Bulk bi-metallic catalysts made from precursors containing an organic agent
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
C10G-045/04
C10G-045/02
C10G-045/44
C10G-047/02
C10G-047/00
C10G-045/60
C10G-045/58
C07C-005/02
C07C-005/00
B01J-027/00
B01J-027/043
B01J-027/04
B01J-031/00
B01J-023/00
출원번호
UP-0227726
(2005-09-14)
등록번호
US-7591942
(2009-10-20)
발명자
/ 주소
Soled, Stuart L.
Miseo, Sabato
Hou, Zhiguo
출원인 / 주소
ExxonMobil Research and Engineering Company
인용정보
피인용 횟수 :
14인용 특허 :
11
초록
Bulk bi-metallic catalysts for use in the hydroprocessing of hydrocarbon feeds, as well as a method for preparing such catalysts. The catalysts are prepared from a catalyst precursor containing an organic agent.
대표청구항▼
The invention claimed is: 1. A bulk bi-metallic catalyst precursor composition represented by the formula: (X)a(Y)b[(CH3CH2)c N(CH3)3]dOz wherein X is a Group VIII non-noble metal, Y is selected from Mo and W, c is an integer from about 10 to about 40, and the molar ratio of a:b is about 0.5/1
The invention claimed is: 1. A bulk bi-metallic catalyst precursor composition represented by the formula: (X)a(Y)b[(CH3CH2)c N(CH3)3]dOz wherein X is a Group VIII non-noble metal, Y is selected from Mo and W, c is an integer from about 10 to about 40, and the molar ratio of a:b is about 0.5/1 to about 3/1; wherein said catalyst composition, after sulfidation, is comprised of stacked layers of (Y)S2, such that the average stack height is about 10 Å to about 20 Å. 2. The catalyst composition of claim 1 wherein the molar ratio of a:b is from about 0.75/1 to about 1.5/1. 3. The catalyst composition of claim 1 wherein c is from about 16 to about 20. 4. The catalyst composition of claim 3 wherein c is about 18. 5. The catalyst composition of claim 1 wherein d is from about 0.5 to about 1.5. 6. The catalyst composition of claim 1 wherein X is selected from Ni and Co. 7. The catalyst composition of claim 6 wherein Y is Mo. 8. A method for preparing a catalyst precursor composition represented by the formula: (X)a(Y)b[(CH3CH2)c N(CH3)3]dOz wherein X is a Group VIII non-noble metal, Y is selected from Mo and W, c is an integer from about 10 to about 40, and the molar ratio of a:b is about 0.5/1 to about 3/1; which method comprises: (a) preparing a first aqueous solution of a Group VIII non-noble metal water soluble salt; (b) preparing a second aqueous solution of a Group VIB metal water soluble salt; (c) heating both said first and second solutions to a temperature from about 60° C. to about 150° C.; (d) adding an effective amount of an organic agent into said first aqueous solution; (e) introducing at least a portion of said second aqueous solution into said first aqueous solution; and (f) heating the resulting solution of step e) to an effective temperature to cause the precipitation of said catalyst precursor composition. 9. The method of claim 8 wherein the Group VIII non-noble metal is selected from Ni and Co. 10. The method of claim 9 wherein the Group VIB metal is selected from Mo and W. 11. The method of claim 10 wherein the Group VIB metal is Mo. 12. The method of claim 8 wherein the salt of the Group VIII non-noble metal is selected from the group consisting of sulfate, nitrate, bromide, chloride, and acetate. 13. The method of claim 8 wherein the Group VIB metal is Mo and the salt used is an ammonium salt selected from the group consisting of ammonium dimolybdate, ammonium tri-, tetra-hepta-, octa-, and tetradeca-molybdate. 14. The method of claim 8 wherein the Group VIB metal is W and the salt is an ammonium para-, meta-, hexa-, and polytungstate. 15. The method of claim 8 wherein the organic agent is selected from the group consisting of aromatic amines, cyclic aliphatic amines and polycyclic aliphatic amines. 16. The method of claim 15 wherein the organic agent is a C4 to C20 aromatic amine. 17. The method of claim 8 wherein the catalyst precursor composition is formed in a suitable catalyst shape and dried. 18. The method of claim 17 wherein the shaped and dried catalyst is calcined at a temperature from about 100° C. to about 600° C. in the presence of oxygen. 19. The method of claim 18 wherein the shaped, dried, and calcined catalyst is sulfided in the presence of a sulfur-containing compound at sulfiding conditions. 