# US 11,027,983 B2 · Chabazite zeolite synthesis with organic templates

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- Number: US 11,027,983 B2
- Document ID: US11027983B2
- Status: Granted
- Kind: B2
- Application number: 16/901,395
- Filed: 2020-06-15
- Published: 2020-12-17
- Granted: 2021-06-08
- Earliest claimed: 2019-06-13
- Assignees: PQ Corporation
- Applicants: Hong-Xin Li; Bjorn Moden; Anton Petushkov
- Inventors: Hong-Xin Li; Bjorn Moden; Anton Petushkov
- Web page: https://patentgrep.com/patent/US11027983B2

## CPC

- C01B 39/48: using at least one organic template directing agent
- B01D 53/8628: {Processes characterised by a specific catalyst}
- B01D 53/9418: {for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas}
- B01J 23/72: Copper
- B01J 23/745: Iron
- B01J 29/763: {CHA-type, e.g. Chabazite, LZ-218}
- B01J 37/0201: {Impregnation}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/30: Ion-exchange
- B01D 2251/206: Ammonium compounds
- B01D 2255/20738: Iron
- B01D 2255/20761: Copper
- B01D 2255/50: Zeolites
- B01D 2257/404: Nitrogen oxides other than dinitrogen oxide
- B01J 29/7015: {CHA-type, e.g. Chabazite, LZ-218}
- B01J 2229/16: to increase the Si/Al ratio; Dealumination
- B01J 2229/186: not in framework positions
- B01J 2229/36: Steaming
- B01J 2235/15: X-ray diffraction
- C01P 2006/12: Surface area
- C01P 2006/16: Pore diameter
- F01N 3/2066: {Selective catalytic reduction [SCR]}
- F01N 2370/04: Zeolitic material
- F01N 2570/14: Nitrogen oxides
- F01N 2610/02: the substance being ammonia or urea
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01D: SEPARATION (separating solids from solids by wet methods B03B, B03D; by pneumatic jigs or tables B03B; by other dry methods B07; magnetic or electrostatic separation of solid materials from solid materials or fluids, separation by high-voltage electric fields B03C; centrifuges, vortex apparatus B04; presses per se for squeezing-out liquid from liquid-containing material B30B9/02; treatment of water C02F, e.g. softening by ion-exchange C02F1/42; {arrangements of air intake cleaners in gas turbine plants F02C7/05} ; arrangements or mounting of filters in air-conditioning, air-humidification or ventilation F24F13/28)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- F01N: GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES (arrangements in connection with gas exhaust of propulsion units in vehicles B60K13/00; combustion-air intake silencers specially adapted for, or arranged on, internal-combustion engines F02M35/00; protecting against, or damping, noise in general G10K11/16)

## Abstract

An as-synthesized microporous material having a CHA structure and containing at least one organic structure directing agent that has the following general structure of the quaternary ammonium cation is disclosed: A microporous crystalline material made from the as-synthesized material is also disclosed. A method of making microporous crystalline material using one or more organic structure directing agents is also disclosed. A method of selective catalytic reduction of nitrogen oxides in exhaust gas that comprises contacting exhaust gases, typically in the presence of ammonia, urea, an ammonia generating compound, or a hydrocarbon compound, with an article comprising the disclosed microporous crystalline is also disclosed.

## Claims

### Claim 1

An as-synthesized microporous material having a CHA structure and comprising a first organic structure directing agent (OSDA) that has a general structure of the quaternary ammonium cation as follows:
where R1 is a C1-C5 derivatized or underivatized alkyl chain, and
R2 is a C2-C5 derivatized or underivatized alkyl chain,
where X is H (hydrogen) or a C1-C3 alkyl substituent group or groups, derivatized or underivatized, attached to at least one carbon atom constituting the hexahydro-1H-azepinium ring.

### Claim 2 (depends on 1)

The as-synthesized microporous material of claim 1, which has a molar silica to alumina ratio (SAR) of about 10 or higher.

### Claim 3 (depends on 2)

The as-synthesized microporous material of claim 2, wherein the SAR ranges from 10 to 50.

### Claim 4 (depends on 1)

The as-synthesized microporous material of claim 1, further comprising at least one second OSDA, wherein the first OSDA and the second OSDA are a hydroxide or a salt chosen from fluoride, chloride, bromide, iodide, or a mixture of thereof.

### Claim 5 (depends on 4)

The as-synthesized microporous material of claim 4, wherein the second OSDA comprises a compound chosen from an amine, monoquaternary ammonium compound, or diquaternary ammonium compound, capable of forming a zeolite with chabazite (CHA) structure.

### Claim 6 (depends on 5)

The microporous crystalline material of claim 5, wherein the second OSDA is chosen from N,N,N-trimethyl-1-adamantylammonium, N,N-dimethyl-N-ethylcyclohexylammonium, N,N-dimethylpyrrolidinium, N,N-dimethylpiperidinium, N,N-dimethylhexahydroazepinium, benzyltrimethylammonium, and mixtures thereof.

