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-0019397
(2013-09-05)
등록번호
US-9199224
(2015-12-01)
발명자
/ 주소
Han, Jinyi
Kuperman, Alexander E.
Maesen, Theodorus Ludovicus Michael
Trevino, Horacio
출원인 / 주소
Chevron U.S.A. Inc.
인용정보
피인용 횟수 :
1인용 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 has molar ratios of metal components Ni:Mo:W in a region defined by five points ABCDE of a ternary phase diagram, and wher
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 has 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=0.72, Mo=0.00, W=0.25), B (Ni=0.25, Mo=0.00, W=0.75), C (Ni=0.25, Mo=0.25, W=0.50), D (Ni=0.60, Mo=0.25, W=0.15), E (Ni=0.72, Mo=0.13, W=0.15).
대표청구항▼
1. A self-supported mixed metal sulfide (MMS) catalyst comprising molybdenum sulfide, nickel sulfide, and tungsten sulfide, and wherein 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 th
1. A self-supported mixed metal sulfide (MMS) catalyst comprising molybdenum sulfide, nickel sulfide, and tungsten sulfide, and wherein 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 in which Ni=0.72, Mo=0.00, W=0.25; B in which Ni=0.25, Mo=0.00, W=0.75; C in which Ni=0.25, Mo=0.25, W=0.50; D in which Ni=0.60, Mo=0.25, W=0.15; and E in which Ni=0.72, Mo=0.13, W=0.15. 2. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized as having a molar ratio of metal components Ni:Mo:W in a range of: 0.33≦Ni/(W+Mo)≦2.57;0.00≦Mo/(Ni+W)≦0.33; and0.18≦W/(Ni+Mo)≦3.00. 3. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized as having a molar ratio of metal components Ni:Mo:W in a range of: 1.08<=Ni/(Mo+W)<=2.030<=Mo/(Ni+W)<=0.18; and0.33<=W/(Mo+Ni)<=0.72. 4. The self-supported MMS catalyst of claim 1, 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. 5. The self-supported MMS catalyst of claim 4, wherein the catalyst has a BET surface area of at least 40 m2/g and a pore volume of at least 0.05 cm3/g. 6. The self-supported MMS catalyst of claim 1, wherein the catalyst after hydrotreating a heavy coker gas oil for at least 0.5 hrs, has a surface area of at least 20% of original surface area before hydrotreating. 7. The self-supported MMS catalyst of claim 1, wherein the catalyst has a Ni surface concentration/Ni bulk concentration ratio of greater than 0.4 as characterized by XPS. 8. The self-supported MMS catalyst of claim 7, wherein the catalyst has a Ni surface concentration/Ni bulk concentration ratio of greater than 0.5 as characterized by XPS. 9. The self-supported MMS catalyst of claim 1, wherein the catalyst has a W surface concentration/W bulk concentration ratio of greater than 0.3 as characterized by XPS. 10. The self-supported MMS catalyst of claim 9, wherein the catalyst has a W surface concentration/W bulk concentration ratio of greater than 0.4 as characterized by XPS. 11. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized by an HDN reaction first order kinetics rate constant of at least 100 g feed hr−1 g catalyst−1, and an HDS reaction first order kinetics rate constant of at least 550 g feed hr−1 g catalyst−1 in hydrotreating of a heavy coker gas oil as a feedstock with properties defined in Table A and under process conditions as defined in Table E: TABLE A(Simulated Distillation)Wt. %(° F.)0.532354161044330493505277055790588956019962499.5629 TABLE EReactor1 L batch autoclaveCatalyst precursororgano metallic compounds of nickel,molybdenum and tungstenSulfiding agentDMDS, CS2Feedheavy coker gas oilSolventhexadecaneAtmosphereH2Stir rate750 rpmSulfidingTemperatureRT → 250° C. (40 min) → 250° C. (2.5Conditionsrampinghr) → 343° C. (70 min) → 343° C. (2 hr)Pressure1800 psigQuenchbelow 100° C. within 2 minReactionTemperatureRT → 382° C. in 2 hrconditionsrampingPressure1800 psigTemperature382° C. (720° F.)Residence time0.5 hrQuenchbelow 100° C. within 2 min. 12. