# US 2014/0154175 A1 · Stabilized microporous crystalline material, the method of making the same, and the use for selective catalytic reduction of nox

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- Number: US 2014/0154175 A1
- Document ID: US20140154175A1
- Status: Published application
- Kind: A1
- Application number: 13/691,710
- Filed: 2012-11-30
- Published: 2014-06-05
- Earliest claimed: 2012-11-30
- Assignees: PQ Corporation
- Applicants: Pq Corporation
- Inventors: Hong-Xin LI; Bjorn MODEN; William E. CORMIER
- Web page: https://patentgrep.com/patent/US20140154175A1

## CPC

- B01J 29/85: Silicoaluminophosphates [SAPO compounds]
- B01D 53/56: Nitrogen oxides (B01D53/60 takes precedence)
- B01D 53/9418: {for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas}
- B01J 29/763: {CHA-type, e.g. Chabazite, LZ-218}
- B01J 35/615: {100-500 m2/g}
- B01J 35/617: {500-1000 m2/g}
- B01D 2251/2062: Ammonia
- B01D 2251/2067: Urea
- B01D 2255/2022: Potassium
- B01D 2255/204: Alkaline earth metals
- B01D 2255/2045: Calcium
- B01D 2255/2063: Lanthanum
- B01D 2255/20738: Iron
- B01D 2255/20761: Copper
- B01D 2255/50: Zeolites
- B01D 2255/92: Dimensions
- B01J 37/30: Ion-exchange
- B01J 2229/183: in framework positions
- B01J 2229/186: not in framework positions
- B01J 2229/36: Steaming
- B01J 2229/40: Special temperature treatment, i.e. other than just for template removal
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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)

## Abstract

There is disclosed a microporous crystalline material having pore opening ranging from 3 to 5 Angstroms, where the material comprises a first metal chosen from alkali earth group, rare earth group, alkali group, or mixtures thereof, and a second metal chosen from iron, copper or mixtures thereof; and has a molar silica to alumina ratio (SAR) from 3 to 10. The microporous crystalline material disclosed herein may comprise a crystal structure having building units of double-6-rings (d6r) and pore opening of 8-rings as exemplified with framework types defined by the Structure Commission of the International Zeolite Association having structural codes of CHA, LEV, AEI, AFT, AFX, EAB, ERI, KFI, SAT, TSC, and SAV. There is also disclosed a method of selective catalytic reduction of nitrogen oxides in exhaust gas, comprising at least partially contacting the exhaust gases with an article comprising the disclosed microporous crystalline material.

## Claims

### Claim 1

A microporous crystalline silicoaluminophosphate (SAPO) material, where said material has a pore opening ranging from 3 to 5 Angstroms and comprises an alkali-earth metal or a rare-earth metal or an alkali metal or mixtures thereof, and copper.

### Claim 2 (depends on 1)

The microporous crystalline material of claim 1, where said material comprises a crystal structure having building units of double-6-rings (d6r) and pore opening of 8-rings.

### Claim 3 (depends on 2)

The microporous crystalline material of claim 2, wherein said crystal structure comprises structural codes of CHA, LEV, AEI, AFT, AFX, EAB, ERI, KFI, SAT, TSC, and SAV.

### Claim 4 (depends on 1)

The microporous crystalline material of claim 1, where said material comprises SAPO-34 or a CHA structure.

### Claim 5 (depends on 1)

The microporous crystalline material of claim 1, where said material comprises SiO2 in an amount ranging from 1 to 20 weight percent of the total weight of said material.

### Claim 6 (depends on 1)

The microporous crystalline material of claim 1, where the alkali-earth metal or rare-earth metal or alkali metal is selected from magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, mixed rare earth oxides, potassium, rubidium, cesium or mixtures thereof.

### Claim 7 (depends on 1)

The microporous crystalline material of claim 1, where said alkali-earth or rare-earth metal or alkali metal comprises an amount of at least 0.2 weight percent of the total weight of said material.

### Claim 8 (depends on 1)

The microporous crystalline material of claim 1, where said metals are introduced by liquid-phase or solid-phase ion exchange, impregnation or incorporated by direct synthesis or combinations thereof.

### Claim 9 (depends on 1)

The microporous crystalline material of claim 1, where said alkali-earth metal comprises calcium in an amount ranging from 0.2 to 5.0 weight percent of the total weight of said material.

### Claim 10 (depends on 1)

The microporous crystalline material of claim 1, where said copper comprises an amount ranging from 0.5 to 10.0 weight percent of the total weight of said material.

### Claim 11 (depends on 1)

The microporous crystalline material of claim 1, where said material comprises a mean crystal size ranging from 0.3 to 10 microns.

### Claim 12 (depends on 1)

The microporous crystalline material of claim 1, where said material retains at least 40% of its surface area and micropore volume after heating in water slurry at 105° C. for 24 hours.

