Process for preparing a catalytic composition for the hydroconversion of petroleum fractions
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
B01J-023/22
B01J-037/03
B01J-023/85
B01J-023/882
B01J-023/883
B01J-035/00
B01J-037/00
B01J-037/08
B01J-037/20
C10G-045/08
C10G-045/50
B01J-035/10
출원번호
US-0065116
(2006-08-22)
등록번호
US-8946110
(2015-02-03)
우선권정보
MX-PA/a/2005/009283 (2005-08-31)
국제출원번호
PCT/MX2006/000091
(2006-08-22)
§371/§102 date
20080610
(20080610)
국제공개번호
WO2007/027079
(2007-03-08)
발명자
/ 주소
Toledo Antonio, José Antonio
Pérez Luna, Miguel
Cortés Jacome, María Antonia
Escobar Aguilar, José
Mosqueira Mondragón, María de Lourdes
Angeles Chávez, Carlos
López Salinas, Esteban
Pérez Moreno, Víctor
Ferrat Torres, Gerardo
Mora Vallejo, Rodolfo Juventino
Lozada y Cassou, Marcelo
출원인 / 주소
Instituto Mexicano del Petroleo
대리인 / 주소
Roylance, Abrams, Berdo & Goodman, L.L.P.
인용정보
피인용 횟수 :
0인용 특허 :
17
초록▼
The invention relates to a method of preparing a catalytic composition comprising at least one non-noble metal from group VIII and at least one metal from group VIB of the periodic table. The invention also relates to the catalytic composition thus produced, which has a high specific activity in rea
The invention relates to a method of preparing a catalytic composition comprising at least one non-noble metal from group VIII and at least one metal from group VIB of the periodic table. The invention also relates to the catalytic composition thus produced, which has a high specific activity in reactions involving the hydroprocessing of light and intermediate fractions, preferably in reactions involving the hydrotreatment of hydrocarbon streams, including hydrodesulphurization (HDS), hydrodenitrogenation (HDN) and hydro-dearomatization (HDA).
대표청구항▼
1. A process for the preparation of a catalytic component consisting of at least one Group VIII non-noble metal and a single Group VIB metal, the process comprising: the step of reacting a solution of a soluble Group VIII metal precursor, a single soluble Group VIB metal precursor and a tetraalkyl q
1. A process for the preparation of a catalytic component consisting of at least one Group VIII non-noble metal and a single Group VIB metal, the process comprising: the step of reacting a solution of a soluble Group VIII metal precursor, a single soluble Group VIB metal precursor and a tetraalkyl quaternary ammonium salt at pH 5-14; evaporating the solution to form a crystallized complex;thermally treating the crystallized complex; andsulfiding the thermally treated crystallized complex to obtain the catalytic component. 2. The process of claim 1, wherein said quaternary ammonium salt is a salt of a tetraalkyl ammonium ion having the formula NR4+ where R is an alkyl. 3. The process of claim 2, wherein each R is independently a C1 to C8 alkyl group. 4. The process of claim 3, wherein each R is independently a C1 to C8 alkyl substituted in a halogen or hydroxyl group. 5. The process of claim 2, wherein said quaternary ammonium salt is a salt of a tetraalkyl ammonium ion having the formula R′NR3+ where R′ is a C12 to C20 alkyl group and each R is independently a C1 to C8 alkyl group. 6. A process of preparing a catalytic component, the process comprising: a) forming a solution and mixture of precursor salts in a solvent selected from the group consisting of water, methanol, ethanol, propanol, butanol, and mixtures thereof, said precursor salt being salts of at least one Group VIII non-noble metal and a single Group VIB metal;b) forming a solution of a tetraalkyl quaternary ammonium salt in a solvent;c) forming a mixture of the solutions obtained in steps (a) and (b);d) adding a basic hydroxide solution and/or ammonium carbonate to the solution (c) at a pH comprised between 5 and 14;e) heating the solution obtained in step (d) to a temperature between 50 and 200° C.;f) homogenizing the solution in step (e);g) crystallizing the solution obtained in step (f) through evaporation of the solvent;h) filtering or