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized by an HDN reaction first order kinetics rate constant of at least 4 hr−1, and an HDS reaction first order kinetics rate constant of at least 5 hr−1 in hydrotreating of a heavy vacuum gas oil as a feedstock with properties defined by Table B and under process conditions as defined by Table F: TABLE B(Simulated Distillation)Wt %° F.0.56275702107373080550855709079097595100299104999.51063 TABLE FReactor1 L batch autoclaveCatalyst precursorhydroxide catalyst precursorSulfiding agentDMDS in straight run diesel with 2.5wt % sulfurFeedheavy vacuum gas oilAtmosphereH2SulfidingTemperature400-500° F. for low temperatureconditionssulfiding followed by 600-700° F. forhigh temperature sulfidingPressure0-2700 psigReactionTemperature700° F.conditionsPressure2300 psigLHSV2 hr−1H2 to feed ratio5000 scf/bbl, once through H2. 13. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized as having an HYD and HYL reaction rate constant of at least 10% higher than that of a catalyst comprising nickel sulfide and molybdenum sulfide, or a catalyst comprising nickel sulfide and tungsten sulfide, when compared on a same metal molar basis in hydrotreating of a diphenylether as a feedstock under process conditions as indicated in Table C: TABLE CReactor1 L batch autoclaveCatalyst precursorOrgano metallic compounds of nickel, molybdenum and tungstenSulfiding agentDMDS, CS2FeeddiphenyletherSolventhexadecaneAtomsphereH2Stir rate750 rpmReactionTemperature rampingRT→382° C. in 2 hrconditionsPressure1800 psigTemperature382° C. (720° F.)Residence time0.5 hrQuenchBelow 100° C. within 2 min 14. The self-supported MMS catalyst of claim 13, wherein a combined HYD and HYL reaction rate constant is at least 15% higher than that of a catalyst comprising nickel sulfide and molybdenum sulfide, or a catalyst comprising nickel sulfide and tungsten sulfide, when compared on the same metal molar basis in hydrotreating of a diphenylether as a feedstock under process conditions as indicated in Table D: TABLE DReactor1 L batch autoclaveCatalyst precursorOrgano metallic compounds of nickel,molybdenum and tungstenSulfiding agentDMDS, CS2FeedbenzeneSolventhexadecaneAtmosphereH2Stir rate750 rpmReactionTemperatureRT → 382° C. in 2 hrconditionsrampingPressure1800 psigTemperature382° C. (720° F.)Residence time0.5 hrQuenchBelow 100° C. within 2 min. 15. The self-supported MMS catalyst of claim 1, wherein the molybdenum sulfide is MoS2+e and the tungsten sulfide is WS2+e, and wherein e has a value between 0 and 1. 16. The self-supported MMS catalyst of claim 1, wherein the catalyst has 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. 17. The self-supported MMS catalyst of claim 16, wherein the molybdenum tungsten sulfide phase comprises at least a layer, and 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. 18. The self-supported MMS catalyst of claim 17, wherein the molybdenum tungsten sulfide phase comprises 1 to 6 layers. 19. The self-supported MMS catalyst of claim 17, wherein the at least a layer comprises tungsten isomorphously substituted into molybdenum sulfide as individual atoms forming an intralayer atomic mixture. 20. The self-supported MMS catalyst of claim 17, wherein the at least a layer comprises tungsten isomorphously substituted into molybdenum sulfide as tungsten domains. 21. The self-supported MMS catalyst of claim 17, wherein the at least a layer comprises molybdenum isomorphously substituted into tungsten sulfide as individual atoms forming an intralayer atomic mixture. 22. The self-supported MMS catalyst of claim 17, wherein the at least a layer comprises molybdenum isomorphously substituted into tungsten sulfide as molybdenum domains. 23. The self-supported MMS catalyst of claim 17, wherein the molybdenum tungsten sulfide phase comprises inter-layer mixtures of tungsten sulfide and molybdenum sulfide. 24. The self-supported MMS catalyst of claim 17, wherein the at least a layer comprises mixtures of individual domains of tungsten sulfide and molybdenum sulfide. 