### Claim 13

A method of selective catalytic reduction of nitrogen oxides in exhaust gas, said method comprising:
at least partially contacting said exhaust gases with an article comprising a microporous crystalline silicoaluminophosphate (SAPO) material having a pore opening ranging from 3 to 5 Angstroms and comprising an alkali-earth metal or a rare-earth metal or an alkali metal or mixtures thereof, and copper.

### Claim 14 (depends on 13)

The method of claim 13, where said contacting step is performed in the presence of ammonia, urea, an ammonia generating compound, or a hydrocarbon compound.

### Claim 15 (depends on 13)

The method of claim 13, where said material comprises a crystal structure having building units of double-6-rings (d6r) and pore opening of 8-rings.

### Claim 16 (depends on 15)

The method of claim 15, wherein said crystal structure comprises structural codes of CHA, LEV, AEI, AFT, AFX, EAB, ERI, KFI, SAT, TSC, and SAV.

### Claim 17 (depends on 13)

The method of claim 13, where said material comprises SAPO-34 or a CHA structure.

### Claim 18 (depends on 13)

The method of claim 13, where said material comprises SiO2 in an amount ranging from 1 to 20 weight percent of the total weight of said material.

### Claim 19 (depends on 13)

The method of claim 13, where the alkali-earth metal or rare-earth metal or alkali metal is selected from magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, mixed rare earth oxides, potassium, rubidium, cesium or mixtures thereof.

### Claim 20 (depends on 13)

The method of claim 13, where said alkali-earth or rare-earth metal or alkali metal comprises an amount of at least 0.2 weight percent of the total weight of said material.

### Claim 21 (depends on 13)

The method of claim 13, where said metals are introduced by liquid-phase or solid-phase ion exchange, impregnation or incorporated by direct synthesis or combinations thereof.

### Claim 22 (depends on 13)

The method of claim 13, where said alkali-earth metal comprises calcium in an amount ranging from 0.2 to 5.0 weight percent of the total weight of said material.

### Claim 23 (depends on 13)

The method of claim 13, where said copper comprises an amount ranging from 0.5 to 10.0 weight percent of the total weight of said material.

### Claim 24 (depends on 13)

The method of claim 13, where said material comprises a mean crystal size ranging from 0.3 to 10 microns.

### Claim 25 (depends on 13)

The method of claim 13, where said material retains at least 40% of its surface area and micropore volume after heating in water slurry at 105° C. for 24 hours.

### Claim 26

A method of making a microporous crystalline silicoaluminophosphate (SAPO) material having a pore opening ranging from 3 to 5 Angstroms and comprising an alkali-earth metal or a rare-earth metal or an alkali metal or mixtures thereof, and copper, said method comprising:
mixing sources of alumina, silica, phosphate, at least one organic structural directing agent, optionally an alkali-earth metal salt or rare-earth metal salt, and water to form a gel;
heating said gel in an autoclave at a temperature ranging from 140 to 220° C. to form a crystalline SAPO product;
calcining said product; and
introducing an alkali-earth metal or a rare-earth metal or an alkali metal or mixtures thereof and copper by liquid-phase or solid-phase ion exchange, impregnation or incorporated by direct synthesis or combinations thereof.

### Claim 27 (depends on 26)

The method of claim 26, where said material comprises a crystal structure having building units of double-6-rings (d6r) and pore opening of 8-rings.

### Claim 28 (depends on 27)

The method of claim 27, wherein said crystal structure comprises structural codes of CHA, LEV, AEI, AFT, AFX, EAB, ERI, KFI, SAT, TSC, and SAV.

### Claim 29 (depends on 26)

The method of claim 26, where said material comprises SAPO-34 or a CHA structure.

### Claim 30 (depends on 26)

The method of claim 26, where said material comprises SiO2 in an amount ranging from 1 to 20 weight percent of the total weight of said material.

### Claim 31 (depends on 26)

The method of claim 26, where the alkali-earth metal or rare-earth metal or alkali metal is selected from magnesium, calcium, strontium, barium, lanthanum, cerium, praseodymium, neodymium, mixed rare earth oxides, potassium, rubidium, cesium or mixtures thereof.

### Claim 32 (depends on 26)

The method of claim 26, where said alkali-earth or rare-earth metal or alkali metal comprises an amount of at least 0.2 weight percent of the total weight of said material.

### Claim 33 (depends on 26)

The method of claim 26, where said metals are introduced by liquid-phase or solid-phase ion exchange, impregnation or incorporated by direct synthesis or combinations thereof.

### Claim 34 (depends on 26)

The method of claim 26, where said alkali-earth metal comprises calcium in an amount ranging from 0.2 to 5.0 weight percent of the total weight of said material.

### Claim 35 (depends on 26)

The method of claim 26, where said copper comprises an amount ranging from 0.5 to 10.0 weight percent of the total weight of said material.

### Claim 36 (depends on 26)

The method of claim 26, where said material comprises a mean crystal size ranging from 0.3 to 10 microns.

### Claim 37 (depends on 26)

The method of claim 26, where said material retains at least 40% of its surface area and micropore volume after heating in water slurry at 105° C. for 24 hours.