Method to synthesize crystalline materials in the presence of ODSO with improved zeolite crystallization rates and enhanced relative crystallinity
The present disclosure is directed to a method of manufacture of zeolite. A sol-gel formulation includes a water-soluble fraction of ODSO as an additional component. The resulting products include zeolite with increased crystallinity relative to comparable sol-gel formulations without ODSO as a precursor. In additional embodiments, the rate of crystallization of the zeolite is greater relative to comparable sol-gel formulations without ODSO.
1. A method for synthesis of crystalline material comprising:
forming a sol-gel composition of precursors, reagents, water and water-soluble oxidized disulfide oil (ODSO) effective for the crystalline material; and
heating the sol-gel composition under conditions and for a time effective to form a precipitate suspended in a supernatant, wherein the precipitate comprises a crystalline material, and wherein
the crystalline material is characterized by a relative crystallinity that is greater than that of a comparative material, and/or crystalline material is formed at a crystallization rate that is greater than that of a comparative material, and wherein the comparative material is formed of approximately equivalent composition of components except for water instead of the added ODSO, and under approximately equivalent conditions and time.
2. The method of claim 1 , wherein the crystalline material is zeolite and precursors and reagents effective for the crystalline material comprise a silica source, an optional alumina source, a mineralizer, an optional structure directing agent an optional seed material,
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, or *UOE, or one or more zeolites synthesized comprising co-crystallized products of two or more types of zeolites identified above, or a zeolite comprising siliceous crystalline materials with a SAR close to infinity,
wherein the zeolite possesses MFI, FAU, *BEA, MOR, or CHA frameworks,
wherein the structure directing agent is one or more of quaternary ammonium ions, trialkylamines, dialkylamines, monoalkylamines, cyclic amines, alkylethanol amines, cyclic diamines, alkyl diamines, alkyl polyamines, and other templates including alcohols, ketones, morpholine and glycerol.
3. The method of claim 2 , wherein the mineralizer comprises is sodium and wherein
the zeolite is a ZSM-5 zeolite and the mass ratio of ODSO to sodium from the mineralizer is in the range of about 0.1-10 and the amount by mass of water in the sol-gel composition can be substituted with ODSO in an amount of up to about 15%.
4. The method of claim 1 , wherein the crystalline material is an AlPO and the precursors and reagents effective for the crystalline material comprise an alumina source, a phosphorus source, an acid medium, an optional structure directing agent and an optional seed material,
wherein the AlPO is one or more of AlPO sub-types: (AEI) including AlPO-18, (AEL) including AlPO-11, (AEN) including AlPO-53, (AET) including AlPO-8, (AFI) including AlPO-5, (AFN) including AlPO-14, (AFO) including AlPO-41, (AFR) including AlPO-40; (AFT) including AlPO-52; (ANA) including AlPO-24; (AST) including AlPO-16; (ATO) including AlPO-31; (ATS) including AlPO-36; (ATT) including AlPO-33; (ATV) including AlPO-25; (AWO) including AlPO-21; (AWW) including AlPO-22; (CHA) including AlPO-34; (ERI) including AlPO-17; (LEV) including AlPO-35; (SOD) including AlPO-20; or (VFI) including AlPO-54,
wherein the structure directing agent is one or more of secondary and tertiary amine derived templates, quaternary ammonium derived templates, azamacrocycle derived templates, spiro templates, diaazabicyclo derived templates, or phosphazine based templates.
5. The method of claim 1 , wherein the crystalline material is a SAPO and the precursors and reagents effective for the crystalline material comprise an alumina source, a silica source, a phosphorus source, an acid medium, an optional structure directing agent and an optional seed material, which are formed as a homogeneous aqueous solution,
wherein the SAPO is one or more of SAPO sub-types: (AEI) including SAPO-18, (AEL) including SAPO-11, (AFI) including SAPO-5, (AFO) including SAPO-41, (AFR) including SAPO-40, (AFX) including SAPO-56, (ATN) including SAPO-39, (ATO) including SAPO-31, (CHA) including SAPO-34 and -47, (FAU) including SAPO-37, (GIS) including SAPO-43, (LEV) including SAPO-35, or (LTA) including SAPO-42,
wherein the structure directing agent is one or more of secondary and tertiary amine derived templates, quaternary ammonium derived templates, azamacrocycle derived templates, spiro templates, diaazabicyclo derived templates, or phosphazine based templates.
