# US 12,006,484 B2 · Method and system for preparing fuel by using high acid value biological oil and fat

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- Number: US 12,006,484 B2
- Document ID: US12006484B2
- Status: Granted
- Kind: B2
- Application number: 17/390,941
- Filed: 2021-07-31
- Published: 2021-11-18
- Granted: 2024-06-11
- Earliest claimed: 2019-02-01
- Assignees: Eco Environmental Energy Research Institute Limited; Tianjin University
- Applicants: ECO Environmental Energy Research Institute Limited; Tianjin University
- Inventors: Bin Xu; Kam Shing Siu; Chunjian Xu; Yongchao He
- Web page: https://patentgrep.com/patent/US12006484B2

## CPC

- C10L 1/026: {for compression ignition}
- B01D 3/009: {in combination with chemical reactions}
- B01D 3/10: Vacuum distillation (B01D3/12 takes precedence)
- B01D 3/143: {by two or more of a fractionation, separation or rectification step}
- B01J 3/006: {Processes utilising sub-atmospheric pressure; Apparatus therefor}
- B01J 6/008: {Pyrolysis reactions (of hydrocarbons C10G9/00)}
- B01J 19/245: {placed in series}
- C10G 3/40: {Thermal non-catalytic treatment}
- C10G 3/42: {Catalytic treatment}
- C10G 3/49: {containing crystalline aluminosilicates, e.g. molecular sieves}
- C10G 3/50: {in the presence of hydrogen, hydrogen donors or hydrogen generating compounds}
- C10G 7/06: Vacuum distillation
- C10L 1/08: for compression ignition
- B01J 2219/0004: Processes in series
- B01J 2219/00051: Controlling the temperature
- B01J 2219/00162: controlling the pressure
- B01J 2219/00166: controlling the residence time inside the reactor vessel
- C10G 2300/1003: Waste materials
- C10G 2300/1011: Biomass
- C10G 2300/1014: of vegetal origin
- C10G 2300/202: Heteroatoms content, i.e. S, N, O, P
- C10G 2300/207: Acid gases, e.g. H2S, COS, SO2, HCN
- C10G 2300/301: Boiling range
- C10G 2300/302: Viscosity
- C10G 2300/308: Gravity, density, e.g. API
- C10G 2300/4018: Spatial velocity, e.g. LHSV, WHSV
- C10G 2400/04: Diesel oil
- C10L 2200/0476: Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
- C10L 2200/0484: Vegetable or animal oils
- C10L 2290/02: Combustion or pyrolysis
- C10L 2290/543: Distillation, fractionation or rectification for separating fractions, components or impurities during preparation or upgrading of a fuel
- Y02P 30/20: using bio-feedstock
- 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
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention provides a method and a system for preparing fuel using high-acid-value biological grease, which can be processed through triple deoxidization steps, i.e., thermal cracking deoxygenation-catalytic cracking deoxygenation-catalytic hydrodeoxygenation. By use of the method and system of the invention, the raw material of the high-acid-value biological grease can be gradually deoxidized to reduce the acid value and thereby prepare a clean fuel with equivalent fuel components as those obtained from crude oil refining or direct hydrodeoxygenation for biological grease.

## Claims

### Claim 1

A method for preparing fuel using high-acid-value biological grease, comprising:
(a) subjecting the high-acid-value biological grease to thermal cracking and deoxidization under a first set of heating conditions;
(b) subjecting a product of step (a) to vacuum distillation to separate water, a high-acid-value fraction, a low-acid-value fraction and a heavy component;
(c) catalytically cracking and deoxidizing the high-acid-value fraction obtained in the step (b) to separate water and non-condensable gas in the presence of a catalytic cracking deoxidization catalyst under a second set of heating conditions; and
(d) catalytically hydrodeoxygenating a mixture of a product obtained in the step (c) and the low-acid-value fraction obtained in the step (b) with hydrogen in the presence of a hydrodeoxygenation catalyst under a third set of heating conditions.

