STA-18, a new member of the SFW family of molecular sieve zeotypes, methods of preparation and use

Patent metadata

Field	Value
Publication number	US-10040690-B2
Application number	US-201715493371-A
Country	US
Kind code	B2
Filing date	Apr 21, 2017
Priority date	Apr 22, 2016
Publication date	Aug 7, 2018
Grant date	Aug 7, 2018

Abstract

STA-18, a molecular sieve having a SFW structure and containing phosphorus in the framework, is described. STA-18AP (as prepared) can have a lower alkyl amine, such as trimethylamine, and one of 1,6-(1,4-diazabicyclo[2.2.2]octane)hexyl cations (from diDABCO-C6) or 1,7-(1,4-diazabicyclo[2.2.2]octane)heptyl cations (from diDABCO-C7) or 1,8-(1,4-diazabicyclo[2.2.2]octane)octyl cations (from diDABCO-C8) as SDAs. A lower alkyl ammonium hydroxide, such as tetrabutylammonium hydroxide, can be used as a pH modifier for making SAPO STA-18. A calcined product, STA-18C, formed from STA-18AP is also described. Methods of preparing STA-18AP, STA-18C and metal containing calcined counterparts of STA-18C are described along with methods of using STA-18C and metal containing calcined counterparts of STA-18C in a variety of processes, such as treating exhaust gases and converting methanol to olefins are described.

First claim

What is claimed is:

1. A molecular sieve (STA-18) comprising an SFW type framework with phosphate within the framework.

2. The molecular sieve of claim 1 , wherein the molecular sieve is a silicoaluminophosphate (SAPO), a metal silicoaluminophosphate (MeSAPO) or a metal aluminophosphate (MeAPO).

3. The molecular sieve of claim 1 , where the SFW structure is free from structural faulting.

4. The molecular sieve of claim 1 , where the molecular sieve comprises at least one metal within the framework where the metal is selected from at least one of the metals of Groups of the Periodic Table IIIA, IB, IIB, VA, VIA, VIIA, VIIIA and combinations thereof.

5. The molecular sieve of claim 1 , where the molecular sieve further comprises at least one extra-framework transition metal selected from the group consisting of Ag, Au, Ce, Co, Cr, Cu, Fe, Ga, In, Ir, Mn, Mo, Nb, Ni, Pd, Pt, Re, Rh, Ru, Sn, Ta, V, W and Zn.

6. The molecular sieve of claim 1 , where the molecular sieve is calcined or contains one of more structure directing agents (SDAs).

7. The molecular sieve of claim 1 , where the molecular sieve is a silicoaluminophosphate.

8. The molecular sieve of claim 7 having the molar relationship: (Si x Al y P z )O 2 , where x is the mole fraction of Si and has a value from 0.05 to 0.3, y is the mole fraction of Al and has a value from 0.4 to 0.6, z is the mole fraction of P and has a value from 0.2 to 0.45, and x+y+z=1.

9. The molecular sieve of claim 8 , where the molecular sieve is a calcined molecular sieve and has at least one property selected from the group consisting of: a characteristic X-ray powder diffraction pattern substantially similar to that shown in FIG. 4 ; and a characteristic X-ray powder diffraction pattern comprising 2-theta positions at 7.8 (vs), 11.0 (vs), 13.0 (vs) and 21.5 (s)±0.2 with the corresponding relative intensity shown in parenthesis, where the corresponding relative intensities are w (weak)<20; m (medium) is ≥20 and <40; s (strong) is ≥40 and <60; and vs (very strong) is ≥60.

10. The molecular sieve of claim 8 , where the molecular sieve further comprises one or more structure directing agents (SDAs).

11. The molecular sieve of claim 10 , where the structure directing agents comprises a lower alkyl amine and a 1,4-diazabicyclo[2.2.2]octane derivative.

12. The molecular sieve of claim 11 , where the lower alkyl amine is trimethylamine or N,N-dimethylethylamine.

13. The molecular sieve of claim 11 , where the 1,4-diazabicyclo[2.2.2]octane derivative is a 1,6-(1,4-diazabicyclo[2.2.2]octane)hexyl cation, or 1,7-(1,4-diazabicyclo[2.2.2]octane)heptyl cation or a 1,8-(1,4-diazabicyclo[2.2.2]octane)octyl cation.

