# US 11,078,427 B2 · Methods and devices for producing biodiesel, diesel-range hydrocarbons, and products obtained therefrom

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- Number: US 11,078,427 B2
- Document ID: US11078427B2
- Status: Granted
- Kind: B2
- Application number: 16/400,777
- Filed: 2019-05-01
- Published: 2019-11-07
- Granted: 2021-08-03
- Earliest claimed: 2018-05-03
- Assignees: Renewable Energy Group, Inc.
- Applicants: Renewable Energy Group, Inc.
- Inventors: James Matthew White; David A. Slade; Martin R. Haverly; Ramin Abhari; Cody J. Ellens
- Web page: https://patentgrep.com/patent/US11078427B2

## CPC

- C10G 3/42: {Catalytic treatment}
- C10G 3/50: {in the presence of hydrogen, hydrogen donors or hydrogen generating compounds}
- C10G 45/58: 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)
- C10G 47/00: Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions (C10G15/00 takes precedence; destructive hydrogenation of non-melting solid carbonaceous or similar materials C10G1/06)
- C10G 65/12: including cracking steps and other hydrotreatment steps
- C11B 7/0008: {by differences of solubilities, e.g. by extraction, by separation from a solution by means of anti-solvents (addition of a minor amount of solvent intended to lower the melting point C11B7/0083, C11B7/0091)}
- C11C 1/025: {by saponification and release of fatty acids}
- C11C 1/10: by distillation
- C11C 3/003: {by esterification of fatty acids with alcohols (C11C3/02 takes precedence)}
- C10G 2300/1011: Biomass
- C10G 2300/4006: Temperature
- C10G 2300/4012: Pressure
- Y02E 50/10: Biofuels, e.g. bio-diesel
- Y02P 30/20: using bio-feedstock
- 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
- C11B: PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES (drying-oils C09F)
- C11C: FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- 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 crude biodiesel from renewable feedstocks (such as fats, oils, and greases) containing unsaponifiable materials; purifying the crude biodiesel through a purification process; recovering a purified biodiesel distillate stream and a less volatile biodiesel residue stream; and further recovering valuable chemicals from the biodiesel residue. Specifically, the present technology relates to the concentration of valuable chemicals in the biodiesel residue product of biodiesel production and the subsequent recovery of these valuable chemicals. The process may further include the conversion of the biodiesel residue into diesel range hydrocarbons using hydrodeoxygenation and the subsequent purification of the hydrocarbon fraction produced thereby.

## Claims

### Claim 1

A process for producing hydrocarbons from a biological feedstock comprising:
a. subjecting the biological feedstock to a pre-treatment process comprising:
i. heating the biological feedstock to a temperature above ambient temperature;
ii. adding an aqueous acid solution to the heated biological feedstock and mixing to produce a mixture; and
iii. separating the mixture to produce a refined biological feedstock;
wherein the biological feedstock comprises a distillation bottoms recovered from a biodiesel distillation process, the distillation bottoms comprising unsaponifiable material at a concentration greater than 2 wt %, and the refined biological feedstock has a reduced concentration of inorganic impurities and reduced alkalinity compared to the biological feedstock;
b. diluting the refined biological feedstock with a hydrocarbon oil to produce a diluted biological feedstock;
c. subjecting the diluted biological feedstock to a hydrodeoxygenation process comprising contacting the diluted biological feedstock with a hydrogen-rich gas and a catalyst at a temperature and pressure which are elevated above an ambient temperature and pressure to produce a reactor effluent; and
d. recovering a hydrocarbons fraction from the reactor effluent.

### Claim 2 (depends on 1)

The process of claim 1 wherein the biological feedstock comprises free fatty acids and fatty acid glyceride esters.

### Claim 3 (depends on 1)

The process of claim 1 wherein the temperature is between about 260 C and 371 C and the pressure is between about 500 and 2,500 psig.

### Claim 4 (depends on 1)

The process of claim 1 wherein the biological feedstock comprises at least 20 wt % high molecular weight components.

### Claim 5 (depends on 4)

The process of claim 4 wherein the high molecular weight components are indicated by 20 wt % boiling above about 400° C. according to at least one of ASTM D2887-18 or ASTM D7169-11 measured on the diluted biological feedstock.

### Claim 6 (depends on 1)

The process of claim 1 wherein the hydrocarbon oil comprises C15, C16, C17, and C18 n-paraffins.

### Claim 7 (depends on 1)

The process of claim 1 wherein the hydrocarbon oil is a petroleum fraction.

