	US 11,964,262 B2
	Phosphorus-containing rare-earth-containing MFI structure molecular sieve rich in mesopore, preparation method, and catalyst containing same and application thereof
Ying Ouyang, Beijing (CN); Yibin Luo, Beijing (CN); Jianqiang Liu, Beijing (CN); Li Zhuang, Beijing (CN); Minggang Li, Beijing (CN); and Xingtian Shu, Beijing (CN)
Assigned to CHINA PETROLEUM & CHEMICAL CORPORATION, Bejing (CN); and RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC, Beijing (CN)
Appl. No. 17/286,758
Filed by CHINA PETROLEUM & CHEMICAL CORPORATION, Beijing (CN); and RESEARCH INSTITUTE OF PETROLEUM PROCESSING, SINOPEC, Beijing (CN)
PCT Filed Oct. 17, 2019, PCT No. PCT/CN2019/111740 § 371(c)(1), (2) Date Apr. 19, 2021, PCT Pub. No. WO2020/078437, PCT Pub. Date Apr. 23, 2020.
Claims priority of application No. 201811217720.8 (CN), filed on Oct. 18, 2018; application No. 201910123049.9 (CN), filed on Feb. 19, 2019; application No. 201910578658.3 (CN), filed on Jun. 28, 2019; and application No. 201910580180.8 (CN), filed on Jun. 28, 2019.
Prior Publication US 2021/0387171 A1, Dec. 16, 2021
This patent is subject to a terminal disclaimer.
Int. Cl. B01J 29/064 (2006.01); B01J 29/035 (2006.01); B01J 29/04 (2006.01); B01J 29/08 (2006.01); B01J 29/46 (2006.01); C07C 4/06 (2006.01); C10G 11/05 (2006.01)

CPC B01J 29/46 (2013.01) [B01J 29/0352 (2013.01); B01J 29/0356 (2013.01); B01J 29/0358 (2013.01); B01J 29/041 (2013.01); B01J 29/042 (2013.01); B01J 29/043 (2013.01); B01J 29/044 (2013.01); B01J 29/045 (2013.01); B01J 29/084 (2013.01); B01J 29/088 (2013.01); C07C 4/06 (2013.01); C10G 11/05 (2013.01); B01J 2229/42 (2013.01); B01J 2229/66 (2013.01)]

25 Claims

1. A modified molecular sieve having a MFI structure, comprising phosphorus, a supported metal M1, and a supported metal M2,

wherein the modified molecular sieve has:

a ratio of (SiO₂)/(Al₂O₃) of more than 15 and less than 70,

a content of phosphorus, calculated as P₂O₅, of 1-15 wt % based on a dry weight of the modified molecular sieve,

a content of supported metal M1, calculated as oxide of the supported metal M1, of 1-10 wt %, based on the dry weight of the modified molecular sieve, and

a content of supported metal M2, calculated as oxide of the supported metal M2, of 0.1-5 wt %, based on the dry weight of the modified molecular sieve,

wherein the supported metal M1 is one or more selected from rare earth elements, and the supported metal M2 is one selected from iron, cobalt, nickel, copper, manganese, zinc, tin, bismuth and gallium,

wherein a volume of mesopores in the modified molecular sieve represents 40-70% by volume of a total pore volume of the modified molecular sieve, the volume of mesopores and the total pore volume of the modified molecular sieve are measured by a nitrogen adsorption BET specific surface area method, and the volume of mesopores is the pore volume of the pores having a diameter of more than 2 nm and less than 100 nm,

wherein the modified molecular sieve has a RE distribution parameter, D, which satisfies 0.9≤D≤1.3, wherein D=RE (S)/RE (C), RE (S) represents a content of rare earth in any region of more than 100 nm²in a distance H inward from an edge of a crystal face of the molecular sieve crystal grain measured by a TEM-EDS method, and RE (C) represents a content of rare earth in any region of more than 100 nm²in a distance H outward from a geometric center of the crystal face of the molecular sieve crystal grain measured by a TEM-EDS method, wherein H is 10% of the distance from a certain point on an edge of the crystal face to the geometric center of the crystal face.