Alkali metal hydroprocessing of heavy oils with enhanced removal of coke products
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-019/02
C10G-019/08
C10G-053/12
출원번호
US-0693222
(2012-12-04)
등록번호
US-8894845
(2014-11-25)
발명자
/ 주소
Vann, Walter David
Leta, Daniel Paul
McConnachie, Jonathan Martin
Demmin, Richard Alan
Hissong, Douglas Wayne
Baird, Jr., William C.
Bearden, Jr., Roby
Bielenberg, James Ronald
Freund, Howard
Wright, Chris Aaron
Raterman, Michael Francis
Rigby, James Ronald
Stone, Brandon Thomas
출원인 / 주소
ExxonMobil Research and Engineering Company
대리인 / 주소
Bordelon, Bruce M.
인용정보
피인용 횟수 :
0인용 특허 :
23
초록▼
Hydrocarbon feedstreams are desulfurized using an alkali metal reagent, optionally in the presence of hydrogen. Improved control over reaction conditions can be achieved in part by controlling the particle size of the alkali metal salt and by using multiple desulfurization reactors. The processes he
Hydrocarbon feedstreams are desulfurized using an alkali metal reagent, optionally in the presence of hydrogen. Improved control over reaction conditions can be achieved in part by controlling the particle size of the alkali metal salt and by using multiple desulfurization reactors. The processes herein allow a simple and effective method for removing the majority of coke formed in the alkali metal reagent reactions with the hydrocarbon feedstreams. This makes it cost effective to run such processes at higher severities (which result in higher coke production) thereby resulting in increased amounts of valuable converted hydrocarbon product yields. The process improvements herein may also be used to increase total throughput through a unit due to the ability to effectively manage higher coke content in the reaction products.
대표청구항▼
1. A process for desulfurizing a hydrocarbon feedstream, comprising: a) mixing at least a portion of a hydrocarbon feedstream having an API gravity of less than 19 with an aqueous alkali metal salt reagent solution to form a first mixed reactor feedstream;b) exposing at least a portion of the first
1. A process for desulfurizing a hydrocarbon feedstream, comprising: a) mixing at least a portion of a hydrocarbon feedstream having an API gravity of less than 19 with an aqueous alkali metal salt reagent solution to form a first mixed reactor feedstream;b) exposing at least a portion of the first mixed reactor feedstream to a first desulfurization reactor operated under first effective desulfurization conditions to form a first desulfurized reactor product stream comprising desulfurized oil, spent alkali metals, and coke;c) separating the first desulfurized reactor product stream to form at least a first low-boiling point vapor fraction and a first reactor product liquid fraction;d) mixing at least a portion of the first reactor product liquid fraction with water to form a first wash water separator feedstream;e) sending the first wash water separator feedstream to a first wash water separator vessel wherein in the first wash water separator vessel, the first wash water separator feedstream forms three distinct layers as flows: a first desulfurized oil product layer, a first emulsion phase layer, and a first aqueous spent alkali metal layer;f) removing each of the three distinct layers separately from the first wash water separator vessel to separately form a first desulfurized oil product stream, a first emulsion phase stream, and a first aqueous spent alkali metal stream;wherein at least 50 wt % of the total coke in the first desulfurized reactor product stream is removed in the first emulsion phase stream, and the first desulfurized oil product stream has a lower sulfur content by wt % than the hydrocarbon feedstream, and the first desulfurized oil product stream has a API gravity of at least 20 and a viscosity of less than or equal to 40 centistokes at 40° C. 2. The process of claim 1, further comprising: heating the first mixed reactor feedstream to a temperature of at least 150° C.;sending the heated first mixed reactor feedstream through a mixing device; andremoving at least at least a portion of the water from the first mixed reactor feedstream prior to step b). 3. The process of claim 1, wherein the alkali metal salt reagent solution comprises an alkali metal sulfide, an alkali metal hydrogen sulfide, an alkali metal hydroxide, or a combination thereof. 4. The process of claim 3, wherein the alkali metal salt reagent solution comprises K2S, KHS, KOH or a mixture thereof. 5. The process of claim 4, wherein the alkali metal salt reagent solution comprises KOH. 6. The process of claim 5, wherein the first aqueous spent alkali metal stream comprises K2S, KHS, KNaS or a mixture thereof. 