Hydroconversion multi-metallic catalysts and method for making thereof
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
B01J-027/051
B01J-027/049
B01J-027/043
B01J-027/047
B01J-035/00
B01J-035/10
출원번호
US-0019444
(2013-09-05)
등록번호
US-9327275
(2016-05-03)
발명자
/ 주소
Han, Jinyi
Kuperman, Alexander E.
Maesen, Theodorus Ludovicus Michael
Trevino, Horacio
출원인 / 주소
CHEVRON U.S.A. INC.
대리인 / 주소
Ross, Michael D.
인용정보
피인용 횟수 :
0인용 특허 :
106
초록▼
The invention relates to a self-supported mixed metal sulfide (MMS) catalyst for hydrotreating hydrocarbon feedstock and to a method for preparing the catalyst. The MMS catalyst is characterized as having a BET surface area of at least 20 m2/g and a pore volume of at least 0.05 cm3/g. In one embodim
The invention relates to a self-supported mixed metal sulfide (MMS) catalyst for hydrotreating hydrocarbon feedstock and to a method for preparing the catalyst. The MMS catalyst is characterized as having a BET surface area of at least 20 m2/g and a pore volume of at least 0.05 cm3/g. In one embodiment, the MMS catalyst is also characterized as having a multi-phased structure comprising five phases: a molybdenum sulfide phase, a tungsten sulfide phase, a molybdenum tungsten sulfide phase, an active nickel phase, and a nickel sulfide phase.
대표청구항▼
1. A self-supported mixed metal sulfide (MMS) catalyst comprising molybdenum (Mo) sulfide, tungsten (W) sulfide, and nickel (Ni) sulfide; wherein the catalyst has a BET surface area of at least 20 m2/g and a pore volume of at least 0.05 cm3/g; andwherein the catalyst is characterized by a Ni surface
1. A self-supported mixed metal sulfide (MMS) catalyst comprising molybdenum (Mo) sulfide, tungsten (W) sulfide, and nickel (Ni) sulfide; wherein the catalyst has a BET surface area of at least 20 m2/g and a pore volume of at least 0.05 cm3/g; andwherein the catalyst is characterized by a Ni surface concentration/Ni bulk concentration ratio of greater than 0.4 as characterized by XPS. 2. The self-supported MMS catalyst of claim 1, wherein the catalyst has a BET surface area of at least 30 m2/g. 3. The self-supported MMS catalyst of claim 2, wherein the catalyst has a BET surface area of at least 40 m2/g. 4. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized by a Ni surface concentration/Ni bulk concentration ratio of greater than 0.5 as characterized by XPS. 5. A self-supported mixed metal sulfide (MMS) catalyst comprising molybdenum (Mo) sulfide, tungsten (W) sulfide, and nickel (Ni) sulfide; wherein the catalyst has a BET surface area of at least 20 m2/g and a pore volume of at least 0.05 cm3/g; andwherein the catalyst is characterized by a W surface concentration/W bulk concentration ratio of greater than 0.3 as characterized by XPS. 6. The self-supported MMS catalyst of claim 5, wherein the catalyst has a BET surface area of at least 30 m2/g. 7. The self-supported MMS catalyst of claim 6, wherein the catalyst has a BET surface area of at least 40 m2/g. 8. The self-supported MMS catalyst of claim 5, wherein the catalyst is characterized by a W surface concentration/W bulk concentration ratio of greater than 0.4 as characterized by XPS. 9. A self-supported mixed metal sulfide (MMS) catalyst comprising molybdenum (Mo) sulfide, tungsten (W) sulfide, and nickel (Ni) sulfide; wherein the catalyst has a BET surface area of at least 20 m2/g and a pore volume of at least 0.05 cm3/g; andwherein the catalyst is characterized as having molar ratios of metal components Ni:Mo:W in a region defined by five points ABCDE of a ternary phase diagram, and wherein the five points ABCDE are defined as: A: Ni=0.80, Mo=0.00, W=0.20, B: Ni=0.25, Mo=0.00, W=0.75, C: Ni=0.25, Mo=0.25, W=0.50, D: Ni=0.63, Mo=0.25, W=0.12, E: Ni=0.80, Mo=0.08, W=0.12. 10. The self-supported MMS catalyst of claim 9, wherein the catalyst is characterized as having a molar ratio of metal components Ni:Mo:W in a range of: 0.33≦Ni/(Mo+W)≦2.57, a range of Mo/(Ni+W) molar ratios of 0.00≦Mo/(Ni+W)≦0.33, and a range of W/(Ni+Mo) molar ratios of 0.18≦W/(Ni+Mo)≦3.00. 