centrifugation of the resulting crystallized suspension obtained in step (g) for the separation of the crystals and recovery of mother liquors in the event that the evaporation has not been completed;i) washing the solid obtained in step (h) with sufficient deionized water and/or water/alcohol mixture;j) drying the solid obtained in step (i) at a temperature between 50 and 300° C.;k) thermally treating the solid obtained in step (j) in inert atmosphere of nitrogen, helium, or argon, at a temperature between 200 and 1000° C.;l) sulfiding of the material obtained step (i) or in step (j) in a gaseous flow made up of 10 vol. % hydrogen sulfide or with a hydrocarbon fraction containing at least 0.2 wt. % sulfur with a hydrogen flow at a temperature between 200 and 600° C., and a pressure between 1 and 100 Kg/cm2 to obtain said catalytic component consisting essentially of at least one Group VIII non-noble metal and a single Group VIB metal. 7. The preparation process in accordance with claim 6, in which the at least one Group VIII non-noble metal and a single Group VIB metal precursor salts are completely dissolved in a liquid used as solvent. 8. The preparation process in accordance with claim 7, in which the completely dissolved precursor salts are mixed with a solution that contains a surface active compound. 9. The preparation process in accordance with claim 6, where the solvent used comprises water and/or alcohol and/or alcohol-water mixture. 10. The preparation process in accordance with claim 6, where the quaternary ammonium salt (R4N+) is chloride, bromide, fluoride, or hydroxide. 11. The preparation process in accordance with claim 6, where the Group VIII non-noble metal includes nickel, cobalt, and/or iron, or a mixture of these metals. 12. The preparation process in accordance with claim 11, where the nickel and/or cobalt represent 100 wt. % of the Group VIII non-noble metals calculated as oxides. 13. The preparation process in accordance with claim 6, where the Group VIB metal is one selected from the group consisting of molybdenum, tungsten and chromium. 14. The preparation process in accordance with claim 6, where the homogenization step of the solutions takes place at a temperature and at a pH such that all the selected precursor salts are in a completely soluble state. 15. The preparation process in accordance with claim 6, where the homogenization step of the solutions takes place at a time between 5 min and 24 h. 16. The preparation process in accordance with claim 6, where the solution's crystallization step is carried out by partial evaporation of the solvent in a crystallizer and/or by total evaporation of the solvent in an evaporator. 17. The preparation process in accordance with claim 6, where the solution's crystallization step is carried out by evaporation of the solvent at a temperature between 80 and 200° C. 18. The preparation process in accordance with claim 6, where the thermal treatment in inert atmosphere stage is carried out at a temperature between 300 and 600° C., in a flow of nitrogen, helium, argon, or mixtures thereof at a flow of at least 0.01 L/g·min. 19. The preparation process in accordance with claim 6, where the thermal treatment is not be carried out in oxidizing atmosphere. 20. The preparation process in accordance with claim 6, where the sulfiding step is carried out either on the dry or thermally treated material in the presence of a liquid fraction of hydrocarbons that contains at least 0.1 wt. % of sulfur and hydrogen at pressures comprised between 1 and 100 Kg/cm2, at temperatures between 200 and 600° C. 21. The preparation process in accordance with claim 6 including an inorganic oxide binder selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, zirconia, zirconia-titania, zirconia-alumina, amorphous silico-aluminates, and/or crystalline clays in the homogenization step of the mixture of precursor salts. 