7. The process of claim 1, wherein the first effective desulfurization conditions are from about 50 to about 3000 psi (345 to 20,684 kPa), and from about 600° F. to about 900° F. (316° C. to 482° C.). 8. The process of claim 1, wherein the first low-boiling point vapor fraction is comprised of a first naphtha fraction, wherein the first naphtha fraction has a T5 boiling point greater than 25° C. (77° F.) and a T95 boiling point less than 235° C. (455° F.). 9. The process of claim 8, wherein at least a portion of the first naphtha fraction is combined with the first desulfurized oil product stream. 10. The process of claim 1, wherein a hydrogen-containing stream, comprised of at least 75 mol % hydrogen is added to the first mixed reactor feedstream either prior to or in the first desulfurization reactor. 11. The process of claim 1, wherein the amount of alkali metal salt (on an alkali metal molar basis) in the aqueous alkali metal salt reagent solution is at least 1.2 times the amount of sulfur (on a sulfur molar basis) of the hydrocarbon feedstream. 12. The process of claim 1, wherein the hydrocarbon feedstream is a heavy oil feedstream having a sulfur content of at least about 3 wt %. 13. The process of claim 1, wherein at least 75 wt % of the total coke generated in step b) is removed in the first emulsion phase stream. 14. The process of claim 13, wherein the amount of alkali metal salt in the first mixed reactor feedstream is at least about 20 wt % of the hydrocarbon feedstream. 15. The process of claim 1, wherein at least 95 wt % of the total coke generated in step b) is removed in the first emulsion phase stream, and the amount of alkali metal salt in the first mixed reactor feedstream is at least about 25 wt % of the hydrocarbon feedstream. 16. The process of claim 1, wherein at least a portion of the first emulsion phase stream is further processed, the steps comprising: sending at least a portion of the first emulsion phase stream to a refinery Coker unit;mixing the first emulsion phase stream with a coker feed stream to form mixed coker feed stream;heating the mixed coker feedstream;sending the mixed coker feedstream to a coker drum; andseparating at least a portion of the coke that was in the first emulsion phase stream from the mixed coker feedstream. 17. The process of claim 1, wherein the first wash water separator vessel comprises an interface level detector selected from a conductivity probe and a specific gravity displacement probe. 18. The process of claim 17, wherein the first wash water separator vessel has more than one draw nozzles equipped with automated control valves for the first emulsion phase layer which are located at different elevations on the first wash water separator vessel and the output from interface level detector is further connected to a controller which sends at least one output to each automated control valves for controlling the flow of the first emulsion phase stream from the first wash water separator vessel. 19. The process of claim 17, wherein the first wash water separator vessel is further comprised of at least one set of internal underflow/overflow weirs for separating the first emulsion phase layer from the first desulfurized oil product layer and first aqueous spent alkali metal layer. 20. A process for desulfurizing a hydrocarbon feedstream, comprising: a) mixing at least a portion of a hydrocarbon feedstream having an API gravity of less than 19 with a first aqueous alkali metal salt reagent solution to form a first mixed reactor feedstream;b) exposing at least a portion of the first mixed reactor feedstream to a first desulfurization reactor operated under first effective desulfurization conditions to form a first desulfurized reactor product stream comprising desulfurized oil, spent alkali metals, and coke;c) separating the first desulfurized reactor product stream to form at least a first low-boiling point vapor fraction and a first reactor product liquid fraction;d) mixing at least a portion of the first reactor product liquid fraction with a second aqueous alkali metal salt reagent solution to form a second mixed reactor feedstream;e) exposing at least a portion of the second mixed reactor feedstream to a second desulfurization reactor operated under second effective desulfurization conditions to form a second desulfurized reactor product stream comprising desulfurized oil, spent alkali metals, and coke;f) separating the second desulfurized reactor product