6. The method of claim 1 , wherein the crystalline material is a MAPO and the precursors and reagents effective for the crystalline material comprise an alumina source, a metal source, a phosphorus source, an acid medium, an optional structure directing agent and an optional seed material, which are formed as a homogeneous aqueous solution,
wherein the MAPO is one or more of MAPO sub-types: (AFI) including MAPO-5; (AFS) including MAPO-46; (ATN) including MAPO-39; (ATO) including MAPO-31; (ATS) including MAPO-36; or (GIS) including MAPO-43,
wherein the structure directing agent is one or more of secondary and tertiary amine derived templates, quaternary ammonium derived templates, azamacrocycle derived templates, spiro templates, diaazabicyclo derived templates, or phosphazine based templates,
wherein the metal source is one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd or Mg.
7. The method of claim 6 , wherein the metal source is one or more of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd or Mg.
8. The method of claim 1 , wherein the precipitate further comprises amorphous material.
9. The method of claim 8 , wherein the amount of crystalline material (C) relative to the amount of amorphous material (A) in the precipitate is calculated by the following equations:
R
p
=
1
0
0
×
S
p
(
ZMV
)
p
∑
i
S
i
(
ZMV
)
i
,
Corr
(
R
p
)
=
R
p
×
W
Std
R
Std
,
A
=
10
0
-
W
Std
-
∑
Corr
(
R
p
)
,
and
C
=
10
0
-
A
,
wherein:
R p =relative proportion of a particular phase,
S=the Rietveld scale factor, which is a parameter that is sample and phase dependent,
Z=the number of formula units per unit cell,
M=the mass of the formula unit,
V=the unit-cell volume,
i=number of phases in sample,
p=a particular phase,
Corr(Rp)=corrected relative proportion of a particular phase,
W Std (%)=the weighed concentration of an internal standard, and
R Std (%)=the Rietveld analyzed concentration of the internal standard.
10. The method of claim 1 , wherein the sol-gel composition can be from a colloidal suspension in appearance to a dense gel or paste.
11. The method of claim 1 , that has an operating pressure in the range of from atmospheric pressure to 17 bar.
12. The method of claim 1 , that has an operating pressure of autogenous pressure.
13. The method of claim 1 , further comprising introducing a nitrogen blanket or purge air prior to heating.
14. The method of 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.
15. The method of claim 1 , wherein the one or more ODSO compounds comprise ODSO compounds having 3 or more oxygen atoms and 1 to 20 carbon atoms, and are contained in a mixture having an average density greater than about 1.0 g/cc and an average boiling point greater than about 80°.
16. The method of 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),
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);
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—SO—SO—OH), (R—SOO—SO—OH); or
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—SO—SO—OH), (R—SOO—SO—OH);
wherein R and R′ are C1-C10 alkyl or C6-C10 aryl groups.
17. A method for synthesis of crystalline material comprising:
forming a sol-gel composition of precursors, reagents, water and water-soluble oxidized disulfide oil (ODSO) effective for the crystalline material; and
heating the sol-gel composition under conditions and for a time effective to form a precipitate suspended in a supernatant, wherein the precipitate comprises a crystalline material, wherein the crystalline material is characterized by a relative crystallinity that is greater than that of a comparative material, and wherein the comparative material is formed of approximately equivalent composition of components except for water instead of the added ODSO, and under approximately equivalent conditions and time.
18. The method of claim 17 , wherein the relative crystallinity of the crystalline material is in the range of from 1-85% greater than that of an equivalent water-only crystalline material synthesis.
19. A method for synthesis of crystalline material comprising:
forming a sol-gel composition of precursors, reagents, water and water-soluble oxidized disulfide oil (ODSO) effective for the crystalline material; and
heating the sol-gel composition mixture under conditions and for a time effective to form precipitate suspended in a supernatant, wherein the precipitate comprises a crystalline material, wherein the crystalline material is formed at a crystallization rate that is greater than that of a comparative material, and wherein the comparative material is formed of approximately equivalent composition of components except for water instead of the added ODSO, and under approximately equivalent conditions and time.
20. The method as in claim 19 , wherein the crystalline material is formed at a crystallization rate that is in the range of from 1-90% greater than that of an equivalent water-only crystalline material synthesis.