### Claim 8 (depends on 1)

The process of claim 1 wherein the reactor effluent comprises less than 5 wt % hydrocarbons boiling above 380° C. according to ASTM D2887-18.

### Claim 9 (depends on 1)

The process of claim 1 wherein the reactor effluent comprises hydrocarbons with acid number below 0.05 mg KOH/g.

### Claim 10 (depends on 1)

The process of claim 1 wherein the biodiesel distillation process purifies biodiesel made by at least one of transesterification and esterification of a lipid feedstock comprised of greater than 10 wt % of an unconventional lipid, wherein the unconventional lipid comprises at least 20 wt % C20+ fatty acids.

### Claim 11 (depends on 1)

The process of claim 1 wherein the distillation bottoms comprises at least 15 wt % C20+ fatty acid alkyl esters.

### Claim 12 (depends on 1)

The process of claim 1 wherein the biological feedstock comprises unsaponifiable material at a concentration greater than 3 wt %.

### Claim 13 (depends on 1)

The process of claim 1 wherein the biological feedstock comprises unsaponifiable material at a concentration greater than 4 wt %.

### Claim 14 (depends on 1)

The process of claim 1 wherein the pretreatment process further comprises water washing the biological feedstock to produce the refined biological feedstock.

### Claim 15 (depends on 1)

The process of claim 1 wherein the pretreatment process reduces the Alkalinity by at least 80%.

### Claim 16 (depends on 1)

The process of claim 1 wherein the catalyst in the hydrodeoxygenation process includes a first catalyst bed having a first activity and a second catalyst bed having a second activity, and the first activity is lower than the second activity, wherein the hydrodeoxygenation process further includes subjecting the diluted biological feedstock to the first catalyst bed before subjecting the diluted biological feedstock to the second catalyst bed.

### Claim 17

A process for producing hydrocarbons from a biological feedstock comprising:
a. subjecting the biological feedstock to a pre-treatment process comprising:
i. heating the biological feedstock to a temperature above ambient temperature;
ii. adding an aqueous acid solution to the heated biological feedstock and mixing to produce a mixture; and
iii. separating the mixture to produce a refined biological feedstock;
wherein the biological feedstock comprises a distillation bottoms recovered from a biodiesel distillation process, the distillation bottoms comprising unsaponifiable material at a concentration greater than 2 wt % and a fatty acid alkyl ester fraction comprising greater than 40 wt % C16 and shorter carbon fatty acid chains, and the refined biological feedstock has a reduced concentration of inorganic impurities and reduced alkalinity compared to the biological feedstock;
b. diluting the refined biological feedstock with a hydrocarbon oil to produce a diluted biological feedstock,
c. subjecting the diluted biological feedstock to a hydrodeoxygenation process comprising contacting the diluted biological feedstock with a hydrogen-rich gas and a catalyst at a temperature and pressure which are elevated above an ambient temperature and pressure to produce a reactor effluent; and
d. recovering a hydrocarbons fraction from the reactor effluent.

### Claim 18 (depends on 17)

The process of claim 17 wherein the temperature is between about 260 C and 371 C and the pressure is between about 500 and 2,500 psig.

### Claim 19 (depends on 17)

The process of claim 17 further comprising separating the reactor effluent into a hydrocarbon phase, a gas phase, and an aqueous phase and using a hydrocarbon stripper to separate the hydrocarbon phase into an overheads fraction and the hydrocarbons fraction.

### Claim 20 (depends on 17)

The process of claim 17 further comprising adding the hydrocarbons fraction to a diesel fuel.

### Claim 21 (depends on 17)

The process of claim 17 further comprising introducing the hydrocarbons fraction to at least one of a hydrocracking and hydroisomerization process to produce a renewable diesel fuel.

### Claim 22 (depends on 17)

The process of claim 17 wherein the biological feedstock comprises unsaponifiable material at a concentration greater than 3 wt %.

### Claim 23 (depends on 17)

The process of claim 17 wherein the biological feedstock comprises unsaponifiable material at a concentration greater than 4 wt %.