11. The self-supported MMS catalyst of claim 9, wherein the catalyst is characterized as having a molar ratio of metal components Ni:Mo:W in a region defined by five points ABCDE of a ternary phase diagram, and wherein the five points ABCDE are defined as: A (Ni=0.72, Mo=0.00, W=0.28), B (Ni=0.55, Mo=0.00, W=0.45), C (Ni=0.48, Mo=0.14, W=0.38), D (Ni=0.48, Mo=0.20, W=0.33), E (Ni=0.62, Mo=0.14, W=0.24). 12. The self-supported MMS catalyst of claim 9, wherein the catalyst is further characterized having a molar ratio of metal components Ni:Mo:W in a range of: 1.24≦Ni/W≦2.68;1.67≦W/Mo≦∞; and0.91≦Ni/(W+Mo)≦2.57. 13. A self-supported mixed metal sulfide (MMS) catalyst comprising molybdenum (Mo) sulfide, tungsten (W) sulfide, and nickel (Ni) sulfide; wherein the catalyst has a BET surface area of at least 20 m2/g and a pore volume of at least 0.05 cm3/g;wherein the catalyst is characterized by a multi-phased structure comprising five phases: a molybdenum sulfide phase, a tungsten sulfide phase, a molybdenum tungsten sulfide phase, an active nickel phase, and a nickel sulfide phase; andwherein the molybdenum tungsten sulfide phase envelopes slabs of Ni9S8 and Ni3S2. 14. The self-supported MMS catalyst of claim 13, wherein the molybdenum tungsten sulfide phase comprises at least a layer, wherein the at least a layer contains at least one of: a) molybdenum sulfide and tungsten sulfide; b) tungsten isomorphously substituted into molybdenum sulfide as individual atoms or as tungsten sulfide domains; c) molybdenum isomorphously substituted into tungsten sulfide as individual atoms or as molybdenum sulfide domains; and d) mixtures thereof. 15. The self-supported MMS catalyst of claim 14, wherein the molybdenum tungsten sulfide phase comprises 1 to 6 layers. 16. The self-supported MMS catalyst of claim 14, wherein the at least a layer comprises tungsten isomorphously substituted into molybdenum sulfide as individual atoms forming an intralayer atomic mixture. 17. The self-supported MMS catalyst of claim 14, wherein the at least a layer comprises tungsten isomorphously substituted into molybdenum sulfide as tungsten domains. 18. The self-supported MMS catalyst of claim 14, wherein the at least a layer comprises molybdenum isomorphously substituted into tungsten sulfide as individual atoms forming an intralayer atomic mixture. 19. The self-supported MMS catalyst of claim 14, wherein the at least a layer comprises molybdenum isomorphously substituted into tungsten sulfide as molybdenum domains. 20. The self-supported MMS catalyst of claim 14, wherein the molybdenum tungsten sulfide phase comprises inter-layer mixtures of tungsten sulfide and molybdenum sulfide. 21. The self-supported MMS catalyst of claim 14, wherein the at least a layer comprises mixtures of individual domains of tungsten sulfide and molybdenum sulfide. 22. The self-supported MMS catalyst of claim 14, wherein the active nickel phase comprises at least one of atomic nickel and reduced nickel substituted into edge of the molybdenum tungsten sulfide phase. 23. The self-supported MMS catalyst of claim 14, wherein the nickel sulfide phase comprises slabs of Ni9S8 and Ni3S2 layers. 24. The self-supported MMS catalyst of claim 14, wherein the nickel sulfide phase serves as support for the molybdenum tungsten sulfide phase. 25. The self-supported MMS catalyst of claim 14, wherein the nickel sulfide phase stabilizes dispersion of the active nickel phase onto the molybdenum tungsten sulfide phase. 26. The self-supported MMS catalyst of claim 14, wherein the catalyst is characterized by an X-ray diffraction pattern showing peaks corresponding to MoS2 phase and WS2 phase. 27. The self-supported MMS catalyst of claim 14, wherein the catalyst is characterized by an X-ray diffraction pattern showing peaks corresponding to Ni3S2 phase. 28. The self-supported MMS catalyst of claim 14, wherein the catalyst is characterized by TEM image showing lattice fringes on nickel sulfide crystals of 4.60±0.5 Å and 2.87±0.5 Å.
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