Methods to produce molecular sieves with LTA topology and compositions derived therefrom

Patent metadata

Field	Value
Publication number	US-10493440-B2
Application number	US-201715730003-A
Country	US
Kind code	B2
Filing date	Oct 11, 2017
Priority date	Mar 10, 2015
Publication date	Dec 3, 2019
Grant date	Dec 3, 2019

Abstract

The present disclosure is directed to processing for preparing crystalline pure-silica and heteroatom-substituted LTA frameworks in fluoride media using a simple organic structure-directing agent (OSDA), having a structure of Formula (I):

where substituents R 1 to R 9 are defined herein. Aluminosilicate LTA is an active catalyst for the methanol to olefins reaction with higher product selectivities to butenes as well as C5 and C6 products than the commercialized catalysts. Titanosilicate LTA is an active catalyst for the epoxidation of allyl alcohol using aqueous H 2 O 2 .

First claim

What is claimed:

1. A calcined crystalline microporous silicate of LTA topology that is an aluminosilicate having a molar ratio of Si : Al in a range of from about 12 to about 42 and containing no germanium oxide or a titanosilicate; wherein
the calcined crystalline microporous silicate of LTA topology is derived from or derivable from:
(a) hydrothermally treating an aqueous composition comprising:
(i) a source of a silicon oxide;
(ii) an optional source of aluminum oxide;
(iii) an optional source of titanium oxide;
(iv) an optional source of one or more of boron oxide, gallium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combination or mixture thereof;
(v) a mineralizing agent; and
(vi) an organic structure directing agent (OSDA) comprising a substituted benzyl-3H-imidazol-1-ium cation of Formula (I):

under conditions effective to crystallize an as-formed crystalline microporous silicate of LTA topology;
wherein
R 1 , R 2 , and R 7 are independently C 1-3 alkyl;
R 3 , R 4 , R 5 , R 6 , R 8 , and R 9 are independently H or C 1-3 alkyl;
(b) isolating the as-formed crystalline microporous silicate of LTA topology; and
(c) calcining the as-formed crystalline microporous silicate of LTA topology to form the calcined calcined aluminosilicate having a molar ratio of Si : Al in a range of from about 12 to about 42 and containing no germanium oxide or the titanosilicate.

2. The calcined crystalline microporous silicate of LTA topology of claim 1 , wherein the organic structure directing agent comprises the structure:

3. The calcined crystalline microporous silicate of claim 1 , that is the aluminosilicate having a molar ratio of Si : Al in a range of from about 33 to about 42 and containing no germanium oxide.

4. The calcined crystalline microporous silicate of claim 1 , that is the aluminosilicate having a molar ratio of Si : Al in a range of from about 12 to about 42 and containing no germanium oxide.

5. A calcined crystalline microporous titanosilicate of LTA topology; wherein
the calcined crystalline microporous titanosilicate of LTA topology is derived from or derivable from:
(a) hydrothermally treating an aqueous composition comprising:
(i) a source of a silicon oxide;
(ii) a source of titanium oxide;
(iii) an optional source of one or more of aluminum oxide, boron oxide, gallium oxide, germanium oxide, hafnium oxide, iron oxide, tin oxide, titanium oxide, indium oxide, vanadium oxide, zinc oxide, zirconium oxide, or combination or mixture thereof;
(vi) a mineralizing agent and
(vii) an organic structure directing agent (OSDA) comprising a substituted benzyl-3H-imidazol-1-ium cation of Formula (I):

under conditions effective to crystallize an as-formed crystalline microporous silicate of LTA topology;
wherein
R 1 , R 2 , and R 7 are independently C 1-3 alkyl;
R 3 , R 4 , R 5 , R 6 , R 8 , and R 9 are independently H or C 1-3 alkyl;
(b) isolating the as-formed crystalline microporous titanosilicate of LTA topology; and
(c) calcining the as-formed crystalline microporous titanosilicate of LTA topology to form the calcined titanosilicate.

6. The calcined crystalline microporous silicate of claim 4 , wherein the aluminosilicate is a pure aluminosilicate.

7. The calcined crystalline microporous aluminosilicate of claim 4 , comprising pores containing Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Be, Al, Ga, In, Zn, Ag, Cd, Ru, Rh, Pd, Pt, Au, Hg, La, Ce, Pr, Nd, Pm, Sm, Eu, or R 4-n N + H n cations, where R is alkyl, and n=0-4.

