Mild hydrodesulfurization integrating gas phase catalytic oxidation to produce fuels having an ultra-low level of organosulfur compounds
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-067/12
B01J-035/02
B01J-023/80
B01J-037/03
B01J-035/10
B01J-035/08
C10G-045/02
C10G-027/04
B01J-023/83
B01J-037/00
B01J-023/00
B01J-035/00
출원번호
US-0741819
(2013-01-15)
등록번호
US-8906227
(2014-12-09)
발명자
/ 주소
Bourane, Abdennour
Koseoglu, Omer Refa
Ismagilov, Zinfer
Yashnik, Svetlana
Kerzhentsev, Mikhail
Parmon, Valentin
출원인 / 주소
Suadi Arabian Oil Company
대리인 / 주소
Abelman, Frayne & Schwab
인용정보
피인용 횟수 :
0인용 특허 :
52
초록▼
Desulfurization of hydrocarbon feeds is achieved by first contacting the entire feed with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone operating under mild conditions; a flashing column downstream of the hydrodesulfurization reaction zone fractionates the effluent to obtai
Desulfurization of hydrocarbon feeds is achieved by first contacting the entire feed with a hydrodesulfurization catalyst in a hydrodesulfurization reaction zone operating under mild conditions; a flashing column downstream of the hydrodesulfurization reaction zone fractionates the effluent to obtain a first fraction which contains refractory organosulfur compounds and a second fraction that is substantially free of organosulfur compounds, since the organosulfur compounds boiling in the range of this fraction were the labile organosulfur compounds which were initially removed by mild hydrodesulfurization. The first fraction is contacted with a gaseous oxidizing agent over an oxidation catalyst having a formula CuxZn1-xAl2O4 in a gas phase catalytic oxidation reaction zone to convert the refractory organosulfur compounds to SOx and low sulfur hydrocarbons. The by-product SOx is subsequently removed, producing a stream containing a reduced level of organosulfur compounds.
대표청구항▼
1. A method of processing a hydrocarbon feed to remove undesired organosulfur compounds comprising: a. subjecting the hydrocarbon feed to a hydrodesulfurizing process to produce a hydrotreated effluent;b. flashing the hydrotreated effluent to provide a low boiling temperature fraction that contains
1. A method of processing a hydrocarbon feed to remove undesired organosulfur compounds comprising: a. subjecting the hydrocarbon feed to a hydrodesulfurizing process to produce a hydrotreated effluent;b. flashing the hydrotreated effluent to provide a low boiling temperature fraction that contains a reduced level of organosulfur compounds and a high boiling temperature fraction having refractory organosulfur compounds;c. separating the high and low boiling temperature fractions; andd. contacting the high boiling temperature fraction with a gaseous oxidizing agent and an oxidizing catalyst having a formula CuxZn1-xAl2O4 wherein x ranges from 0 to 1 to convert refractoryorganosulfur compounds including dibenzothiophenes, alkyl derivatives of dibenzothiophenes and long-chain alkylated derivatives of benzothiophene having a boiling point in the range of the high boiling temperature fraction, to SOxby breaking the C—S bonds. 2. The method of claim 1, wherein the oxidizing catalyst comprises 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 highly dispersed crystalline ZnO and CuO. 3. The method of claim 1, wherein the temperature cut point in step (b) is about 340° C. 4. The method of claim 1, wherein the low boiling temperature fraction includes aliphatic organosulfur compounds. 5. The method of claim 4, wherein the aliphatic organosulfur compounds include sulfides, disulfides, and mercaptans. 6. The method of claim 4, wherein the low boiling temperature fraction further includes thiophene and alkyl derivatives of thiophene. 7. The method of claim 1, wherein the high boiling temperature fraction includes dibenzothiophene, alkyl derivatives of dibenzothiophene and long-chain alkylated derivatives of benzothiophene having a boiling point in the range of the high boiling temperature fraction. 8. The method of claim 1, wherein the hydrocarbon feed is a straight run gas oil boiling in the range of about 180° C. to about 450° C. 9. The method of claim 8, wherein the hydrodesulfurizing process is operated at mild operating conditions. 10. The method of claim 9, wherein the hydrogen partial pressure is less than about 55 bars. 11. The method of claim 9, wherein the hydrogen partial pressure is about 25 bars to about 40 bars. 12. The method of claim 9, wherein the operating temperature is about 300° C. to about 400° C. 13. The method of claim 9, wherein the operating temperature is about 320° C. to about 380° C. 14. The method of claim 9, wherein the hydrogen feed rate in the hydrodesulfurizing process step is from about 100 liters of hydrogen per liter of oil to about 1000 liters of hydrogen per liter of oil. 15. The method of claim 9, wherein the hydrogen feed rate in the hydrodesulfurizing process step is from about 200 liters of hydrogen per liter of oil to about 300 liters of hydrogen per liter of oil. 16. The method of claim 8, wherein step (d) occurs substantially in gas phase. 