14. The molecular sieve of claim 13 , where the lower alkyl amine is trimethylamine or N,N-dimethylethylamine and the 1,4-diazabicyclo[2.2.2]octane derivative is a 1,7-(1,4-diazabicyclo[2.2.2]octane)heptyl cation, where the molecular sieve has at least one property selected from the group consisting of: a characteristic X-ray powder diffraction pattern substantially similar to that shown in FIG. 5 ; and a characteristic X-ray powder diffraction pattern comprising 2-theta positions at 7.7 (vs), 10.8 (s-vs), 12.3 (m-s), 16.9 (s), 17.6 (s), 19.9 (s-vs), 21.3 (vs) and 26.7 (m-s)±0.2 with the corresponding relative intensity shown in parenthesis, where the corresponding relative intensities are w (weak)<20; m (medium) is ≥20 and <40; s (strong) is ≥40 and <60; and vs (very strong) is ≥60.

15. The molecular sieve of claim 13 , where the lower alkyl amine is trimethylamine or N,N-dimethylethylamine and the 1,4-diazabicyclo[2.2.2]octane derivative is a 1,8-(1,4-diazabicyclo[2.2.2]octane)octyl cation, where the molecular sieve has at least one property selected from the group consisting of: a characteristic X-ray powder diffraction pattern substantially similar to that shown in FIG. 7 ; and a characteristic X-ray powder diffraction pattern comprising 2-theta positions at 7.8 (vs), 10.8 (s), 12.3 (s), 16.9 (s), 17.7 (s-vs), 19.9 (v-vs), 21.4 (vs) and 26.7 (s)±0.2 with the corresponding relative intensity shown in parenthesis, where the corresponding relative intensities are w (weak)<20; m (medium) is ≥20 and <40; s (strong) is ≥40 and <60; and vs (very strong) is ≥60.

16. The molecular sieve of claim 11 , where the lower alkyl amine is trimethylamine or N,N-dimethylethylamine and the 1,4-diazabicyclo[2.2.2]octane derivative is a 1,6-(1,4-diazabicyclo[2.2.2]octane)hexyl cation, where the molecular sieve has at least one property selected from the group consisting of: a characteristic X-ray powder diffraction pattern substantially similar to that shown in FIG. 1 ; and a characteristic X-ray powder diffraction pattern comprising 2-theta positions at 7.7 (vs), 10.8 (vs), 12.3 (m-s), 16.9 (s), 17.6 (s), 19.9 (s-vs), 21.3 (vs) and 26.6 (s)±0.2 with the corresponding relative intensity shown in parenthesis, where the corresponding relative intensities are w (weak)<20; m (medium) is ≥20 and <40; s (strong) is ≥40 and <60; and vs (very strong) is ≥60.

17. A catalyst comprising a molecular sieve of claim 1 .

18. A catalyst article for treating exhaust gas comprising a catalyst composition of claim 17 , where the catalyst is disposed on and/or within a honeycomb structure.

19. A method for synthesizing a molecular sieve of claim 1 , the method comprising:
a. forming heating a reaction mixture comprising: (a) at least one source of alumina, (b) at least one source of silica, (c) at least one source of phosphorus, and (d) one or more structure directing agents (SDAs);
b. forming molecular sieve crystals having a SFW framework and the structure directing agent, and
c. recovering at least a portion of the molecular sieve crystals from the reaction mixture,
wherein the reaction mixture is a gel having a molar compositional ratio of:

P/A
 0.5-0.99

MeO 2 /A
0.02-1.0

SDA1 (1,4-diazabicyclo[2.2.2]octane derivative)/A
 0.1-06

SDA2 (lower alkyl amine)/A
 0.1-0.6

Lower alkyl ammonia hydroxide/A
 0.1-0.6

H 2 O/A
  20-200

where P the source of phosphorous and is calculated as being in the oxide form (P 2 O 5 ), A is Al, Fe, Cr, B, Ga or combinations thereof and is calculated as being in the oxide form (A 2 O 3 ); and Me is Si, Ge, Mg or combinations thereof and is calculated as being in the oxide form (MO 2 ).

20. A method for treating an exhaust gas comprising contacting a combustion exhaust gas containing NO x and/or NH 3 with a catalyst according to claim 1 to selectively reduce at least a portion of the NO x into N 2 and H 2 O and/or oxidize at least a portion of the NH 3 .

21. A method for treating an exhaust gas comprising contacting a combustion exhaust gas containing NO x with a passive NOx absorber comprising a molecular sieve of claim

Assignees

• Johnson Matthey Plc

Inventors

• Casci John
• Turrina Alessandro
• Garcia Salas Raquel
• Wright Paul

Classifications

• C09C1/343

  containing silicon or associated with silicon containing material, except when silicon only occurs in a thin coating of the particles · CPC title

• B01J29/83

  Aluminophosphates [APO compounds] · CPC title

• B01J29/82

  Phosphates {(B01J29/005 takes precedence)} · CPC title

• G01N23/20

  by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials · CPC title

• C01B39/54 Primary

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