20. The method of claim 19 wherein the sulfur-containing compound is selected from the group consisting of elementary sulfur, hydrogen sulfide, and polysulfides. 21. A process wherein a hydrocarbon feedstock is hydroprocessed at hydroprocessing conditions, which process comprises: reacting said feedstock at hydroprocessing conditions in the presence of a bulk bi-metallic bulk multimetallic catalyst composition derived from a catalyst precursor composition represented by the formula: (X)a(Y)b[(CH3CH2)c N(CH3)3]dOz wherein X is a Group VIII non-noble metal, Y is selected from Mo and W, c is an integer from about 10 to about 40, and the molar ratio of a:b is about 0.5/1 to about 3/1; and wherein said catalyst composition, after sulfidation, is comprised of stacked layers of (Y)S2, such that the average stack height is about 10 to about 20 Å. 22. The process of claim 21 wherein hydroprocessing is selected from the group consisting of hydrodemetallation, hydrodewaxing, hydrotreating, hydrogenation, hydrodesulfurization, hydrodenitrogenation, hydrodearomatization, hydroisomerization, and hydrocracking. 23. The process of claim 21 wherein the Group VIII non-noble metal is selected from Ni and Co. 24. The process of claim 23 wherein the Group VIB metal is selected from Mo and W. 25. The process of claim 21 wherein the hydrocarbon feedstock is selected from the group consisting of whole and reduced petroleum crudes, atmospheric and vacuum residua, propane deasphalted residua, cycle oils, fluid cat cracked tower bottoms, gas oils, light to heavy distillates, hydrocrackates, hydrotreated oils, dewaxed oils, slack waxes, Fischer-Tropsch waxes, raffinates, naphthas, and mixtures thereof. 26. The process of claim 21 wherein the hydroprocessing is performed at temperatures from about 200° to about 450° C., hydrogen pressures from about 5 to about 300 bar, liquid hourly space velocities from about 0.05 to about 10 h-1, and hydrogen treat gas rates from about 200 to about 10,000 standard cubic feet per barrel. 27. The process of claim 21 which is conducted in two or more stages, which two or more stages can be the same or different hydroprocessing processes.
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이 특허에 인용된 특허 (11)
Halbert Thomas R. (Annandale NJ) Stiefel Edward I. (Bridgewater NJ) Chianelli Russell R. (Somerville NJ) Ho Teh C. (Bridgewater NJ), Desulfurization of hydrocarbons using molybdenum or tungsten sulfide catalysts promoted with low valent group VIII metal.
Kaneshima Tokitaka (Kurashiki JPX) Takahashi Takashi (Kurashiki JPX) Matsubara Kazuhiro (Kurashiki JPX), Oleophilic molybdenum compound for use in hydroconversion of a hydrocarbon and a method for producing the same.
Halbert Thomas R. (Annandale NJ) Stiefel Edward I. (Bridgewater NJ) Chianelli Russell R. (Somerville NJ) Ho Teh C. (Bridgewater NJ), Promoted molybdenum and tungsten sulfide catalysts, their preparation and use.
Chianelli Russell R. (Somerville NJ) Ho Teh C. (Bridgewater NJ) Jacobson Allan J. (Princeton NJ) Young Archie R. (Montclair NJ), Supported chromium-molybdenum and tungsten sulfide catalysts.
Hanks, Patrick L.; Lewis, William Ernest; Ellis, Edward Stanley; Cole, Kathryn Younger, Ebullating bed methods for treatment of biocomponent feedstocks.
Soled, Stuart L.; Miseo, Sabato; Baumgartner, Joseph E.; Nistor, Iulian; Nandi, Partha; Guzman, Javier; Levin, Doron; Wilson, Keith; Bergweff, Jacob Arie; Huiberts, Ronald Jan; Van Loevezijn, Arnold, Hydroprocessing catalysts and their production.
Soled, Stuart L.; Miseo, Sabato; Baumgartner, Joseph E.; Nistor, Iulian; Venkataraman, Pallassana S.; Kliewer, Chris E.; Chimenti, Robert J.; Guzman, Javier; Kennedy, Gordon; Levin, Doron, Hydroprocessing catalysts and their production.
Soled, Stuart L.; Miseo, Sabato; Baumgartner, Joseph E.; Nistor, Iulian; Venkataraman, Pallassana S.; Kliewer, Chris E.; Chimenti, Robert J.; Guzman, Javier; Kennedy, Gordon; Levin, Doron, Hydroprocessing catalysts and their production.
Coupard, Vincent; Uzio, Denis; Petit-Clair, Carine; Fischer, Lars; Portejole, Frederic, Process for the preparation of multimetallic catalysts that can be used in reactions for transformation of hydrocarbons.
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