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 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.
2. 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.
3. The method according to claim 2 , wherein the intermittent operation of step (c) employs a multi-distillation tank circulation reaction.
4. The method according to claim 2 , wherein the continuous operation of step (c) employs a continuous catalytic distillation reaction.
5. 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.
6. 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%.
7. The method according to claim 1 , wherein the first set of heating conditions in step (a) is from 100° C. to 600° C.
8. 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.
9. 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.
10. 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.
11. 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.
12. 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).
13. The method according to claim 1 , wherein step (b) is carried out at a pressure of −0.05 MPa to −0.3 MPa.
14. The method according to claim 1 , wherein step (b) is carried out at a temperature ranging from 100° C. to 500° C.
15. 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.
16. 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.
17. 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.
18. 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.
19. 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.
20. The method according to claim 1 , wherein step (a) further comprises a step of preheating the high-acid-value biological grease.
21. The method according to claim 1 , wherein the hydrodeoxygenation catalyst is a supported metal catalyst or metal sulfide.
22. 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).
23. The method according to claim 1 , wherein the product obtained in step (c) has an acid value of <50 mgKOH/g.