# US 10,118,886 B2 · Biofuels production from bio-derived carboxylic-acid esters

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- Number: US 10,118,886 B2
- Document ID: US10118886B2
- Status: Granted
- Kind: B2
- Application number: 15/297,610
- Filed: 2016-10-19
- Published: 2017-02-16
- Granted: 2018-11-06
- Earliest claimed: 2012-12-20
- Assignees: Archer Daniels Midland Company
- Applicants: Archer Daniels Midland Company
- Inventors: Kenneth Stensrud; Padmesh Venkitasubramanian
- Web page: https://patentgrep.com/patent/US10118886B2

## CPC

- C07C 67/08: by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
- C07C 29/149: with hydrogen or hydrogen-containing gases
- C07C 67/297: by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07D 307/08: Preparation of tetrahydrofuran
- C10G 3/50: {in the presence of hydrogen, hydrogen donors or hydrogen generating compounds}
- C10L 1/02: essentially based on components consisting of carbon, hydrogen, and oxygen only
- C10L 1/023: {for spark ignition}
- C10L 1/04: essentially based on blends of hydrocarbons
- C10L 1/06: for spark ignition
- C07C 29/147: of carboxylic acids or derivatives thereof
- C07D 307/33: in position 2, the oxygen atom being in its keto or unsubstituted enol form
- C10L 2200/0469: Renewables or materials of biological origin
- C10L 2290/26: Composting, fermenting or anaerobic digestion fuel components or materials from which fuels are prepared
- C12P 7/40: containing a carboxyl group {including Peroxycarboxylic acids}
- C12P 7/46: Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
- C12P 7/48: Tricarboxylic acids, e.g. citric acid
- Y02E 50/10: Biofuels, e.g. bio-diesel
- Y02P 20/54: using solvents, e.g. supercritical solvents or ionic liquids
- Y02P 30/20: using bio-feedstock
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- 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
- 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
- C12P: FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE {(brewing of beer C12C; producing vinegar C12J; producing specific peptides or proteins C07K; producing enzymes C12N9/00; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; measuring or testing processes involving enzymes or microorganisms C12Q; measuring or testing processes involving nucleic acid amplification reactions C12Q1/6844; fermentation processes to form a food composition, A21 or A23; compounds in general, see the relevant compound class, e.g. C01, C07)}
- 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

## Abstract

A process for producing biofuels compounds directly from carboxylic acid esters recovered from a fermentation system is described. The process involves taking a fermentation broth that has been reduced to a dry powder containing free organic acids; reacting the carboxylic acid in the powder with an alcohol solvent under a CO2-containing atmosphere in substantial absence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for at least one of the alcohol or CO2 to synthesize an ester, then subjecting the ester to either hydrogenolysis or hydrogenation to form a biofuel.

## Claims

### Claim 1

A process for producing a biofuel comprising: a) using a fermentation broth containing at least one free carboxylic acid; b) synthesizing an ester by reacting said free carboxylic acid with an alcohol solvent under a CO2 atmosphere in substantial absence of any other acid catalyst at either a reaction temperature or pressure or both that is at a supercritical, critical or near critical condition for at least one of the alcohol or CO2; and c) subjecting said ester to either hydrogenolysis or hydrogenation to form a biofuel.

### Claim 2 (depends on 1)

The process according to claim 1, further comprising recovering said biofuel.

### Claim 3 (depends on 1)

The process according to claim 1, wherein said biofuel is an alkane or an alcohol.

### Claim 4 (depends on 3)

The process according to claim 3, wherein said biofuel includes at least one of the following: ethane, ethanol, propane, propanol, butane, 1-butanol, octane, and octanol.

### Claim 5 (depends on 1)

The process according to claim 1, further comprising drying said fermentation broth into a powder before ester synthesis.

### Claim 6 (depends on 1)

The process according to claim 1, further comprising concentrating said ester before either hydrogenolysis or hydrogenation.

### Claim 7 (depends on 1)

The process according to claim 1, further comprising purifying said ester to at least 90% purity.

### Claim 8 (depends on 1)

The process according to claim 1, wherein said fermentation broth is at a pH in a range between about 1.5 and about 4.5.

### Claim 9 (depends on 1)

The process according to claim 1, wherein said alcohol solvent has an R-group of C1-C20, and is at least one of a saturated, unsaturated, cyclic, or aromatic species.

### Claim 10 (depends on 1)

The process according to claim 1, wherein said carboxylic acid is selected from the group consisting of: formic acid, acetic acid, propionic acid, lactic acid, butyric acid, isobutyric acid, valeric acid, hexanoic acid, heptanoic acid, decanoic acid, lauric acid, myristic acid, and C15-C18 fatty acids, fumaric acid, itaconic acid, malic acid, succinic acid, maleic acid, malonic acid, glutaric acid, glucaric acid, oxalic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, glutaconic acid, ortho-phthalic acid, isophthalic acid, terephthalic acid, citric acid, isocitric acid, aconitic acid, tricarballylic acid, and trimesic acid.

### Claim 11 (depends on 1)

The process according to claim 1, wherein said carboxylic acid is a polycarboxylic acid.

### Claim 12 (depends on 11)

The process according to claim 11, wherein said carboxylic acid is a dicarboxylic or a tricarboxylic acid.

### Claim 13 (depends on 11)

The process according to claim 11, wherein when said carboxylic acid is a polycarboxylic acid, said ester is at least a diester.

### Claim 14 (depends on 11)

The process according to claim 11, wherein said polycarboxylic acid is converted to a corresponding ester at a rate of at least 50% of said polycarboxylic acid.

### Claim 15 (depends on 1)

The process according to claim 1, wherein said reaction temperature is between about 150° C. and about 250° C., and said pressure is in a range between about 400 psi and 3,000 psi.

### Claim 16 (depends on 1)

The process according to claim 1, wherein said free carboxylic acids are not subject to activation with a halide to form an acyl halide.