### Claim 7 (depends on 1)

The as-synthesized microporous material of claim 1, wherein at least one of R1 and R2 is ethyl.

### Claim 8 (depends on 1)

The as-synthesized microporous material of claim 1, wherein the first OSDA comprises N,N-diethylhexahydro-1H-azepinium.

### Claim 9 (depends on 1)

A microporous crystalline material made by calcining and optionally ammonium-exchanging the as-synthesized microporous material of claim 1.

### Claim 10 (depends on 9)

The microporous crystalline material of claim 9, further comprising at least one catalytically active metal.

### Claim 11 (depends on 10)

The microporous crystalline material of claim 10, where the at least one catalytically active metal comprises copper or iron.

### Claim 12 (depends on 11)

The microporous crystalline material of claim 11, wherein the catalytically active metal comprises copper Cu, which is present as CuO in an amount of 1-10 wt % of the microporous crystalline material.

### Claim 13 (depends on 11)

The microporous crystalline material of claim 11, wherein the catalytically active metal comprises iron Fe, which is present as Fe2O3 in an amount of 0.2-10 wt % of the microporous crystalline material.

### Claim 14 (depends on 11)

A method of selective catalytic reduction of nitrogen oxides in exhaust gas, said method comprising contacting said exhaust gases with an article comprising a microporous crystalline material according to claim 11.

### Claim 15 (depends on 14)

The method of claim 14, where said contacting is performed in the presence of ammonia, urea, an ammonia generating compound, or a hydrocarbon compound.

### Claim 16

A method of synthesizing a microporous crystalline material having a CHA structure and comprising a first organic structure directing agent (OSDA) that has a general structure of the quaternary ammonium cation as follows:
where R1 is a C1-C5 derivatized or underivatized alkyl chain, and
R2 is a C2-C5 derivatized or underivatized alkyl chain,
where X is H (hydrogen) or a C1-C3 alkyl substituent group or groups, derivatized or underivatized, attached to at least one carbon atom constituting the hexahydro-1H-azepinium ring, the method comprising:
mixing sources of alumina, silica, one or more OSDAs, optionally alkali containing additive, water and optionally a seed material to form a gel; and
heating the gel in an autoclave to form a crystalline CHA product.

### Claim 17 (depends on 16)

The method of claim 16, wherein the microporous crystalline material has a molar silica to alumina ratio (SAR) of about 10 or higher.

### Claim 18 (depends on 17)

The method of claim 17, wherein the SAR ranges from 10 to 50.

### Claim 19 (depends on 16)

The method of claim 16, further comprising at least one second OSDA, wherein the first OSDA and the second OSDA are a hydroxide or a salt chosen from fluoride, chloride, bromide, iodide, or a mixture of thereof.

### Claim 20 (depends on 19)

The method of claim 19, wherein the second OSDA comprises a compound chosen from an amine, monoquaternary ammonium compound, or diquaternary ammonium compound, capable of forming a zeolite with chabazite (CHA) structure.

### Claim 21 (depends on 20)

The method of claim 20, wherein the second OSDA is chosen from N,N,N-trimethyl-1-adamantylammonium, N,N-dimethyl-N-ethylcyclohexylammonium, N,N-dimethylpyrrolidinium, N,N-dimethylpiperidinium, N,N-dimethylhexahydroazepinium, benzyltrimethylammonium, and mixtures thereof.

### Claim 22 (depends on 16)

The method of claim 16, wherein at least one of R1 and R2 is ethyl.

### Claim 23 (depends on 16)

The method of claim 16, wherein the first OSDA comprises N,N-diethylhexahydro-1H-azepinium.

### Claim 24 (depends on 16)

The method of claim 16, further comprising calcining said CHA product; and optionally ammonium-exchanging said CHA product.

### Claim 25 (depends on 24)

The method of claim 24, further comprising introducing at least one catalytically active metal into the microporous crystalline material by liquid-phase or solid-phase ion exchange, impregnation, direct synthesis or combinations thereof.

### Claim 26 (depends on 25)

The method of claim 25, where the at least one catalytically active metal comprises copper or iron.

### Claim 27 (depends on 26)

The method of claim 26, wherein the catalytically active metal comprises copper Cu, which is present as CuO in an amount of 1-10 wt % of the microporous crystalline material.

### Claim 28 (depends on 26)

The method of claim 26, wherein the catalytically active metal comprises iron Fe, which is present as Fe2O3 in an amount of 0.2-10 wt % of the microporous crystalline material.

### Claim 29 (depends on 16)

The method of claim 16, where the alkali containing additive comprises a source of potassium or sodium, or a mixture of thereof.