22. The preparation process in accordance with claim 6, further comprising the addition of an inorganic oxide binder, after the crystallization stage in the wet and/or dry material. 23. The preparation process in accordance with claim 6, further comprising the addition of an inorganic oxide as a binder, after the material has been thermally treated and/or sulfided. 24. The preparation process in accordance with claim 6, further comprising extruding the material containing an inorganic oxide as a binder. 25. The process of claim 6, wherein said tetraalkyl ammonium salt is a salt of a tetraalkyl ammonium cation having the formula NR4+ where R is independently a C1 to C8 alkyl group. 26. The process of claim 25, wherein R is a substituted alkyl containing a halogen or hydroxy group. 27. The process of claim 6, wherein said tetraalkyl ammonium salt is a salt of a tetraalkyl ammonium cation having the formula R′NR3+ where R′ is a C12 to C20 alkyl group and R is independently a C1 to C8 alkyl group. 28. A process for producing a catalytic composition comprising the steps of: forming a first solution of a soluble Group VIII non-noble metal precursor and only one Group VIB metal precursor;forming a second solution containing a component selected from the group consisting of an ionic surfactant and a tetraalkyl quaternary ammonium salt, and mixing with said first solution of said Group VIII and Group VIB precursors;removing said solvent and crystallizing the resulting solid product;thermally treating the resulting solid product in an inert atmosphere at a temperature of 200° C. to 1000° C. to obtain a heat-treated product; andsulfiding the heat-treated product to obtain the catalytic composition comprising a catalytic component consisting essentially of a Group VIII non-noble metal and one Group VIB metal. 29. The process of claim 28, wherein said second solution is a solution of said tetraalkyl quaternary ammonium salt of a tetraalkyl quaternary ammonium ion having the formula NR4+ where R is independently a C1 to C8 alkyl group. 30. The process of claim 28, wherein said second solution is a solution of a tetraalkyl quaternary ammonium salt of a tetraalkyl quaternary ammonium having the formula R′NR3+ where R′ is a C12 to C20 alkyl group and R is independently a C1 to C8 alkyl group. 31. The process of claim 28, wherein said solution is a solution of a cationic, anionic or neutral surfactant.
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이 특허에 인용된 특허 (17)
Chianelli Russell R. (Somerville NJ) Pecoraro Theresa A. (Danville CA), Carbon-containing molybdenum and tungsten sulfide catalysts.
Pecoraro Theresa A. (Danville CA) Chianelli Russell R. (Somerville NJ), Hydrogenation processes using carbon-containing molybdenum and tungsten sulfide catalysts.
Stiefel Edward I. (Bridgewater NJ) Pan Wie-Hin (Fanwood NJ) Chianelli Russell R. (Somerville NJ) Ho Teh C. (Scotch Plains NJ), Hydrotreating using self-promoted molybdenum and tungsten sulfide catalysts formed from bis(tetrathiometallate) precurso.
Eijsbouts, Sonja; Oogjen, Bob Gerardus; Homan Free, Hermannus Willem; Cerfontain, Marinus Bruce; Riley, Kenneth Lloyd; Soled, Stuart Leon; Miseo, Sabato, Mixed metal catalyst, its preparation by co-precipitation, and its use.
Eijsbouts, Sonja; Oogjen, Bob Gerardus; Homan Free, Harmannus Willem; Cerfontain, Marinus Bruce; Riley, Kenneth Lloyd; Soled, Stuart Leon; Miseo, Sabato, Process for preparing a mixed metal catalyst composition.
Plantenga, Frans Lodewijk; Eijsbouts, Sonja; Cerfontain, Marinus Bruce, Process for preparing an additive-based mixed metal catalyst, its composition and use.
Ho Teh C. (Scotch Plains NJ) Pan Wie-Hin (Fanwood NJ), Supported, self-promoted molybdenum and tungsten sulfide catalysts formed from bis(tetrathiometallate) precursors, and t.
Jacobson Allan J. (Princeton NJ) Chianelli Russell R. (Somerville NJ) Pecoraro Theresa A. (Danville CA), Transition metal sulfide promoted molybdenum or tungsten sulfide catalysts and their uses for hydroprocessing.
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