IP Library Granted Patent US 12,128,389
Granted Patent B2
US 12,128,389 · App. 17/630,535 · Granted Oct 29, 2024

Chabazite synthesis method including organic and inorganic structure directing agents and chabazite zeolite with flake-like morphology

Inventors: Rajamani P. Gounder (Lafayette, IN); John Rocco Di Iorio (Cambridge, MA); Casey Benjamin Jones (West Lafayette, IN); Claire Townsend Nimlos (West Lafayette, IN); Vivek Vattipalli (Florham Park, NJ); Subramanian Prasad (Florham Park, NJ); Eduard L. Kunkes (Florham Park, NJ); Ahmad Moini (Florham Park, NJ)
Assignee: BASF Mobile Emissions Catalysts LLC
B01J29/783B01D53/9418B01J29/7015B01J29/74B01J29/763B01J35/393B01J37/0018B01J37/036B01J37/04B01J37/08B01D2255/20761B01D2255/50F01N3/2066F01N3/2803F01N2370/04
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Quick Facts
Patent No.
US 12,128,389
App. No.
17/630,535
Granted
Oct 29, 2024
Kind
B2
Abstract

The disclosure generally provides zeolites having the CHA crystalline framework and methods of preparing the same. Provided herein are CHA zeolites containing intergrowths, a controlled framework aluminum distribution, or both. Further provided are CHA zeolites wherein crystals of the zeolite material have a predominantly flake-like morphology as determined by scanning electron microscopy (SEM). Further provided are catalyst compositions, articles, and systems including CHA zeolites promoted with a metal.

Claims (39)

1. A method of synthesizing a zeolite having a CHA crystalline framework, the method comprising:

preparing a mixture of water, an aluminum source, a silica source, a source of an organic structure directing agent, and an inorganic structure-directing agent to form a synthesis gel, wherein the inorganic structure-directing agent is a source of potassium cations; and

subjecting the synthesis gel to a crystallization process to crystallize the zeolite having the CHA crystalline framework,

wherein the source of the organic structure-directing agent is N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAda) and an amount of TMAda and an amount of the potassium cation source is such that a molar ratio of potassium cations to N,N,N-trimethyl-1-adamantylammonium cations are in a molar ratio ranging from about 1 to about 20.

2. The method of claim 1 , wherein the source of the potassium cations is potassium hydroxide.

3. The method of claim 1 , wherein preparing comprises:

a first mixing step comprising adding the source of the organic structure-directing agent, the source of the inorganic structure-directing agent, and the source of aluminum to the water to form an aluminum-containing aqueous solution;

mixing the aqueous solution for a first time period; and

a second mixing step comprising adding the source of silicon to the aluminum-containing aqueous solution and mixing for a second time period to form an aluminosilicate-containing solution.

4. The method of claim 1 , wherein the crystallization process comprises mixing the synthesis gel at a temperature ranging from about 140° C. to about 200° C. for a time period of from about 24 hours to about 6 days.

5. The method of claim 1 , wherein a OH/Si ratio of the synthesis gel is from about 0.1 to about 0.5.

6. The method of claim 1 , wherein a ratio of the silicon source to the aluminum source to TMAda to the potassium cation source to the water is represented by the formula:

1SiO 2 /0.033Al 2 O 3 /X TMA da OH/0.5*(0.5−X)K 2 O/44 H 2 O;

wherein the value of X is from 0.01 to 0.25.

7. The method of claim 1 , wherein:

the zeolite having the CHA crystalline framework is an intergrowth zeolite comprising a first CHA phase and a second CHA phase;

the first CHA phase and the second CHA phase each independently have a unit cell volume of from about 2338 Å 3 to 2489 Å 3 ; and

the unit cell volume of the first CHA phase is different from the unit cell volume of the second CHA phase.

8. The method of claim 7 , wherein:

the first CHA phase and the second CHA phase each independently have a silica-to-alumina ratio (SAR) of from about 4 to about 100; and

the SAR of the first CHA phase is different from the SAR of the second CHA phase.

9. The method of claim 7 , wherein:

the first CHA phase represents from about 5% to about 95% of the intergrowth zeolite;

the first CHA phase has a potassium cation to aluminum ratio of greater than 0.5; and

the second CHA phase has a potassium cation to aluminum ratio of less than about 0.5.

10. The method of claim 7 , wherein the intergrowth zeolite crystal size ranges from about 0.1 to about 15 μm.

11. A method of synthesizing a zeolite material having a CHA crystalline framework and a predominantly flake-like morphology, the method comprising:

preparing a mixture of water, an aluminum source, a silicon source, an organic structure directing agent, and an inorganic structure directing agent to form a synthesis gel, wherein the inorganic structure directing agent comprises potassium cations; and

subjecting the synthesis gel to a crystallization process to crystallize the zeolite material,

wherein the inorganic structure directing agent is potassium hydroxide and the organic structure directing agent is N,N,N-trimethyl-1-adamantylammonium hydroxide (TMAdaOH), and an amount of TMAdaOH and an amount of potassium cations present in the synthesis ge I is such that a molar ratio of potassium cations to TMAdaOH is about 10 or greater.

12. The method of claim 11 , wherein preparing comprises:

a first mixing step comprising adding the organic structure-directing agent, the inorganic structure-directing agent, and the source of aluminum to the water to form an aluminum-containing aqueous solution;

mixing the aqueous solution for a first time period; and

a second mixing step comprising adding the source of silicon to the aluminum-containing aqueous solution and mixing for a second time period to form an aluminosilicate-containing solution.

13. The method of claim 11 , wherein the crystallization process comprises mixing the synthesis gel at a temperature ranging from about 100° C. to about 200° C. for a time period ranging from about 12 hours to about 6 days.

14. The method of claim 13 , wherein the temperature ranges from about 160° C. to about 180° C.

15. The method of claim 11 , wherein the organic structure-directing agent further comprises at least one selected from the group consisting of trimethylcyclohexylammonium hydroxide, tetraethylammonium hydroxide, benzyltrimethylammonium hydroxide, 1,1,3,5-tetramethylpiperidinium hydroxide, choline hydroxide, N,N-dimethyl piperidinium hydroxide, trimethyl-2-ammonium exo-norbornane, and N-methyl-3-quinuclidinol.

16. The method of claim 11 , wherein the source of aluminum selected from the group consisting of a zeolite, aluminum isopropoxide, and aluminum hydroxide.

17. The method of claim 11 , wherein the source of silicon is selected from the group consisting of colloidal silica, a silicon alkoxide, fumed silica, amorphous silica, and an aluminosilicate, and combination thereof.

Assignments (3)
NUNC PRO TUNC ASSIGNMENT Recorded Aug 8, 2024
From: BASF CORPORATION
To: BASF MOBILE EMISSIONS CATALYSTS LLC
Reel/Frame 068518/0394 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 27, 2022
From: VATTIPALLI, VIVEK; KUNKES, EDUARD L.; MOINI, AHMAD; PRASAD, SUBRAMANIAN
To: BASF CORPORATION
Reel/Frame 058786/0058 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jan 27, 2022
From: GOUNDER, RAJAMANI P.; DI LORIO, JOHN ROCCO; JONES, CASEY BENJAMIN; NIMLOS, CLAIRE TOWNSEND
To: PURDUE RESEARCH FOUNDATION
Reel/Frame 058786/0268 →
Continuity (3)
Provisional Application 63002595 · Mar 31, 2020
Provisional Application 62882108 · Aug 2, 2019
Related Publication 20220266228A1 · Aug 25, 2022