Method for preparing fuel by using biological oils and fats

Patent metadata

Field	Value
Publication number	US-9938468-B2
Application number	US-201214126007-A
Country	US
Kind code	B2
Filing date	Jun 12, 2012
Priority date	Jun 13, 2011
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

A new method of producing fuel from biological oils and fats is provided, which comprises the following steps: (a) proceeding with a catalytic cracking-deoxygenation reaction for the biological oils and fats under heating in the presence of a cracking-deoxygenation catalyst; (b) mixing the product of step (a) with hydrogen gas; and (c) proceeding with a catalytic hydrodeoxygenation reaction for the mixture from step (b) under heating in the presence of a hydrodeoxygenation catalyst. By means of the method of the present invention, clean fuel produced by using biological oils and fats as raw materials is compatible with the fuel composition produced from crude oil refining.

First claim

What is claimed is:

1. A method for preparing fuel from a biological oil or fat, comprising:
(a) heating and gasifying a raw material comprising a biological oil or fat in a distillation still to produce a gasified raw material;
(b) passing the gasified raw material into a catalytic distillation tower and subjecting the gasified raw material to catalytic cracking-deoxygenation by heating the gasified raw material in the presence of a catalytic cracking-deoxygenation catalyst to produce a product, wherein the catalytic cracking-deoxygenation takes place in the gas phase;
(c) mixing the product of step (b) with hydrogen gas to produce a mixture; and
(d) subjecting the mixture from step (c) to a catalytic hydrodeoxygenation by heating the mixture in the presence of a hydrodeoxygenation catalyst to produce a hydrodeoxygenation product comprising said fuel.

2. The method according to claim 1 , wherein step (b) is operated continuously or in batch.

3. The method according to claim 1 , wherein the catalytic cracking-deoxygenation in the catalytic distillation tower is a continuous process and the catalytic hydrodeoxygenation is a continuous process.

4. The method according to claim 1 , wherein the raw material is from animal origin, plant origin, microorganism origin or mixtures thereof.

5. The method according to claim 1 , wherein the catalytic cracking-deoxygenation catalyst is selected from aluminum oxide, molecular sieves or a mixture thereof.

6. The method according to claim 5 , wherein the catalytic cracking-deoxygenation catalyst is a molecular sieve, wherein the molecular sieve is selected from the group consisting of HY, Hβ, SAPO-31, HZSM-5, and HZSM-22.

7. The method according to claim 5 , wherein the catalytic cracking-deoxygenation catalyst is a mixture of aluminum oxide and molecular sieve, and wherein the molecular sieve content of the catalytic cracking-deoxygenation catalyst is 5-70 wt %.

8. The method according to claim 1 , wherein the catalytic cracking-deoxygenation catalyst is a formed catalyst and a ratio of equivalent diameter of the catalytic cracking-deoxygenation catalyst to the diameter of the catalytic distillation tower is less than 0.1.

9. The method according to claim 1 , wherein a mass ratio of the catalytic cracking-deoxygenation catalyst in step (b) to the gasified raw material of step (b) is selected from the group consisting of 1:5, 1:10, 1:15, 1:20, 1:30, 1:40, and 1:50.

10. The method according to claim 1 , wherein the catalytic cracking-deoxygenation catalyst is water resistant.

11. The method according to claim 1 , wherein the catalytic cracking-deoxygenation takes place at 450-600° C.

12. The method according to claim 1 , wherein the product of step (b) comprises alkenes, alkanes, carbon monoxide, carbon dioxide, water or combinations thereof.

13. The method according to claim 1 , wherein the hydrodeoxygenation catalyst comprises a supported metal catalyst comprising one or more metals selected from the group consisting of Group IIIB metals, Group IVB metals, Group VB metals, Group VIB metals, Group VIIB metals, Group VIII metals, and alloys thereof.

14. The method according to claim 1 , wherein the catalytic hydrodeoxygenation takes place at 200-400° C.

15. The method according to claim 1 , further comprising: (e) fractionating the hydrodeoxygenation product comprising said fuel to obtain gasoline and diesel.

16. The method according to claim 1 , wherein the product produced by the catalytic cracking-deoxygenation comprises dry gas, wherein the dry gas is used for heating the gasified raw material in step (b) and heating the mixture in step (d).

17. The method according to claim 1 , wherein the catalytic hydrodeoxygenation takes place in a hydrodeoxygenation reactor and wherein the product of step (b) passes through a feeding pump before mixing with hydrogen gas in step (c), and then enters into the hydrodeoxygenation reactor through a heat exchanger.

18. The method according to claim 1 , wherein the distillation still is operated at a temperature between 450° C. and 600° C., the catalytic cracking-deoxygenation catalyst is a mixture of aluminum oxide and molecular sieves, and the mass ratio of the catalytic cracking-deoxygenation catalyst to the gasified raw material of step (b) is between 1:5 and 1:20.

19. The method according to claim 1 , wherein step (d) takes place in a hydrodeoxygenation reactor, the hydrodeoxygenation catalyst is a supported metal catalyst, the mixture is heated to 200-400° C. in the hydrodeoxygenation reactor, the partial pressure of hydrogen gas in the hydrodeoxygenation reactor is 1-6 MPa, the volume space velocity in the hydrodeoxygenation reactor is 0.5-4.0 h −1 , and the hydrogen/oil volume ratio in the hydrodeoxygenation reactor is in the range of from 200:1 to 1200:1.

20. The method according to claim 1 , wherein the gasified raw material comprises free fatty acids and triglycerides and wherein the catalytic cracking-deoxygenation comprises the following reactions:

in which R, R′, and R″ are each an alkyl of C 10-22 .

21. The method according to claim 1 , wherein the mixture of step (c) comprises alkenes, free fatty acids, and triglycerides, and wherein the catalytic hydrodeoxygenation comprises the following reactions:

in which R, R′, and R″ are each an alkyl of C 10-22 .

Assignees

• Liang Changhai
• Xu Bin
• Siu Philip
• Wang Lei
• Chen Xiao
• Shao Zhengfeng
• Xiao Zihui
• Eco Environmental Energy Res Institute Limited
• Univ Dalian Tech

Inventors

• Liang Changhai
• Xu Bin
• Siu Philip
• Wang Lei
• Chen Xiao
• Shao Zhengfeng
• Xiao Zihui

Classifications

• C10G3/50 Primary

  in the presence of hydrogen, hydrogen donors or hydrogen generating compounds · CPC title

• C10G3/42

  Catalytic treatment · CPC title

• C10G11/05

  Crystalline alumino-silicates, e.g. molecular sieves · CPC title

• C10G65/12

  including cracking steps and other hydrotreatment steps · CPC title

• C11B3/12

  by distillation · CPC title