stream to form at least a second low-boiling point vapor fraction and a second reactor product liquid fraction;g) mixing at least a portion of the second reactor product liquid fraction with water to form a first wash water separator feedstream;h) sending the first wash water separator feedstream to a first wash water separator vessel wherein in the first wash water separator vessel, the first wash water separator feedstream forms three distinct layers as flows: a first desulfurized oil product layer, a first emulsion phase layer, and a first aqueous spent alkali metal layer;i) removing each of the three distinct layers separately from the first wash water separator vessel to separately form a first desulfurized oil product stream, a first emulsion phase stream, and a first aqueous spent alkali metal stream;wherein at least 50 wt % of the total coke in the first and second desulfurized reactor product streams is removed in the first emulsion phase stream, and the first desulfurized oil product stream has a lower sulfur content by wt % than the hydrocarbon feedstream, and the first desulfurized oil product stream has a API gravity of at least 20 and a viscosity of less than or equal to 40 centistokes at 40° C. 21. The process of claim 20, wherein the alkali metal salt reagent solutions comprise an alkali metal sulfide, an alkali metal hydrogen sulfide, an alkali metal hydroxide, or a combination thereof. 22. The process of claim 21, wherein the alkali metal salt reagent solutions comprise K2S, KHS, KOH or a mixture thereof. 23. The process of claim 22, wherein the alkali metal salt reagent solutions comprise KOH. 24. The process of claim 23, wherein the aqueous spent alkali metal streams comprise K2S, KHS, KNaS or a mixture thereof. 25. The process of claim 20, wherein the first and second effective desulfurization conditions are from about 50 to about 3000 psi (345 to 20,684 kPa), and from about 600° F. to about 900° F. (316° C. to 482° C.). 26. The process of claim 20, wherein a first hydrogen-containing stream, comprised of at least 75 mol % hydrogen is added to the first mixed reactor feedstream either prior to or in the first desulfurization reactor and a second hydrogen-containing stream, comprised of at least 75 mol % hydrogen is added to the second mixed reactor feedstream either prior to or in the second desulfurization reactor. 27. The process of claim 20, wherein the amount of alkali metal salt (on an alkali metal molar basis) in the first aqueous alkali metal salt reagent solution is at least 1.2 times the amount of sulfur (on a sulfur molar basis) of the hydrocarbon feedstream. 28. The process of claim 20, wherein the hydrocarbon feedstream is a heavy oil feedstream having a sulfur content of at least about 3 wt %. 29. The process of claim 20, wherein at least 75 wt % of the total coke in the first and second desulfurized reactor product streams is removed in the first emulsion phase stream, and the amount of alkali metal salt in the first mixed reactor feedstream is at least about 20 wt % of the hydrocarbon feedstream. 30. The process of claim 20, wherein at least 95 wt % of the total coke in the first and second desulfurized reactor product streams is removed in the first emulsion phase stream, and the amount of alkali metal salt in the first mixed reactor feedstream is at least about 25 wt % of the hydrocarbon feedstream. 31. A process for desulfurizing a hydrocarbon feedstream, comprising: a) mixing at least a portion of a hydrocarbon feedstream having an API gravity of less than 19 with an aqueous alkali metal salt reagent solution to form a first mixed reactor feedstream;b) exposing at least a portion of the first mixed reactor feedstream to a first desulfurization reactor operated under first effective desulfurization conditions to form a first desulfurized reactor product stream comprising desulfurized oil, spent alkali metals, and coke;c) separating the first desulfurized reactor product stream to form at least a first low-boiling point vapor fraction and a first reactor product liquid fraction;d) mixing at least a portion of the first reactor product liquid fraction with water to form a first wash water separator feedstream;e) sending the first wash water separator feedstream to a first wash water separator vessel wherein in the first wash water separator vessel, the first wash water separator feedstream forms three distinct layers as flows: a first desulfurized oil product layer, a first emulsion phase layer, and a first aqueous spent alkali metal layer;f) removing each of the three distinct