8. The calcined crystalline microporous aluminosilicate of claim 4 , comprising pores containing scandium, yttrium, titanium, zirconium, vanadium, manganese, chromium, molybdenum, tungsten, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, or a mixture thereof, each as a metal, oxide, or salt.

9. The calcined crystalline microporous aluminosilicate of claim 4 , comprising pores containing copper as a metal, oxide, or salt.

10. The calcined crystalline microporous aluminosilicate of claim 4 , exhibiting a powder XRD pattern having at least five peaks selected from the group consisting of 7.3°±0.3° 2-theta; 10.4°±0.3° 2-theta; 12.8°±0.3° 2-theta; 16.6°±0.3° 2-theta; 21.1°±0.3° 2-theta; 22.4°±0.3° 2-theta; and 24.7°±0.3° 2-theta.

11. The calcined crystalline microporous aluminosilicate of claim 4 , further exhibiting at least one of:
(a) an XRD diffraction pattern as those shown in FIG. 12 ; and/or
(b) an 27 Al MAS spectrum as shown in FIG. 13(A) or (B).

12. A process for catalyzing a reaction using a crystalline microporous silicate of claim 4 , the process comprising (a) carbonylating dimethyl ether (DME) with CO at low temperatures, (b) reducing NOx with methane, (c) cracking or hydrocracking a hydrocarbon, (d) dehydrogenating, (e) converting paraffins to aromatics, (f) converting methanol to olefins, (g) isomerizing xylenes, (h) disproportionating toluene, (i) alkylating aromatic hydrocarbons, (j) oligomerizing alkenes, (k) aminating lower alcohols, ( 1 ) separating and sorbing lower alkanes, (m) dewaxing a hydrocarbon feedstock, (n) isomerizing an olefin, (o) producing a higher molecular weight hydrocarbon from lower molecular weight hydrocarbon, (p) reforming a hydrocarbon, converting a lower alcohol or other oxygenated hydrocarbon to produce an olefin products, (q) epoxiding olefins with hydrogen peroxide, (r) reducing the content of an oxide of nitrogen contained in a gas stream in the presence of oxygen, or (s) separating nitrogen from a nitrogen-containing gas mixture by contacting the respective feedstock with the a catalyst comprising the calcined crystalline microporous aluminosilicate of claim 2 under conditions sufficient to affect the named transformation.

13. The process of claim 12 , comprising reducing NO x with methane, the method comprising contacting a mixture containing NO x and methane with a catalyst comprising the calcined crystalline microporous aluminosilicate of claim 2 under conditions sufficient to reduce the NOx content of the mixture.

14. A process for converting a lower alcohol or other oxygenated hydrocarbon to produce an olefin product, the process comprising contacting the lower alcohol or other oxygenated hydrocar with a catalyst comprising the calcined crystalline microporous aluminosilicate of claim 4 under conditions sufficient to produce the olefin product.

15. The process of claim 14 , wherein the lower alcohol or other oxygenated hydrocarbon is methanol.

16. The calcined crystalline microporous aluminosilicate of LTA topology of claim 4 that is derived or derivable from:
(a) hydrothermally treating an aqueous composition comprising:
(i) a source of a silicon oxide;
(ii) a source of aluminum oxide; and
(iii) an organic structure directing agent (OSDA) comprising the structure:

under conditions effective to crystallize an as-formed crystalline microporous aluminosilicate of LTA topology;
(b) isolating the as-formed crystalline microporous aluminosilicate of LTA topology; and
(c) calcining the as-formed crystalline microporous alum

Assignees

• California Inst Of Techn

Inventors

• Boal Ben W
• Davis Mark E
• Schmidt Joel E

Classifications

• C01B37/02

  Crystalline silica-polymorphs, e.g. silicalites {dealuminated aluminosilicate zeolites} · CPC title

• C07C2529/70

  of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 · CPC title

• B01J29/7007

  Zeolite Beta · CPC title

• C07D301/12

  with hydrogen peroxide or inorganic peroxides or peracids · CPC title

• B01D2255/50

  Zeolites · CPC title