# US 11,027,264 B2 · Fluid catalytic cracking catalysts for increasing butylene yields

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- Number: US 11,027,264 B2
- Document ID: US11027264B2
- Status: Granted
- Kind: B2
- Application number: 16/701,371
- Filed: 2019-12-03
- Published: 2020-04-02
- Granted: 2021-06-08
- Earliest claimed: 2015-11-24
- Assignees: BASF SE
- Applicants: BASF Corporation
- Inventors: Karl C. Kharas
- Web page: https://patentgrep.com/patent/US11027264B2

## CPC

- B01J 29/084: {Y-type faujasite}
- B01J 29/088: {Y-type faujasite}
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/51: Spheres
- B01J 37/0246: {Coatings comprising a zeolite}
- B01J 37/10: in the presence of water, e.g. steam
- B01J 37/30: Ion-exchange
- C01B 39/02: Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B 39/54: Phosphates, e.g. APO or SAPO compounds
- C10G 11/05: Crystalline alumino-silicates, e.g. molecular sieves
- C10G 11/18: according to the "fluidised-bed" technique
- B01J 23/02: of the alkali- or alkaline earth metals or beryllium
- B01J 35/70: characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00)
- B01J 37/0201: {Impregnation}
- B01J 2229/186: not in framework positions
- B01J 2229/20: to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
- B01J 2229/36: Steaming
- B01J 2229/37: Acid treatment
- B01J 2229/64: in or on refractory materials
- B01J 2235/15: X-ray diffraction
- C07C 2529/08: of the faujasite type, e.g. type X or Y
- C07C 2529/85: Silicoaluminophosphates (SAPO compounds)
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

A microspherical fluid catalytic cracking catalyst includes zeolite, and alkali metal ion or alkaline earth metal ion.

## Claims

### Claim 1

A method of making a microspherical fluid catalytic cracking catalyst, the method comprising:
mixing microspheres with a barium solution to form a barium-microsphere mixture; and
calcining the barium-microsphere mixture to form a first calcined material;
wherein:
prior to the mixing with the barium solution, the microspheres comprise Y-zeolite crystallized as a layer on the surface of a porous alumina-containing matrix; and
the mixing with the barium solution is conducted at acidic pH conditions.

### Claim 2 (depends on 1)

The method of claim 1, wherein the mixing with the barium solution is conducted at pH=3.

### Claim 3 (depends on 1)

The method of claim 1, wherein the mixing with the barium solution is conducted at a temperature above room temperature.

### Claim 4 (depends on 1)

The method of claim 1, wherein calcining the barium-microsphere mixture is conducted for at least about 15 minutes.

### Claim 5 (depends on 1)

The method of claim 1, wherein calcining the barium-microsphere mixture is conducted at a temperature of from about 500° C. to about 700° C.

### Claim 6 (depends on 1)

The method of claim 1, further comprising mixing the microspheres with an ammonium solution prior to the mixing with the barium solution, wherein the microspheres comprise Y-zeolite in the sodium form prior to the mixing with the ammonium solution.

### Claim 7 (depends on 6)

The method of claim 6, wherein the mixing with the ammonium solution is conducted at acidic pH conditions.

### Claim 8 (depends on 6)

The method of claim 6, wherein the mixing with the ammonium solution is conducted at pH=3.

### Claim 9 (depends on 6)

The method of claim 6, wherein the mixing with the ammonium solution is conducted at a temperature above room temperature.

### Claim 10 (depends on 1)

The method of claim 1, further comprising mixing the first calcined material with another ammonium solution to form an ammoniated material.

### Claim 11 (depends on 10)

The method of claim 10, wherein the mixing with another ammonium solution is conducted at acidic pH conditions.

### Claim 12 (depends on 10)

The method of claim 10, wherein the mixing with another ammonium solution is conducted at pH=3.

### Claim 13 (depends on 10)

The method of claim 10, wherein the mixing with another ammonium solution is conducted at a temperature above room temperature.

### Claim 14 (depends on 10)

The method of claim 10, further comprising calcining the ammoniated material to form a second calcined material.

### Claim 15 (depends on 14)

The method of claim 14, wherein calcining the ammoniated material is conducted for at least about 15 minutes.

### Claim 16 (depends on 14)

The method of claim 14, wherein calcining the ammoniated material is conducted at a temperature of from about 500° C. to about 700° C.

### Claim 17 (depends on 1)

The method of claim 1, further comprising steam-treating.

### Claim 18 (depends on 17)

The method of claim 17, wherein the steam-treating is conducted at a temperature of at least about 600° C.

### Claim 19 (depends on 17)

The method of claim 17, wherein the steam-treating is conducted for at least about two hours.

### Claim 20 (depends on 17)

The method of claim 17, wherein the steam-treating is conducted in a fluidized bed reactor.

### Claim 21 (depends on 1)

The method of claim 1, wherein the microspherical fluid catalytic cracking catalyst comprises Y-zeolite comprising a Y-zeolite unit cell having an ion exchange site III, and the Y-zeolite unit cell comprises barium ion at the ion exchange site III.