layers separately from the first wash water separator vessel to separately form a first desulfurized oil product stream, a first emulsion phase stream, and a first aqueous spent alkali metal stream;g) mixing at least a portion of the first desulfurized oil product stream with water to form a second wash water separator feedstreamh) sending the second wash water separator feedstream to a second wash water separator vessel wherein in the second wash water separator vessel, the second wash water separator feedstream forms three distinct layers as flows: a second desulfurized oil product layer, a second emulsion phase layer, and a second aqueous spent alkali metal layer;i) removing each of the three distinct layers separately from the second wash water separator vessel to separately form a second desulfurized oil product stream, a second emulsion phase stream, and a second aqueous spent alkali metal stream;wherein at least 50 wt % of the total coke in the first desulfurized reactor product stream is removed in the first and second emulsion phase streams, and the first and second desulfurized oil product streams each have a lower sulfur content by wt % than the hydrocarbon feedstream, and the first and second desulfurized oil product streams each have an API gravity of at least 20 and a viscosity of less than or equal to 40 centistokes at 40° C. 32. The process of claim 31, wherein the alkali metal salt reagent solution comprises an alkali metal sulfide, an alkali metal hydrogen sulfide, an alkali metal hydroxide, or a combination thereof. 33. The process of claim 32, wherein the alkali metal salt reagent solution comprises K2S, KHS, KOH or a mixture thereof. 34. The process of claim 33, wherein the first and second aqueous spent alkali metal streams comprise K2S, KHS, KNaS or a mixture thereof. 35. The process of claim 31, wherein the first effective desulfurization conditions are from about 50 to about 3000 psi (345 to 20,684 kPa), and from about 600° F. to about 900° F. (316° C. to 482° C.), and a hydrogen-containing stream, comprised of at least 75 mol % hydrogen is added to the first mixed reactor feedstream either prior to or in the first desulfurization reactor. 36. The process of claim 31, wherein the amount of alkali metal salt (on an alkali metal molar basis) in the alkali metal salt reagent solution is at least 1.2 times the amount of sulfur (on a sulfur molar basis) of the hydrocarbon feedstream. 37. The process of claim 31, wherein the hydrocarbon feedstream is a heavy oil feedstream having a sulfur content of at least about 3 wt %. 38. The process of claim 31, wherein at least 75 wt % of the total coke in the first desulfurized reactor product stream is removed in the first and second emulsion phase streams, and the amount of alkali metal salt in the first mixed reactor feedstream is at least about 20 wt % of the hydrocarbon feedstream. 39. The process of claim 31, wherein at least 95 wt % of the total coke in the first desulfurized reactor product stream is removed in the first and second emulsion phase streams, and the amount of alkali metal salt in the first mixed reactor feedstream is at least about 25 wt % of the hydrocarbon feedstream. 40. The process of claim 31, wherein at least a portion of the first and second aqueous spent alkali metal streams are combined, the alkali metal salts are regenerated, and at least a portion of the regenerated alkali metal salts are contacted with the hydrocarbon feedstream, and wherein at least a portion of the second aqueous spent alkali metal stream is contacted with the first desulfurized oil product stream.
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이 특허에 인용된 특허 (23)
Baird ; Jr. William C. (Baton Rouge LA) Bearden ; Jr. Roby (Baton Rouge LA), Combined desulfurization and hydroconversion with alkali metal hydroxides.
Brons Glen B. (Phillipsburg NJ) Myers Ronald (Calgary CAX) Bearden ; Jr. Roby (Baton Rouge LA), Continuous in-situ combination process for upgrading heavy oil.
Baird ; Jr. William C. (Baton Rouge LA) Beardon ; Jr. Roby (Baton Rouge LA), Desulfurization and hydroconversion of residua with sodium hydride and hydrogen.
Rodriguez Domingo (Edo Miranda VEX) Gomez Cebers (San Antonio de los Altos VEX), Process for removing vanadium and sulphur during the coking of a hydrocarbon feed.
Meyers Robert A. (Tarzana CA) Hart Walter D. (Upland CA) Van Nice ; deceased Leslie J. (late of ; Manhattan Beach CA by Norma R. Van Nice ; executor) Van Nice ; heir Leslie J. (Coos Bay OR), Process for upgrading coal.
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