25. The self-supported MMS catalyst of claim 16, wherein the active nickel phase comprises at least one of atomic nickel and reduced nickel substituted into the molybdenum tungsten sulfide phase. 26. The self-supported MMS catalyst of claim 16, wherein the active nickel phase comprises NiSx nanoparticles dispersed onto the molybdenum tungsten sulfide phase or decorating the molybdenum tungsten sulfide phase. 27. The self-supported MMS catalyst of claim 16, wherein the nickel sulfide phase comprises slabs of Ni9S8 and Ni3S2 layers. 28. The self-supported MMS catalyst of claim 16, wherein the nickel sulfide phase serves as support for the molybdenum tungsten sulfide phase. 29. The self-supported MMS catalyst of claim 27, wherein the molybdenum tungsten sulfide phase envelopes the slabs of Ni9S8 and Ni3S2 layers. 30. The self-supported MMS catalyst of claim 16, wherein the nickel sulfide phase stabilizes dispersion of the active nickel phase onto the molybdenum tungsten sulfide phase. 31. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized by an X-ray diffraction pattern showing peaks corresponding to MoS2 phase and WS2 phase. 32. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized by an X-ray diffraction pattern showing peaks corresponding to Ni3S2 phase. 33. The self-supported MMS catalyst of claim 1, wherein the catalyst is characterized by TEM image showing lattice fringes on nickel sulfide of 4.60±0.5 Å and 2.87±0.5 Å.
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Lopez Jaime (Benicia CA) Pasek Eugene A. (Export PA) Cugini Anthony V. (Pittsburgh PA), Heavy oil hydroprocess including recovery of molybdenum catalyst.
Aldridge Clyde L. (Baton Rouge LA) Lewis William E. (Baton Rouge LA) Bearden ; Jr. Roby (Baton Rouge LA) Mayer Francis X. (Baton Rouge LA), Hydroconversion process.
Bearden ; Jr. Roby (Baton Rouge LA) Aldridge Clyde L. (Baton Rouge LA) Mayer Francis X. (Baton Rouge LA) Taylor James H. (Baton Rouge LA) Lewis William E. (Baton Rouge LA), Hydroconversion process using a sulfided molybdenum catalyst concentrate.
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Eadie Donald T. (North Vancouver CAX) Fefer Michael A. (Whitby CAX), Increasing VI of lube oil by hydrotreating using bulk Ni/Mn/Mo or Ni/Cr/Mo sulfide catalysts prepared from ligated metal.
Gardner Timothy J. ; Lott Stephen E. ; Lockwood Steven J. ; McLaughlin Linda I., Material and system for catalytic reduction of nitrogen oxide in an exhaust stream of a combustion process.
Hatfield W. Robert (Westfield NJ) Heck Ronald M. (Frenchtown NJ) Hsiung Thomas H. (Piscataway NJ), Method for recovering platinum in a nitric acid plant.
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.
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Plantenga, Frans Lodewijk; Eijsbouts, Sonja; Cerfontain, Marinus Bruce, Process for preparing an additive-based mixed metal catalyst, its composition and use.
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Erpenbach, Heinz; Gehrmann, Klaus; Lork, Winfried; Prinz, Peter, Process for recovering noble metals belonging to group VIII of the Periodic System of the elements from a contaminated catalyst solution originating from the carbonylation of methyl acetate and/or di.
Bnger Heinrich (Siegburg DEX) Cordes Rudolf (Niederkassel DEX) Hoffmann Gerhard (Niederkassel DEX), Process for the recovery and reuse of heavy metal oxidation catalyst from residues in the Witten DMT process.
Ebel Robert Henry (Riverside CT) Lento ; Jr. Louis Leonard (Upper Saddle River NJ), Stable alumina catalyst support, process therefor, and promoted support.
Halbert Thomas R. (Annandale NJ) Chianelli Russell R. (Somerville NJ) Stiefel Edward I. (Bridgewater NJ) Jacobson Allan J. (Princeton NJ), Transition metal tris-dithiolene and related complexes as precursors to active catalysts.
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