Promotor for active phase metals dispersion in hydroprocessing catalysts and method of making the catalyst
A composition comprising a promotor component is disclosed comprising a mixture of one or more catalytically active components and one or more oxidized disulfide oil (ODSO) compounds, including a water-soluble fraction of ODSO. A composition comprising an aqueous solution of one or more catalytically active components and a promotor component is also disclosed. In certain embodiments the ODSO is obtained from the effluent of an enhanced MEROX process. The compositions facilitate transfer of catalytically active components (or components that will be catalytically active in the finished solid catalyst material) onto the surface of support materials.
1. A method for manufacture of catalyst material comprising:
providing a support material in the form of powder, particulates, granules, extrudates or a combination of said forms, the support material being porous and including outer surfaces and pore inner surfaces for receiving catalytically active components;
contacting the support material with a promotor component composition including one or more oxidized disulfide oil (ODSO) compounds to produce enhanced support material; and
contacting the enhanced support material with an aqueous solution of the catalytically active components, precursors of the catalytically active components or a combination thereof, as an impregnating solution to disperse the catalytically active components on the outer surfaces and pore inner surfaces of the support material and transfer thereto to form support material loaded with the catalytically active components.
2. The method of claim 1 , wherein the catalytically active components are selected from Periodic Table IUPAC groups 4-14.
3. The method of claim 1 , wherein the catalytically active components are one or more of Co, Ni, Mo, W, Pt, or Pd.
4. The method of claim 1 , wherein the promotor component comprises ODSO compounds and water at a ratio (V %) of ODSO:H 2 O in the range of from 100:0, to 0.1:99.9.
5. The method of claim 1 , wherein the promotor component comprises ODSO and one or more other promotor compounds selected from the group consisting of citric acid, ethylenediaminotetraacetic acid (EDTA), malic acid, oxalic acid and formic acid.
6. The method of claim 5 , wherein the one or more additional acidic promotor components has a pKa in the range of from about 1-10.
7. The method as claim 1 , wherein the mass ratio of ODSO compounds to the support material is in the range of from 0.001-1 and the mass ratio of the active components to the support material is in the range of from 0.001-1.
8. The method as in claim 1 wherein the loaded support material has a pore volume in the range of about (cc/gm) 0.15-1.70; a specific surface area in the range of about (m 2 /g) 100-900; and an average pore diameter of at least about 10 angstrom units.
9. The method as in claim 1 , wherein said support material comprises a zeolite component and a binder component, wherein said binder component comprises or more amorphous inorganic oxide materials selected from the group consisting of alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorus-alumina, silica-alumina-boria, phosphorus-alumina-boria, phosphorus-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.
10. The method as in claim 9 , wherein the zeolite is one or more of zeolites identified by the International Zeolite Association, including those with the identifiers ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFV, AFX, AFY, AHT, ANA, ANO, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AVE, AVL, AWO, AWW, BCT, BEC, BIK, BOF, BOG, BOZ, BPH, BRE, BSV, CAN, CAS, CDO, CFI, CGF, CGS, CHA, -CHI, -CLO, CON, CSV, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EEI, EMT, EON, EPI, ERI, ESV, ETL, ETR, ETV, EUO, EWO, EWS, EZT, FAR, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFO, IFR, -IFT, -IFU, IFW, IFY, IHW, IMF, IRN, IRR, -IRY, ISV, ITE, ITG, ITH, ITR, ITT, -ITV, ITW, IWR, IWS, IWV, IWW, JBW, JNT, JOZ, JRY, JSN, JSR, JST, JSW, KFI, LAU, LEV, LIO, -LIT, LOS, LOV, LTA, LTF, LTJ, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MOZ, MRT, MSE, MSO, MTF, MTN, MTT, MTW, MVY, MWF, MWW, NAB, NAT, NES, NON, NPO, NPT, NSI, OBW, OFF, OKO, OSI, OSO, OWE, -PAR, PAU, PCR, PHI, PON, POR, POS, PSI, PTO, PTT, PTY, PUN, PWN, PWO, PWW, RHO, -RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAF, SAO, SAS, SAT, SAV, SBE, SBN, SBS, SBT, SEW, SFE, SFF, SFG, SFH, SFN, SFO, SFS, SFW, SGT, SIV, SOD, SOF, SOR, SOS, SOV, SSF, SSY, STF, STI, STT, STW, -SVR, SVV, SWY, -SYT, SZR, TER, THO, TOL, TON, TSC, TUN, UEI, UFI, UOS, UOV, UOZ, USI, UTL, UWY, VET, VFI, VNI, VSV, WEI, -WEN, YFI, YUG, ZON, *BEA, *CTH, *-EWT, *-ITN, *MRE, *PCS, *SFV, *—SSO, *STO, *—SVY, *UOE, silicalites, or one or more zeolites synthesized comprising co-crystallized products of two or more types of zeolites.
11. The method of claim 9 , wherein the zeolite is USY zeolite.
12. The method as in claim 1 , wherein the ODSO is derived from oxidation of disulfide oil compounds present in an effluent refinery hydrocarbon stream recovered following catalytic oxidation of mercaptans present in a mercaptan-containing hydrocarbon stream.
13. The method as in claim 1 , wherein the ODSO compounds have 3 or more oxygen atoms and include one or more compounds selected from the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (R′—SO—SO—OR), (R′—SOO—SO—OR), (R′—SO—SOO—OR) and (R′—SOO—SOO—OR), wherein R and R′ are the same or different C1-C10 alkyl or C6-C10 aryl.
14. The method as in claim 1 , wherein the ODSO compounds have 3 or more oxygen atoms and include two or more compounds selected from the group consisting of (R—SOO—SO—R′), (R—SOO—SOO—R′), (R—SO—SOO—OH), (R—SOO—SOO—OH), (R—SOO—SO—OH), (R′—SO—SO—OR), (R′—SOO—SO—OR), (R′—SO—SOO—OR) and (R′—SOO—SOO—OR), wherein R and R′ are the same or different C1-C10 alkyl or C6-C10 aryl.
15. The method as in claim 1 , further comprising subjecting the enhanced support material to one or more heat treatments prior to contacting with the aqueous solution of catalytically active components.
16. A method for manufacture of catalyst material comprising:
providing a support material in the form of powder, particulates, granules, extrudates or a combination of said forms, the support material being porous and including outer surfaces and pore inner surfaces for receiving catalytically active components;
contacting the support material with an aqueous solution of the catalytically active components, precursors of the catalytically active components or a combination thereof, as an impregnating solution to disperse on porous support material having outer surfaces and pore inner surfaces, the solution comprising one or more catalytically active components and one or more oxidized disulfide oil (ODSO) compounds as a promotor component for dispersion of the catalytically active components on the outer surfaces and pore inner surfaces of the support material transfer thereto to form support material loaded with the catalytically active components.
17. The method as in claim 16 , further wherein the support material is subjected to heating before contact with the composition.
18. The method as in claim 17 , wherein the composition is contacted with support material in one or more steps.
19. The method of claim 18 , wherein the support material is subjected to one or more heat treatments in between the one or more steps.