of alkyl compounds, comprising:
a) preparing ketene;
b) dimerizing the ketene to diketene;
c) hydrogenating the diketene to butyric acid;
d) ketonizing the butyric acid to heptanone; and
e) hydrogenating the heptanone to the alkyl compound or a mixture of alkyl compounds.

### Claim 23 (depends on 22)

The method of claim 22 where the preparing the ketene comprises:
a) converting synthesis gas to methanol;
b) carbonylating the methanol to acetic acid; and
c) dehydrating the acetic acid to ketene.

### Claim 24 (depends on 22)

The method of claim 22 where step (d) is performed in the presence of a catalyst selected from the group consisting of gamma-alumina, ceria, magnesia, hydrotalcite and zeolites.

### Claim 25 (depends on 24)

The method of claim 24 where the catalyst is gamma-alumina containing lanthanum oxide.

### Claim 26 (depends on 22)

The method of claim 22 where each of steps c) and e) is performed in the presence of a transition metal catalyst.

### Claim 27 (depends on 26)

The method of claim 26 where the transition metal catalyst contains a main group metal.

### Claim 28 (depends on 27)

The method of claim 27 where the transition metal catalyst is a copper zinc oxide catalyst.

### Claim 29

A method for preparing a hydrocarbon product comprising:
a) preparing ketene;
b) dimerizing the ketene to diketene;
c) hydrogenating the diketene to butyric acid;
d) ketonizing the butyric acid to 4-heptanone;
e) hydrogenating the 4-heptanone to 4-heptanol;
f) dehydrating the 4-heptanol to 3-heptene; and
g) hydrogenating the 3-heptene to the hydrocarbon product.