Sphere-like super-macroporous mesoporous material and polyolefin catalyst containing same

Patent metadata

Field	Value
Publication number	US-12528890-B2
Application number	US-202018000716-A
Country	US
Kind code	B2
Filing date	Oct 30, 2020
Priority date	Jun 5, 2020
Publication date	Jan 20, 2026
Grant date	Jan 20, 2026

Abstract

Disclosed are a sphere-like super-macroporous mesoporous material, a polyolefin catalyst, and a preparation method therefor and an olefin polymerization process. The sphere-like super-macroporous mesoporous material has a two-dimensional hexagonal ordered pore channel structure. The mesoporous material has an average pore size of 10 nm to 15 nm, a specific surface area of 300 m 2 /g to 400 m 2 /g, and an average particle size of 1 μm to 3 μm, based on the total mass of the mesoporous material. The mass content of water in the mesoporous material is <1 ppm. The mass content of oxygen in the mesoporous material is <1 ppm. When a polyolefin catalyst prepared with the mesoporous material as a carrier is used for an olefin polymerization reaction, a polyolefin product with a narrow molecular weight distribution and a good melt index can be obtained.

First claim

We claim:

1 . A mesoporous silica material, which comprises a two-dimensional hexagonal ordered channel structure, wherein the mesoporous silica material has an average pore diameter of from 10 nm to 15 nm, a specific surface area of from 300 m 2 /g to 400 m 2 /g, and an average particle size of from 1 μm to 3 μm; the mass content of water in the mesoporous silica material is less than 1 ppm, and a mass content of oxygen gas in the mesoporous silica material is less than 1 ppm, based on the total mass of the mesoporous silica material.

2 . The mesoporous silica material as claimed in claim 1 , having at least one of the following features:
the mesoporous silica material has a water contact angle of 101° to 130°; the mesoporous silica material has a crushing strength of 0.001 N/cm to 0.6 N/cm; the mesoporous silica material has a pore volume of 1 mL/g to 2 mL/g, the mesoporous silica material has a particle size distribution of 0.01 to 3.

3 . The mesoporous silica material as claimed in claim 1 , wherein the mesoporous silica material is obtained by treatment with a chlorine-containing silane.

4 . The mesoporous silica material as claimed in claim 3 , wherein the chlorine-containing silane is at least one selected from the group consisting of dichlorodimethoxysilane, monochlorotrimethoxysilane, dichlorodiethoxysilane, and monochlorotriethoxysilane.

5 . The mesoporous silica material as claimed in claim 1 , wherein the mesoporous silica material has an average pore diameter of from 11 nm to 13 nm, a specific surface area of from 310 m 2 /g to 380 m 2 /g, and an average particle size of from 1.1 μm to 2.9 μm.

6 . A method for preparing a mesoporous silica material, comprising:
(1) mixing and contacting a silicon source, an acid agent, ammonium fluoride and heptane in the presence of a template agent and water, and subjecting the mixture resulting from the mixing and contacting in sequence to crystallization, filtering and drying, to obtain a raw powder of the mesoporous silica material; and (2) subjecting the raw powder of the mesoporous silica material in sequence to a template agent-removing treatment, a primary thermal activation treatment and a secondary thermal activation treatment, to obtain the mesoporous silica material.

7 . The method as claimed in claim 6 , having at least one of the following features:
in step (2), conditions for the primary thermal activation treatment include: in an inert atmosphere, a treatment temperature of from 250° C. to 900° C., and a treatment time of from 1 to 48 hours; in step (2), conditions for the secondary thermal activation treatment include: in an inert atmosphere, a treatment temperature of from 250° C. to 900° C., and a treatment time of from 1 to 48 hours; and in step (2), the conditions for the primary thermal activation treatment are the same as conditions for the secondary thermal activation treatment.

8 . The method as claimed in claim 7 , wherein in step (2), the conditions for the primary thermal activation treatment include: in an inert atmosphere, a treatment temperature of from 250° C. to 700° C., and a treatment time of from 4 to 48 hours; and/or in step (2), the conditions for the secondary thermal activation treatment include: in an inert atmosphere, a treatment temperature of 250° C. to 700° C., and a treatment time of from 4 to 48 hours.

