# US 11,111,152 B2 · Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst

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- Number: US 11,111,152 B2
- Document ID: US11111152B2
- Status: Granted
- Kind: B2
- Application number: 15/750,403
- Filed: 2016-08-04
- Published: 2018-08-09
- Granted: 2021-09-07
- Earliest claimed: 2015-08-05
- Assignees: PetroChina Company Limited
- Applicants: PetroChina Company Limited
- Inventors: Xionghou Gao; Shuhong Sun; Yunfeng Zheng; Xiaoliang Huang; Aiguo Lin; Xiaoyan Li; Lin Wang; Gengzhen Cao; Conghua Liu; Zhishuang Pan; Wei Ding; Yahong Wang; Dong Wang; Qiuxia Teng; Haitao Zhang
- Web page: https://patentgrep.com/patent/US11111152B2

## CPC

- C01B 39/24: Type Y {(C01B39/205 takes precedence)}
- B01J 29/084: {Y-type faujasite}
- B01J 29/088: {Y-type faujasite}
- B01J 29/146: {Y-type faujasite}
- B01J 29/405: {containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead}
- B01J 29/46: Iron group metals or copper
- B01J 37/0236: {Drying, e.g. preparing a suspension, adding a soluble salt and drying}
- B01J 37/031: {Precipitation}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- C01B 39/38: Type ZSM-5
- C10G 11/05: Crystalline alumino-silicates, e.g. molecular sieves
- B01J 2229/186: not in framework positions
- B01J 2229/42: Addition of matrix or binder particles
- C10G 2300/1033: Oil well production fluids
- C10G 2300/1048: Middle distillates
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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

## Abstract

A preparation method for modified molecular sieve and a modified molecular sieve-containing catalytic cracking catalyst. The preparation method comprises: mixing molecular sieve slurry, a compound solution containing ions of group IIIB metals of the periodic table of elements, organic complexing agent and/or dispersing agent and precipitating agent to obtain mixed slurry containing molecular sieve and precipitates of group IIIB elements in the periodic table of elements; and drying, and roasting or not roasting to obtain molecular sieve modified by the group IIIB elements. A weight ratio of group IIIB elements calculated based on oxides to molecular sieve dry basis is equal to (0.3-10):100, a molar ratio of organic complexing agent to ions of group IIIB metals is equal to (0.3-10):1, and a molar ratio of dispersing agent to the ions of group IIIB metals is equal to (0.2-16):1. Also related to is the catalytic cracking catalyst containing the modified molecular sieve prepared according to the method. The molecular sieve prepared by the method or the catalytic cracking catalyst containing same has good activity stability and heavy metal pollution resistance.

## Claims

### Claim 1

A preparation method of a modified molecular sieve, wherein the preparation method comprises: mixing a molecular sieve slurry, a compound solution containing Group IIIB metal ion of the periodic table, an organic complexing agent, a dispersant and a precipitating agent to obtain a mixed slurry containing the precipitate of Group IIIB element of the periodic table and the molecular sieve, followed by drying and optionally calcining, to obtain the Group IIIB element-modified molecular sieve, wherein the weight ratio of the Group IIIB element in terms of oxide to the molecular sieve on dry basis is 0.3 to 10: 100, the molar ratio of the organic complexing agent to the Group IIIB metal ion is 0.3 to 10: 1, and the molar ratio of the dispersant to the Group IIIB metal ion is 0.2 to 16: 1; wherein the mixing of the molecular sieve slurry, the compound solution containing the Group IIIB metal ion of the periodic table, the organic complexing agent, the dispersant and the precipitating agent is carried out by uniformly mixing the compound solution containing the Group IIIB metal ion of the periodic table, the organic complexing agent, the dispersant with the molecular sieve slurry, adding the precipitating agent and stirring for at least 10 minutes.

