OXIDATIVE DESULFURIZATION IN FLUID CATALYTIC CRACKING PROCESS

• US 20130026071A1
• Filed: 07/27/2012
• Published: 01/31/2013
• Est. Priority Date: 07/29/2011
• Status: Active Grant

• Current Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Original Assignee: Saudi Arabian Oil Company (Government of Saudi Arabia)
• Inventors: Koseoglu, Omer Refa, Bourane, Abdennour
• Granted Patent: US 9,062,259 B2
• Time in Patent Office: Days
• US Class Current: 208/120.01
• CPC Class Codes: C10G 11/18 according to the "fluidised-bed" technique
• CPC Class Codes: C10G 11/182 Regeneration
• CPC Class Codes: C10G 2300/202 Heteroatoms content, i.e. S, N, O, P
• CPC Class Codes: C10G 2300/4056 Retrofitting operations
• CPC Class Codes: C10G 27/04 with oxygen or compounds generating oxygen
• CPC Class Codes: C10G 27/10 in the presence of metal-containing organic complexes, e.g. chelates, or cationic ion-exchange resins
• CPC Class Codes: C10G 55/00 Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one refining process and at least one cracking process
• CPC Class Codes: C10G 55/06 including at least one catalytic cracking step

Abstract

A process for catalytically cracking and oxidatively desulfurizing a hydrocarbon feedstock containing organosulfur compounds is provided. Oxygen containing gas is introduced with a cracking catalyst and the feed to form a suspension. At least a portion of organosulfur compounds in the hydrocarbon feedstock are oxidized to form oxidized organosulfur compounds, carbon-sulfur bonds of oxidized organosulfur compounds are cleaved to form sulfur-free hydrocarbon compounds and sulfur oxides, and oxidized and unoxidized compounds are catalytically cracked into hydrocarbon compounds of lower boiling points. Cracked components and the cracking catalyst particles are separated and recovered for regeneration and reuse.

Claims

1. A process for catalytically cracking and oxidatively desulfurizing a hydrocarbon feedstock containing organosulfur compounds to thereby recover a product stream including lower boiling hydrocarbon components and having a reduced concentration of organosulfur compounds as compared to the hydrocarbon feedstock, the process comprising the steps of:

a. combining the hydrocarbon feedstock, an effective amount of oxygen containing gas, an effective amount of heated cracking catalyst and optionally an effective amount of heterogeneous catalyst additive containing oxidation functionality to form a suspension;

b. maintaining the suspension through a reaction zone of a fluid catalytic cracking reactor apparatus to

oxidize at least a portion of organosulfur compounds in the hydrocarbon feedstock to form oxidized organosulfur compounds,

cleave carbon-sulfur bonds of oxidized organosulfur compounds to form sulfur-free hydrocarbon compounds and sulfur oxide, and

catalytically crack oxidized and unoxidized compounds, including unoxidized sulfur-free hydrocarbon compounds, unoxidized organosulfur compounds, and oxidized organosulfur compounds, into hydrocarbon compounds of lower boiling points,

wherein catalytic cracking occurs under conditions that favor catalytic cracking over thermal cracking of compounds in the hydrocarbon feedstock;

c. separating and recovering cracked components and the cracking catalyst particles;

d. regenerating at least a portion of the separated cracking catalyst particles; and

e. returning at least a portion of the regenerated cracking catalyst particles with the hydrocarbon feedstock and oxygen containing gas in step (a).

2. The process of claim 1, wherein step (a) further comprises adding an effective quantity of heterogeneous catalyst additive containing oxidation functionality.

3. The process of claim 1 or 2, further comprising adding an effective quantity of homogeneous catalyst additive containing oxidation functionality to the feedstock upstream of step (a).

4. The process of claim 1, wherein the reaction zone is operated at a temperature in the range of from about 400°

C. to about 565°

C.

5. The process of claim 4, wherein the reaction zone is operated at a residence time in the range of from about 1 second to about 60 seconds.

6. The process of claim 1, wherein the reaction zone is operated at a temperature in the range of from about 500°

C. to about 650°

C.

7. The process of claim 6, wherein the reaction zone is operated at a residence time in the range of from about 0.1 second to about 5 seconds.

8. The process of claim 1, wherein the recovered cracked components have a sulfur reduction of up to 50 weight %.

9. The process of claim 1, wherein the weight ratio of cracking catalyst to hydrocarbon feedstock is in the range of from 1:

1 to 40;

1.

10. The process of claim 1, wherein the weight ratio of cracking catalyst to hydrocarbon feedstock is in the range of from 1:

1 to 15;

1.

11. The process of claim 1, wherein the molar ratio of oxygen in the oxygen containing gas to sulfur compounds present in the hydrocarbon feedstock is in the range of from 1:

5 to 1;

500.

12. The process of claim 1, wherein the heterogeneous catalyst is in the range of from about 0 weight % to about 100 weight % of the cracking catalyst.

13. The process of claim 3, wherein the homogenous catalyst is in the range of up to about 30 weight % of the hydrocarbon feedstock.