Integrated hydrocarbon desulfurization with oxidation of disulfides and conversion of SO2 to elemental sulfur
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-027/06
B01D-053/50
B01D-053/52
C01B-017/50
C10G-019/02
C01B-017/04
출원번호
US-0552222
(2014-11-24)
등록번호
US-9580661
(2017-02-28)
발명자
/ 주소
Koseoglu, Omer Refa
출원인 / 주소
Saudi Arabian Oil Company
대리인 / 주소
Abelman, Frayne & Schwab
인용정보
피인용 횟수 :
0인용 특허 :
8
초록▼
A process to produce a sulfur-free hydrocarbon product stream from a liquid hydrocarbon disulfide product, e.g., of the Merox Process, includes subjecting the hydrocarbon disulfide to a catalytic oxidation step to produce SO2 which is separated from the remaining desulfurized hydrocarbons that form
A process to produce a sulfur-free hydrocarbon product stream from a liquid hydrocarbon disulfide product, e.g., of the Merox Process, includes subjecting the hydrocarbon disulfide to a catalytic oxidation step to produce SO2 which is separated from the remaining desulfurized hydrocarbons that form the clean sulfur-free hydrocarbon product stream; the SO2 is introduced into a Claus processing unit with the required stoichiometric amount of hydrogen sulfide (H2S) gas to produce elemental sulfur.
대표청구항▼
1. In the process for treating a liquid hydrocarbon feedstream to remove mercaptans present in the stream by a. contacting the mercaptan-containing hydrocarbon feedstream with an aqueous caustic solution to oxidize the mercaptans and produce a spent caustic solution and mercaptan-free hydrocarbons;b
1. In the process for treating a liquid hydrocarbon feedstream to remove mercaptans present in the stream by a. contacting the mercaptan-containing hydrocarbon feedstream with an aqueous caustic solution to oxidize the mercaptans and produce a spent caustic solution and mercaptan-free hydrocarbons;b. subjecting the spent caustic and hydrocarbons to a wet air oxidation step to regenerate the spent caustic and produce a liquid hydrocarbon disulfide product;c. separating the regenerated aqueous caustic solution from the hydrocarbon disulfide and recycling the caustic to step (a); the improvement comprising: d. oxidizing the hydrocarbon disulfide product to sulfur dioxide and a hydrocarbon product stream that is substantially free of sulfur;e. separating and recovering the hydrocarbon product stream;f. reacting the sulfur dioxide with H2S in a predetermined stoichiometric ratio to produce an elemental sulfur product and water; andg. recovering the sulfur. 2. The process of claim 1 in which the caustic is selected from the group consisting of aqueous solutions of sodium hydroxide, ammonia, potassium hydroxide, and combinations thereof. 3. The process of claim 1 which includes subjecting the H2S to an oxidation reaction to convert a predetermined portion of the H2S to sulfur dioxide in order to achieve a stoichiometric ratio of 2H2S:SO2 to complete the sulfur-producing reaction: 2H2S+SO2→3S+2H2O. 4. The process of claim 1 in which the hydrocarbon disulfide is oxidized in the presence of a catalyst. 5. The process of claim 4 in which the catalyst is selected from the group consisting of catalytic compositions comprising copper oxide in an amount ranging from 10 weight percent (wt %) to 50 wt %, zinc oxide in an amount ranging from 5 wt % to less than 20 wt %, and aluminum oxide in an amount ranging from 20 wt % to 70 wt %, wherein said catalytic composition has an X-ray amorphous oxide phase, and a formula CuxZn1−xAl2O4, wherein x ranges from 0 to 1, highly dispersed crystalline ZnO and CuO alone and said composition further comprises CeO2 in the form of particles ranging in diameter from 5 nm to 10 nm, in an amount ranging from 0.1 wt % to 10 wt % of said catalytic composition, and combinations thereof. 6. The process of claim 5 in which the catalyst composition comprises from 20 wt % to 45 wt % CuO, from 10 wt % to less than 20 wt % ZnO, and from 20 wt % to 70 wt % Al2O3. 7. The process of claim 6 in which the catalyst composition comprises from 30 wt % to 45 wt % CuO, from 12 wt % to less than 20 wt % ZnO, and from 20 wt % to 40 wt % Al2O3. 8. The process of claim 4 in which the oxidation catalyst is CuCr2O4/CeO2/Al2O3. 9. The process of claim 1 in which the liquid hydrocarbon disulfide product has a sulfur content in the range of from 10 to 60 wt %. 10. The process of claim 1 in which the hydrocarbon disulfide is contacted with the oxidation catalyst at a temperature in the range of from 200° C. to 600° C. 11. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O2:C in a range of from 1:100 to 1:10 and a molar ratio of O2:S is in the range of from 1:1 to about 150:1. 12. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a weight hourly space velocity (WHSV) that is in the range of from 1 h−1 to 100 h−1. 13. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a gas hourly space velocity (GHSV) that is in the range of from 1,000 h−1 to 25,000 h−1. 14. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include an operating pressure that is in the range of from 1 bar to 30 bars. 15. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include an operating pressure that is in the range of from 1 bar to 5 bars, a weight hourly space velocity (WHSV) that is in the range of from 10h−1 to 30h−1, and a as hourly space velocity (GHSV) that is in the range of from 5,000 h−1 to 10,000 h−1. 16. The process of claim 1. in which the hydrocarbon disulfide is contacted with the oxidation catalyst at a temperature in the range of from about 250° C. to about 550° C. 17. The process of claim 1 in which the hydrocarbon disulfide is contacted with the oxidation catalyst at a temperature in the range of from about 300° C. to about 500° C. 18. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O2:C in a range of from 1:50 to 1:10 and a molar ratio of O2:S is in the range of from 1:1 to about 150:1. 19. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O2:C in a range of from 1:20 to 1:10 and a molar ratio of O2:S is in the range of from 1:1 to about 150:1. 20. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O2:C in a range of from 1:100 to 1:10, and a molar ratio of O2:S is in the range of from 10:1 to 100:1. 21. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a molar ratio of O2:C in a range of from 1:100 to 1:10 and a molar ratio of O2:S is in the range of from 20:1 to 50:1. 22. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a weight hourly space velocity (WHSV) that is in the range of from 5 h−1 to 50 h−1. 23. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a weight hourly space velocity (WHSV) that is in the range of from 10 h−1 to 30 h−1. 24. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a gas hourly space velocity (GHSV) that is in the range of from 5,000 h−1 to 15,000 h−1. 25. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include a gas hourly space velocity (GHSV) that is in the range of from 5,000 h−1 to 10,000 h−1. 26. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include an operating pressure that is in the range of from 1 bar to 10 bars. 27. The process of claim 4 in which the hydrocarbon disulfide is contacted with the oxidation catalyst under conditions that include an operating pressure that is in the range of from 1 bar to 5 bars.
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이 특허에 인용된 특허 (8)
Carlsson, Anders, Method for disposal of di-sulphide compounds.
Audeh Costandi A. (Princeton NJ) Greco Saverio G. (Princeton Junction NJ), Method for treating sulfur-containing effluents resulting from petroleum processing.
Kvasnikoff Georges (Monein FRX) Nougayrede Jean (Pau FRX) Philippe Andre (Orthez FRX), Process for the production of sulphur from at least one sour gas containing hydrogen sulphide and a fuel effluent and th.
Sibeud Jacques Pierre (Princeton NJ) Ruff Charles David (Highland Park NJ), Process for the removal of hydrogen sulfide and mercaptans from liquid and gaseous streams.
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