### Claim 2 (depends on 1)

The preparation method according to claim 1, wherein the preparation method comprises: mixing the molecular sieve slurry, the compound solution containing Group IIIB metal ion of the periodic table, the organic complexing agent, the dispersant and the precipitating agent at a temperature of 5 to 100° C. and stirring for at least 10 minutes to obtain the mixed slurry containing the precipitate of Group IIIB element of the periodic table and the molecular sieve, followed by drying and optionally calcining, to obtain the Group IIIB element-modified molecular sieve, wherein the weight ratio of the Group IIIB element in terms of oxide to the molecular sieve on dry basis is 0.3 to 10: 100, the molar ratio of the organic complexing agent to the Group IIIB metal ion is 0.3 to 10: 1, and the molar ratio of the dispersant to the Group IIIB metal ion is 0.2 to 16: 1.

### Claim 3 (depends on 2)

The preparation method according to claim 2, wherein the temperature is 5 to 60° C., and the stirring is carried out for 10 to 40 minutes to obtain the mixed slurry containing the precipitate of Group IIIB element of the periodic table and the molecular sieve.

### Claim 4 (depends on 2)

The preparation method according to claim 2, wherein the weight ratio of Group IIIB element in terms of oxide to the molecular sieve on dry basis is 0.3 to 8: 100.

### Claim 5 (depends on 2)

The preparation method according to claim 2, wherein the molar ratio of the organic complexing agent to the Group IIIB metal ion is 0.5 to 6: 1; the molar ratio of the dispersant to the Group IIIB metal ion is 1 to 11: 1.

### Claim 6 (depends on 2)

The preparation method according to claim 2, wherein the precipitating agent is a substance capable of chemically reacting with the Group IIIB metal ion in the system and making the product thereof slightly soluble or insoluble in the system, in a chemical precipitation reaction.

### Claim 7 (depends on 6)

The preparation method according to claim 6, wherein the precipitating agent is one or more of compounds capable of providing or generating hydroxide ions, carbonate ions, bicarbonate ions, phosphate ions, hydrogen phosphate ions, dihydrogen phosphate ions, or oxalate ions.

### Claim 8 (depends on 6)

The preparation method according to claim 6, wherein the precipitating agent is one or more of oxalic acid, ammonium oxalate, ammonium carbonate, ammonium bicarbonate, carbon dioxide, aqueous ammonia, phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate and urea.

### Claim 9 (depends on 2)

The preparation method according to claim 2, wherein the organic complexing agent is selected from one or more of formic acid, acetic acid, adipic acid, citric acid, tartaric acid, benzoic acid, ethylenediamine tetraacetic acid, salicylic acid and salts thereof, acetylacetone, diethanolamine, and triethanolamine.

### Claim 10 (depends on 2)

The preparation method according to claim 2, wherein the dispersant is a surfactant having both lipophilic and hydrophilic properties in the molecule, which can uniformly disperse solid particles that are insoluble in the liquid while preventing the sedimentation and agglomeration of the solid particles, and form a material needed for stabilizing the suspension, and the dispersant does not form precipitates with the Group IIIB metal ion.

### Claim 11 (depends on 10)

The preparation method according to claim 10, wherein the dispersant is selected from one or more of monohydric or dihydric alcohol having 2 to 8 carbon atoms, polyethylene glycol, cellulose derivative, polyacrylamide and derivatives thereof, and guar gum.

### Claim 12 (depends on 11)

The preparation method according to claim 11, wherein the cellulose derivative is one or more of carboxymethylcellulose sodium, methyl hydroxyethyl cellulose, and hydroxypropyl methyl cellulose; and the monohydric or dihydric alcohol having 2 to 8 carbon atoms is one or more of ethanol, ethylene glycol, isopropanol, butanol, and methylpentanol.

### Claim 13 (depends on 2)

The preparation method according to claim 2, wherein the condition for the calcination process is: calcining the molecular sieve in an atmosphere of 100% steam at a calcination temperature of 450-700° C. for a calcination time of 0.5 to 4 hours.

### Claim 14 (depends on 2)

The preparation method according to claim 2, wherein the molecular sieve slurry is a sodium-reduced molecular sieve slurry.

### Claim 15 (depends on 9)

The preparation method according to claim 9, wherein the organic complexing agent is selected from one or more of citric acid, ammonium citrate, ammonium dihydrogen citrate, diammonium hydrogen citrate, and ethylenediamine tetraacetic acid.