# US 2019/0375646 A1 · Magnesium Modified Y-Type Molecular Sieve, Preparation Thereof and Catalyst Comprising the Same

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- Number: US 2019/0375646 A1
- Document ID: US20190375646A1
- Status: Published application
- Kind: A1
- Application number: 16/484,880
- Filed: 2018-02-12
- Published: 2019-12-12
- Earliest claimed: 2017-02-21
- Assignees: China Petroleum & Chemical Corporation; Research Institute of Petroleum Processing, Sinopec
- Applicants: China Petroleum & Chemical Corporation; Research Institute of Petroleum Processing, Sinopec
- Inventors: Lingping ZHOU; Weilin ZHANG; Mingde XU; Zhenyu CHEN; Huiping TIAN; Yuxia ZHU
- Web page: https://patentgrep.com/patent/US20190375646A1

## CPC

- C01B 39/24: Type Y {(C01B39/205 takes precedence)}
- B01J 29/005: {Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89}
- B01J 29/084: {Y-type faujasite}
- B01J 29/088: {Y-type faujasite}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 35/647: {2-50 nm}
- B01J 35/651: {50-500 nm}
- B01J 37/30: Ion-exchange
- C01B 39/023: {Preparation of physical mixtures or intergrowth products of zeolites chosen from group C01B39/04 or two or more of groups C01B39/14 - C01B39/48}
- C10G 11/05: Crystalline alumino-silicates, e.g. molecular sieves
- B01J 21/04: Alumina
- B01J 23/02: of the alkali- or alkaline earth metals or beryllium
- B01J 2229/16: to increase the Si/Al ratio; Dealumination
- B01J 2229/18: to introduce other elements into or onto the molecular sieve itself
- B01J 2229/183: in framework positions
- B01J 2229/186: not in framework positions
- B01J 2229/24: to stabilize the molecular sieve structure
- B01J 2229/32: Reaction with silicon compounds, e.g. TEOS, siliconfluoride
- B01J 2229/36: Steaming
- B01J 2229/42: Addition of matrix or binder particles
- C01P 2006/14: Pore volume
- C01P 2006/17: Pore diameter distribution
- C01P 2006/37: Stability against thermal decomposition
- 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
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

A magnesium modified Y-type molecular sieve has a rare earth oxide content of about 4% to about 11% by weight, a magnesium oxide content of about 0.1% to about 4% by weight, a sodium oxide content of about 0.3% to about 0.8% by weight, a total pore volume of about 0.33 mL/g to about 0.39 mL/g, a percentage of the pore volume of secondary pores having a pore size of 2-100 nm to the total pore volume of the modified Y-type molecular sieve of about 10% to about 30%, a lattice constant of about 2.440 nm to about 2.455 nm, a percentage of non-framework aluminum content to the total aluminum content of the modified Y-type molecular sieve of no more than about 20%, and a lattice collapse temperature of not lower than about 1045° C.

## Claims

### Claim 1

A magnesium modified Y-type molecular sieve, having a rare earth oxide content of about 4% to about 11% by weight, a magnesium oxide content of about 0.1% to about 4% by weight, a sodium oxide content of about 0.3% to about 0.8% by weight, a total pore volume of about 0.33 mL/g to about 0.39 mL/g, a percentage of the pore volume of secondary pores having a pore size of 2-100 nm to the total pore volume of the modified Y-type molecular sieve of about 10% to about 30%, a lattice constant of about 2.440 nm to about 2.455 nm, a percentage of non-framework aluminum content to the total aluminum content of the modified Y-type molecular sieve of no more than about 20%, and a lattice collapse temperature of not lower than about 1045° C.

### Claim 2 (depends on 1)

The modified Y-type molecular sieve according to claim 1, wherein the modified Y-type molecular sieve has a percentage of the pore volume of secondary pores having a pore size of 2-100 nm to the total pore volume of about 15-25%.

### Claim 3 (depends on 1)

The modified Y-type molecular sieve according to claim 1, wherein the modified Y-type molecular sieve has a percentage of non-framework aluminum content to the total aluminum content of about 13-19%, and a framework silica-alumina ratio of about 7 to about 14 calculated on the basis of SiO2/Al2O3 molar ratio.

### Claim 4 (depends on 1)

The modified Y-type molecular sieve according to claim 1, wherein the modified Y-type molecular sieve has a lattice collapse temperature of about 1045-1075° C.

### Claim 5 (depends on 1)

The modified Y-type molecular sieve according to claim 1, wherein the magnesium oxide content is from about 0.5% to about 3% by weight.

### Claim 6 (depends on 1)

The modified Y-type molecular sieve according to claim 1, wherein the modified Y-type molecular sieve shows a relative crystallinity retention of about 30% or more after aging at 800° C. under atmospheric pressure in 100% steam atmosphere for 17 hours.

### Claim 7 (depends on 1)

The modified Y-type molecular sieve according to claim 1, wherein the modified Y-type molecular sieve has a relative crystallinity of about 55% to about 68%.

### Claim 8 (depends on 1)

The modified Y-type molecular sieve according to claim 1, wherein the modified Y-type molecular sieve has a rare earth oxide content of about 4.5% to about 10% by weight, a sodium oxide content of about 0.4% to about 0.6% by weight, a lattice constant of 2.442-2.451 nm, and a framework silica-alumina ratio of about 8.5 to about 12.6 calculated on the basis of SiO2/Al2O3 molar ratio.