9 . The method as claimed in claim 6 , having at least one of the following features:
in step (1), the mixing and contacting are carried out as follows: the silicon source, the acid agent, the ammonium fluoride and the heptane are stirred in the presence of the template agent and water at a temperature of 25° C. to 60° C. for a period of time of 4 minutes or more, and then the resulting mixture is left stand still for 1 hour or more; in step (1), the acid agent is at least one of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid; in step (1), the silicon source is at least one of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol; a molar ratio of the template agent to the silicon source to the acid agent to the ammonium fluoride to the heptane is 1:2 to 500:100 to 2000:0.7 to 200:20 to 1650; the template agent is a triblock copolymer of polyoxyethylene-polyoxypropylene-polyoxyethylene (EO 2 PO 70 EO 20 ); the conditions for the crystallization include a crystallization temperature of 90° C. to 180° C. and a crystallization time of 10 h to 40 h; and in step (2), the template agent-removing treatment includes washing the raw powder of the mesoporous silica material with an alcohol at 90 to 120° C. for 10 to 40 hours.

10 . The method as claimed in claim 6 , wherein the method further comprises, step b) mixing a thermally activated mesoporous silica material from step b) with a chlorine-containing silane.

11 . The method as claimed in claim 10 , wherein the chlorine-containing silane is at least one selected from the group consisting of dichlorodimethoxysilane, monochlorotrimethoxysilane, dichlorodiethoxysilane, and monochlorotriethoxysilane.

12 . The method as claimed in claim 6 , wherein the method does not comprise a grinding step after the thermal activation treatment.

13 . The mesoporous silica material as claimed in claim 1 , wherein the mass content of water in the mesoporous silica material is less than 0.5 ppm, and the mass content of oxygen gas in the mesoporous silica material is less than 0.5 ppm, based on the total mass of the mesoporous silica material.

14 . A polyolefin catalyst comprising a magnesium component and a titanium component and an optional supported on a carrier, wherein the carrier comprises the mesoporous silica material as claimed in claim 1 .

15 . The polyolefin catalyst as claimed in claim 14 , having at least one of the following features:
the content of the carrier is from 20 wt. % to 90 wt. %, based on the total weight of the polyolefin catalyst; the content of the magnesium component in terms of magnesium element is from 1 wt. % to 50 wt. %, based on the total weight of the polyolefin catalyst; the content of the titanium component in terms of titanium element is from 1 wt. % to 50 wt. %, based on the total weight of the polyolefin catalyst; the polyolefin catalyst has a pore volume of from 0.5 mL/g to 1 mL/g; the polyolefin catalyst has a specific surface area of from 120 m 2 /g to 300 m 2 /g; the polyolefin catalyst has a most probable pore diameter of from 7 nm to 12 nm; the polyolefin catalyst has an average particle size of from 3 μm to 25 μm; and the polyolefin catalyst has a particle size distribution value of from 0.85 to 0.95.

16 . The polyolefin catalyst as claimed in claim 15 , having at least one of the following features:
the content of the carrier is from 30 wt. % to 70 wt. %, based on the total weight of the polyolefin catalyst; the content of the magnesium component in terms of magnesium element is from 1 wt. % to 30 wt. %, based on the total weight of the polyolefin catalyst; and the content of the titanium component in terms of titanium element is from 1 wt. % to 30 wt. %, based on the total weight of the polyolefin catalyst.

17 . A method for preparing the polyolefin catalyst as claimed in claim 14 , comprising:
(i) under an inert atmosphere, (ia) conducting impregnation treatment of the mesoporous silica material with a solution containing a magnesium component and then with a solution containing a titanium component, (ib) conducting impregnation treatment of the mesoporous silica material with a solutio

Assignees

• China Petroleum & Chem Corp
• Beijing Res Inst Chemical Ind China Petroleum & Chemical Corp

Inventors

• Kang Yu
• Lyu Xinping
• Liu Dongbing
• Guo Zifang
• Liu Hongmei
• Li Bingyi
• Wang Ruen

Classifications

• B01J35/40

  characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77) · CPC title

• B01J35/51

  Spheres · CPC title

• C08F2410/04

  Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene · CPC title

• C08F4/605

  Component covered by group C08F4/60 with a metal or compound covered by group C08F4/44, not provided for in a single group of groups C08F4/602 or C08F4/603 {(C08F4/60003 - C08F4/60196 take precedence)} · CPC title

• C08F2410/06

  Catalyst characterized by its size · CPC title