### Claim 2 (depends on 1)

The method according to claim 1, wherein the steps (a), (b) and (d) are operated continuously, and the step (c) is operated continuously or intermittently.

### Claim 3 (depends on 2)

The method according to claim 2, wherein the intermittent operation of step (c) employs a multi-distillation tank circulation reaction.

### Claim 4 (depends on 2)

The method according to claim 2, wherein the continuous operation of step (c) employs a continuous catalytic distillation reaction.

### Claim 5 (depends on 1)

The method according to claim 1, wherein the high-acid-value biological grease is of an animal source, a plant source, a microbial source or a mixture of the foregoing.

### Claim 6 (depends on 5)

The method according to claim 5, wherein the high-acid-value biological grease has an acid value of ≥80 mgKOH/g or a free fatty acid content of ≥40%.

### Claim 7 (depends on 1)

The method according to claim 1, wherein the first set of heating conditions in step (a) is from 100° C. to 600° C.

### Claim 8 (depends on 1)

The method according to claim 1, wherein the high-acid-value biological grease in step (a) is subjected to thermal cracking deoxidization for 1 to 60 minutes.

### Claim 9 (depends on 1)

The method according to claim 1, wherein the products of step (a) comprise olefins, alkanes, ketones, aliphatic acids, aliphatic alcohols, carbon monoxide, carbon dioxide, and water.

### Claim 10 (depends on 1)

The method according to claim 1, wherein the high-acid-value fraction obtained in step (b) has an acid value in the range of 80 to 120 mgKOH/g, and the low-acid-value fraction has an acid value in the range of 10 to 50 mgKOH/g.

### Claim 11 (depends on 1)

The method according to claim 1, wherein the products of step (b) comprise water, a high-acid-value fraction, a low-acid-value fraction, a heavy component, carbon dioxide, and carbon monoxide.

### Claim 12 (depends on 1)

The method according to claim 1, wherein the heavy component of step (b) can be treated as a waste material or mixed with a raw material as the raw material for step (a).

### Claim 13 (depends on 1)

The method according to claim 1, wherein step (b) is carried out at a pressure of −0.05 MPa to −0.3 MPa.

### Claim 14 (depends on 1)

The method according to claim 1, wherein step (b) is carried out at a temperature ranging from 100° C. to 500° C.

### Claim 15 (depends on 1)

The process according to claim 1, wherein catalytic cracking deoxidization catalyst of step (c) is selected from the group consisting of alumina, molecular sieves, silicon carbide or mixtures thereof.

### Claim 16 (depends on 1)

The method according to claim 1, wherein the second set of heating conditions in step (c) is carried out, at a temperature ranging from 100° C. to 500° C.

### Claim 17 (depends on 1)

The method according to claim 1, wherein the third set of heating conditions in step (d) is carried out, at a temperature ranging from 200° C. to 400° C., a hydrogen partial pressure of 1 MPa to 6 MPa, a volume space velocity of 0.5 h−1 to 4.0 h−1, and a hydrogen oil volume ratio of 200 to 1200:1.

### Claim 18 (depends on 1)

The method according to claim 1, further comprising:
(e) fractionating a product of step (d) to obtain a gasoline component, a diesel component and a heavy component of >365° C.

### Claim 19 (depends on 18)

The method according to claim 18, wherein the heavy component of >365° C. is mixed with the high-acid-value fraction of step (b) as part of the raw material for the catalytic cracking deoxidization reaction.

### Claim 20 (depends on 1)

The method according to claim 1, wherein step (a) further comprises a step of preheating the high-acid-value biological grease.

### Claim 21 (depends on 1)

The method according to claim 1, wherein the hydrodeoxygenation catalyst is a supported metal catalyst or metal sulfide.

### Claim 22 (depends on 4)

The method according to claim 4, wherein the fraction obtained from the continuous catalytic distillation reaction of step (c) is used as a raw material for the catalytic hydrodeoxygenation reaction in step (d).

### Claim 23 (depends on 1)

The method according to claim 1, wherein the product obtained in step (c) has an acid value of <50 mgKOH/g.