### Claim 9 (depends on 1)

A method for the preparation of a magnesium modified Y-type molecular sieve according to claim 1, comprising the steps of:
(1) contacting a NaY molecular sieve with a rare earth salt solution for ion-exchange reaction, to obtain a rare earth modified Y-type molecular sieve having a reduced sodium oxide content;
(2) subjecting the Y-type molecular sieve obtained in the step (1) to roasting at a temperature of about 350-480° C. in an atmosphere containing about 30 vol % to about 90 vol % of steam for about 4.5 hours to about 7 hours, to obtain a Y-type molecular sieve having a reduced lattice constant;
(3) contacting and reacting the Y-type molecular sieve obtained in the step (2) with gaseous silicon tetrachloride to obtain a high-silica ultra-stable Y-type molecular sieve under the following conditions: a weight ratio of SiCl4:the Y-type molecular sieve on a dry basis of about 0.1:1 to about 0.7:1, a reaction temperature of about 200° C. to about 650° C., and a reaction time of about 10 minutes to about 5 hours; and
(4) subjecting the high-silica ultra-stable Y-type molecular sieve obtained in the step (3) to modification with a magnesium compound, to obtain the magnesium modified Y-type molecular sieve.

### Claim 10 (depends on 9)

The method according to claim 9, wherein the rare earth modified Y-type molecular sieve having a reduced sodium oxide content obtained in the step (1) has a lattice constant of about 2.465-2.472 nm, and a sodium oxide content of no more than about 9.5 wt %.

### Claim 11 (depends on 9)

The method according to claim 9, wherein the rare earth modified Y-type molecular sieve having a reduced sodium oxide content obtained in the step (1) has a rare earth content of about 4.5% to about 13% by weight on the basis of RE2O3, a sodium oxide content of about 5-9.5% by weight and a lattice constant of about 2.465-2.472 nm.

### Claim 12 (depends on 9)

The method according to claim 9, wherein, in the step (1), the ion-exchange reaction of the NaY molecular sieve with the rare earth solution is carried out under the following conditions: a weight ratio of NaY molecular sieve:rare earth salt:H2O of about 1:0.01-0.18:5-15, an ion-exchange temperature of about 15-95° C., and an ion-exchange time of about 30-120 minutes.

### Claim 13 (depends on 9)

The method according to claim 9, wherein, in the step (2), the roasting temperature is about 380-460° C., the roasting atmosphere is an atmosphere containing about 40-80% steam, and the roasting time is about 5-6 hours.

### Claim 14 (depends on 9)

The method according to claim 9, wherein the Y-type molecular sieve having a reduced lattice constant obtained in the step (2) has a lattice constant of about 2.450-2.462 nm, and a water content of no more than about 1% by weight.

### Claim 15 (depends on 9)

The method according to claim 9, wherein the rare earth salt is rare earth chloride and/or rare earth nitrate; the magnesium compound is magnesium chloride and/or magnesium nitrate.

### Claim 16 (depends on 9)

The method according to claim 9, wherein the modification with the magnesium compound of the step (4) comprises: adding the molecular sieve to a solution containing a magnesium salt at a weight ratio of water to the molecular sieve of about 1-6, a weight ratio of the magnesium salt on the basis magnesium oxide to the molecular sieve of about 0.001-0.04; stirring at about 5-50° C. for about 10-120 minutes, adding ammonia water to adjust the pH of the solution to about 7.5-10, then filtering and subject the filter cake to roasting at about 500-650° C. for at least about 1 hour, to obtain the magnesium modified Y-type molecular sieve.

### Claim 17 (depends on 1)

A catalytic cracking catalyst, comprising a modified Y-type molecular sieve according to claim 1.

### Claim 18 (depends on 17)

The catalytic cracking catalyst according to claim 17, wherein the catalyst comprises about 10% to about 50% by weight, on a dry basis, of the modified Y-type molecular sieve, about 10% to about 40% by weight on the basis of alumina of an alumina binder, and about 10% to about 80% by weight, on a dry basis, of clay.

### Claim 19 (depends on 17)

The catalytic cracking catalyst according to claim 17, wherein the catalyst comprises about 10% to about 50% by weight, on a dry basis, of the modified Y-type molecular sieve, about 2% to about 40% by weight on a dry basis of an additive-containing alumina and about 10% to about 80% by weight, on a dry basis, of clay; wherein on a dry basis and based on the weight of the additive-containing alumina, the additive-containing alumina comprises about 60% to about 99.5% by weight of alumina and about 0.5% to about 40% by weight of an additive, wherein the additive is one or more selected from the group consisting of compounds containing alkaline earth metal, lanthanide metal, silicon, gallium, boron, and/or phosphorus.

### Claim 20 (depends on 19)

The catalytic cracking catalyst according to claim 19, wherein the catalyst comprises about 25-40% by weight, on a dry basis, of the modified Y-type molecular sieve, about 2-20% by weight on a dry basis of an additive-containing alumina, about 5-30% by weight on a dry basis of an alumina binder, and about 30-50% by weight on a dry basis of clay.