### Claim 24

A process for producing a purified biodiesel from a feedstock containing unsaponifiable material, said method comprising:
a. introducing the feedstock to a first pre-treatment process to produce a pretreated feedstock;
b. introducing the pretreated feedstock to a FFA refining process to produce a refined feedstock;
c. reacting the refined feedstock in a transesterification reactor with an alcohol to produce a crude biodiesel;
d. purifying the crude biodiesel by distillation to produce a purified biodiesel and a distillation bottoms having a concentration of inorganic impurities;
e. subjecting the distillation bottoms to a second pre-treatment process comprising:
i. heating the distillation bottoms to a temperature above ambient temperature;
ii. adding an aqueous acid solution to the heated distillation bottoms and mixing to produce a mixture; and
iii. separating the mixture to produce a refined biological feedstock;
wherein the distillation bottoms comprise unsaponifiable material at a concentration greater than 2 wt %, and the refined biological feedstock has a reduced concentration of inorganic impurities and reduced alkalinity compared to the biological feedstock;
f. diluting the refined biological feedstock with a hydrocarbon oil to produce a diluted biological feedstock;
g. subjecting the diluted biological feedstock to a hydrodeoxygenation process by contacting the diluted biological feedstock with a hydrogen-rich gas and a catalyst at a temperature and pressure which are elevated above an ambient temperature and pressure to produce a reactor effluent;
h. recovering a hydrocarbons fraction from the reactor effluent.

### Claim 25 (depends on 24)

The process of claim 24 further comprising separating the reactor effluent into a hydrocarbon phase, a gas phase, and an aqueous phase and using a hydrocarbon stripper to separate the hydrocarbon phase into an overheads fraction and the hydrocarbons fraction.

### Claim 26 (depends on 24)

The process of claim 24 further comprising adding the hydrocarbons fraction to a diesel fuel.

### Claim 27 (depends on 24)

The process of claim 24 further comprising introducing the hydrocarbons fraction to at least one of a hydrocracking and hydroisomerization process to produce a renewable diesel fuel.

### Claim 28 (depends on 24)

The process of claim 24 wherein the pretreatment process further comprises water washing the distillation bottoms to produce the refined distillation bottoms.

### Claim 29 (depends on 24)

The process of claim 24 wherein the pretreatment process reduces the Alkalinity by at least 80%.

### Claim 30 (depends on 24)

The process of claim 24 wherein the catalyst in the hydrodeoxygenation process includes a first catalyst bed having a first activity and a second catalyst bed having, a second activity, and the first activity is lower than the second activity, wherein the hydrodeoxygenation process further includes subjecting the diluted biological feedstock to the first catalyst bed before subjecting the diluted distillation bottoms to the second catalyst bed.

### Claim 31

A process for producing stripped hydrocarbons from a biological feedstock comprising:
a. subjecting the biological feedstock to a pre-treatment process comprising:
i. heating the biological feedstock to a temperature above ambient temperature;
ii. adding an aqueous acid solution to the heated biological feedstock and mixing to produce a mixture; and
iii. separating the mixture to produce a refined biological feedstock;
wherein the biological feedstock comprises a distillation bottoms recovered from a biodiesel distillation process, the distillation bottoms comprising unsaponifiable material at a concentration greater than 2 wt %, and the refined biological feedstock has a reduced concentration of inorganic impurities and reduced alkalinity compared to the biological feedstock;
b. diluting the refined biological feedstock with a hydrocarbon oil to provide a diluted biological feedstock;
c. subjecting the diluted biological feedstock to a hydrodeoxygenation process by contacting the diluted biological feedstock with a hydrogen-rich gas and a catalyst at a temperature and pressure which are elevated above an ambient temperature and pressure to produce a reactor effluent;
d. separating the reactor effluent into a hydrocarbon phase, a gas phase, and an aqueous phase;
e. using a hydrocarbon stripper to separate the hydrocarbon phase into a stripper overheads fraction and a stripped hydrocarbons fraction.

### Claim 32 (depends on 31)

The process of claim 31 wherein the biological feedstock comprises free fatty acids and fatty acid glyceride esters.

### Claim 33 (depends on 31)

The process of claim 31 wherein the temperature is between about 260 C and 371 C and the pressure is between about 500 and 2,500 psig.

### Claim 34 (depends on 31)

The process of claim 31 further comprising adding the stripped hydrocarbons fraction to a diesel fuel.

### Claim 35 (depends on 31)

The process of claim 31 further comprising introducing the stripped hydrocarbons fraction to at least one of a hydrocracking and hydroisomerization process to produce a renewable diesel fuel.

### Claim 36 (depends on 31)

The process of claim 31 wherein the biological feedstock comprises unsaponifiable material at a concentration greater than 3 wt %.

### Claim 37 (depends on 31)

The process of claim 31 wherein the biological feedstock comprises unsaponifiable material at a concentration greater than 4 wt %.