Method to synthesize crystalline materials in the presence of ODSO with improved zeolite crystallization rates and enhanced relative crystallinity

Patent metadata

Field	Value
Publication number	US-12410062-B2
Application number	US-202318152379-A
Country	US
Kind code	B2
Filing date	Jan 10, 2023
Priority date	Jan 10, 2023
Publication date	Sep 9, 2025
Grant date	Sep 9, 2025

Abstract

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.

First claim

What is claimed is:

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

Assignees

• Saudi Arabian Oil Co

Inventors

• Hodgkins Robert Peter
• Koseoglu Omer Refa
• Zaarour Moussa
• Martinez Javier Ruiz
• Ould-Chikh Samy

Classifications

• C01B39/54

  Phosphates, e.g. APO or SAPO compounds · CPC title

• C01B25/265

  General methods for obtaining phosphates · CPC title

• C01B25/45

  containing plural metal, or metal and ammonium · CPC title

• C01B37/08

  Silicoaluminophosphates [SAPO compounds] {, e.g. CoSAPO} · CPC title

• C01B39/40 Primary

  using at least one organic template directing agent · CPC title