17. The method of claim 1, wherein the oxidizing agent is selected from the group consisting of oxides of nitrogen, oxygen, and air. 18. The method of claim 1, further comprising recovering the hydrotreated effluent from step (a). 19. The method of claim 1 wherein the catalytic composition used in step (d) further comprises —Ce2O3 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. 20. The method of claim 1 wherein the catalytic composition used in step (d) is in granular form. 21. The method of claim 1 wherein the catalytic composition used in step (d) is formed as a cylinder, a sphere, a trilobe, or having a quadrilobate shape. 22. The method of claim 21 wherein particles of the catalytic composition have effective diameter of from 1 mm to 4 mm. 23. The method of claim 21 wherein particles of the catalytic composition have having a specific surface area of from 10 m2/g to 100 m2/g. 24. The method of claim 21 wherein particles of the catalytic composition have having a specific surface area of from 50 m2/g to 100 m2/g. 25. The method of claim 21 wherein particles of the catalytic composition have pores with effective diameters of from 8 nm to 12 nm. 26. The method of claim 21 wherein particles of the catalytic composition have pores with effective diameters of from 8 nm to 10 nm. 27. The method of claim 21 wherein particles of the catalytic composition have pores with a volume of from about 0.1 cm3/g to about 0.5 cm3/g. 28. The method of claim 1 wherein the catalytic composition used in step (d) comprises from 20 wt % to 45 wt % CuO, from 10 wt % to less than 20 wt % ZnO, and from 20 wt % to 70 wt % of Al2O3. 29. The method of claim 1 wherein the catalytic composition used in step (d) 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. 30. The method of claim 1 wherein x in the catalytic composition used in step (d) is from 0.1 to 0.6. 31. The method of claim 1 wherein x in the catalytic composition used in step (d) is from 0.2 to 0.5. 32. The method of claim 1, further comprising e. removing the by-product SOx in a separation zone from the sulfur-free hydrocarbons; andf. recovering an ultra-low sulfur level hydrocarbon product. 33. The method of claim 32, further comprising combining effluents from steps (a) and (f).
연구과제 타임라인
LOADING...
LOADING...
LOADING...
LOADING...
LOADING...
이 특허에 인용된 특허 (52)
Rudolf W. Gunnerman, Continuous process for oxidative desulfurization of fossil fuels with ultrasound and products thereof.
James J. Schorfheide ; Edward S. Ellis ; Michele S. Touvelle ; Ramesh Gupta, Countercurrent desulfurization process for refractory organosulfur heterocycles.
McVicker Gary B. ; Baird ; Jr. William C. ; Schorfheide James J. ; Daage Michel ; Klein Darryl P. ; Ellis Edward S. ; Vaughan David E. W. ; Chen Jingguang, Desulfurization of petroleum streams containing condensed ring heterocyclic organosulfur compounds.
Rafael Vazquez Duhalt MX; Maria del Pilar Bremauntz MX; Eduardo Barzana MX; Raunel Tinoco MX, Enzymatic oxidation process for desulfurization of fossil fuels.
Fletcher David L. (Turnersville NJ) Hilbert Timothy L. (Sewell NJ) Sarli Michael S. (Haddonfield NJ) Shih Stuart S. (Cherry Hill NJ), Gasoline upgrading process.
Marc Lemaire FR; Michele Monnet FR; Michel Vrinat FR; Valerie Lamure FR; Emmanuelle Sanson FR; Alexandra Milenkovic FR, Method for separating benzothiophene compounds from hydrocarbon mixture containing them, and hydrocarbon mixture obtained by said method.
Grossman Matthew J. ; Siskin Michael ; Ferrughelli David T. ; Lee M. Kathryn ; Senius James D., Method for the removal of organic sulfur from carbonaceous materials.
Ho Teh Chung ; Hsu Chang Samuel ; Dupre Gerald Dennis ; Liotta Ronald ; Buchholz Viktor, Process for deep desulfurization using combined hydrotreating-oxidation.
Courty Philippe (Houilles FRX) Travers Christine (Rueil-Malmaison FRX) Durand Daniel (Rueil-Malmaison FRX) Forestire Alain (Vernaison FRX) Chaumette Patrick (Rueil-Malmaison FRX), Process for manufacturing catalysts containing copper, zinc and aluminum, useful for producing methanol from synthesis g.
Wittenbrink Robert J. ; Klein Darryl P. ; Touvelle Michele S. ; Daage Michel ; Berlowitz Paul J., Process for the production of high lubricity low sulfur distillate fuels.
Yoo Jin Sun (South Holland IL) Voss Andrew P. (South Holland IL), Process for “sulfur reduction of an oxidized hydrocarbon by forming a metal-sulfur-containing compound”.
Euzen, Patrick; Bourges, Patrick; Gueret, Christophe; Bobin, Carole; Chaumonnot, Alexandra; Dulot, Hugues, Zeolitic catalyst with a controlled doping element content, and improved process for processing hydrocarbon feeds.
※ AI-Helper는 부적절한 답변을 할 수 있습니다.