Method and system for preparing fuel by using high acid value biological oil and fat
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.
1. A system for preparing fuel using high-acid-value biological grease, comprising:
a thermal cracking reactor, the thermal cracking reactor configured to:
i. receive high-acid-value biological grease, and
ii. subject the high-acid-value biological grease to thermal cracking and deoxidization under a first set of heating conditions;
a vacuum distillation column connected to the thermal cracking reactor, the vacuum distillation column configured to:
i. receive a product obtained from the thermal cracking reactor; and
ii. perform vacuum distillation so as to separate water, a high-acid-value fraction, a low-acid-value fraction and a heavy component;
a catalytic cracking deoxidization reactor connected to the vacuum distillation column, the catalytic cracking deoxidization reactor configured to catalytically crack and deoxidize the high-acid-value fraction obtained from the vacuum distillation so as to separate water and non-condensable gas in the presence of a catalytic cracking deoxidization catalyst under a second set of heating conditions; and
a hydrorefining reaction column configured to:
i. receive a product from the catalytic cracking deoxidization reactor and the low-acid-value fraction from the vacuum distillation column,
ii. mix the product from the catalytic cracking deoxidization reactor and the low-acid-value fraction from the vacuum distillation column, and
iii. perform catalytic hydrodeoxygenation reaction with hydrogen, in the presence of a hydrodeoxygenation catalyst, under a third set of heating conditions.
2. The system according to claim 1 , wherein the catalytic cracking deoxidization reactor employs a multi-distillation tank or a catalytic distillation column.
3. The system 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.
4. The system according to claim 1 , wherein the high-acid-value biological grease has an acid value ≥80 mgKOH/g or a free fatty acid content ≥40%.
5. The system according to claim 1 , wherein the first set of heating condition in the thermal cracking reactor is from 100° C. to 600° C., and the residence time of the high-acid-value biological grease in the thermal cracking reactor is from 1 to 60 minute.
6. The system according to claim 1 , wherein the products of the thermal cracking reactor comprise olefins, alkanes, ketones, aliphatic acids, aliphatic alcohols, carbon monoxide, carbon dioxide, and water.
7. The system according to claim 1 , wherein a high-acid-value fraction obtained from the vacuum distillation column has an acid value in the range of 80 to 120 mgKOH/g, and a low-acid-value fraction has an acid value in the range of 10 to 50 mgKOH/g.
8. The system according to claim 1 , wherein the products of the vacuum distillation column comprise water, a high-acid-value fraction, a low-acid-value fraction, a heavy component, carbon dioxide, and carbon monoxide.
9. The system according to claim 1 , wherein the heavy component obtained from the vacuum distillation column is treated as a waste material or mixed with a raw material as the raw material of the thermal cracking reactor.
10. The system according to claim 1 , wherein the pressure in the vacuum distillation column is from −0.05 MPa to −0.3 MPa, and the temperature is from 200° C. to 500° C.
11. The system according to claim 1 , wherein the catalytic cracking deoxidization catalyst is selected from the group consisting of alumina, molecular sieves, silicon carbide, or mixtures thereof.
12. The system according to claim 1 , wherein the catalytic cracking deoxidization reactor is heated at a temperature ranging from 100° C. to 500° C.
13. The system according to claim 1 , wherein the hydrodeoxygenation catalyst is a supported metal catalyst or metal sulfide.
14. The system according to claim 1 , wherein the hydrorefining reaction column has a heating condition of 200° C. to 400° C., a hydrogen partial pressure of 1 MPa to 6 MPa, a volumetric space velocity of 0.5 h −1 to 4.0 h −1 , and a hydrogen oil volume ratio of 200 to 1200:1.
15. The system according to claim 1 , wherein the system further comprises an atmospheric distillation column connected to the hydrorefining reaction column for fractionating the product of the hydrorefining reaction column to obtain a gasoline component, a diesel component and a heavy component of >365° C.
16. The system according to claim 15 , wherein a heavy component of >365° C. can be mixed with the high-acid-value fraction obtained from the vacuum distillation column as part of feed to the catalytic cracking deoxidization reactor.
17. The system according to claim 1 , wherein the system further comprises a preheater connected to the thermal cracking reactor for preheating the high-acid-value biological grease entering the thermal cracking reactor.
18. The system according to claim 1 , wherein the hydrodeoxygenation catalyst is a supported metal catalyst or metal sulfide.
19. The system according to claim 1 , wherein the product of the catalytic cracking deoxidization reactor has an acid value of <50 mgKOH/g.
20. A system for preparing fuel using high-acid-value biological grease, comprising:
a thermal cracking reactor, the thermal cracking reactor configured to:
subject a high-acid-value biological grease to thermal cracking under a first set of heating conditions;
a vacuum distillation column connected to the thermal cracking reactor, the vacuum distillation column configured to:
i. receive a product obtained from the thermal cracking reactor; and
ii. perform vacuum distillation so as to separate high-acid-value fraction and low-acid-value fraction from the product obtained from the thermal cracking reactor;
a catalytic cracking deoxidization reactor connected to the vacuum distillation column, the catalytic cracking deoxidization reactor configured to catalytically crack and deoxidize the high-acid-value fraction obtained from the vacuum distillation so as to separate water and non-condensable gas in the presence of a catalytic cracking deoxidization catalyst under a second set of heating conditions; and
a preheater connected to the thermal cracking reactor, the preheater configured to heat the high-acid-value biological grease entering the thermal cracking reactor.
21. The system of claim 20 , further comprising:
an atmospheric distillation column, the atmospheric distillation column configured to fractionate a downstream output after the catalytic cracking deoxidization reactor so as to obtain a gasoline component, a diesel component and a heavy component.
22. The system of claim 21 , wherein the downstream output after the catalytic cracking deoxidization reactor is an output from a hydrorefining reaction column;
wherein the hydrorefining reaction column is configured to:
i. receive and mix a product from the catalytic cracking deoxidization reactor and the low-acid-value fraction from the vacuum distillation column, and
ii. perform catalytic hydrodeoxygenation reaction with hydrogen, in the presence of a hydrodeoxygenation catalyst, under a third set of heating conditions.