Modified Y-type molecular sieve, preparation thereof and catalyst comprising the same

Patent metadata

Field	Value
Publication number	US-11052381-B2
Application number	US-201816484063-A
Country	US
Kind code	B2
Filing date	Feb 12, 2018
Priority date	Feb 21, 2017
Publication date	Jul 6, 2021
Grant date	Jul 6, 2021

Abstract

A modified Y-type molecular sieve has a rare earth oxide content of about 4% to about 12% by weight, a phosphorus content of about 0% to about 10% by weight, a sodium oxide content of no more than about 1.0% by weight, a total pore volume of about 0.36 to 0.48 mL/g, a percentage of the pore volume of secondary pores to the total pore volume of about 20% to about 40%, a lattice constant of about 2.440 nm to about 2.455 nm, a percentage of the non-framework aluminum content to the total aluminum content of no more than about 10%, a lattice collapse temperature of not lower than about 1060° C., and a ratio of Brønsted acid to Lewis acid of no less than about 3.50. The preparation of the molecular sieve includes ion-exchange with rare earth, hydrothermal roasting, gas phase ultra-stabilization, acid treatment, and an optional phosphorus modification.

First claim

The invention claimed is:

1. A modified Y-type molecular sieve, having a rare earth oxide content of about 4% to about 12% by weight, a phosphorus content of about 0% to about 10% by weight on the basis of P 2 O 5 , a sodium oxide content of no more than about 1.0% by weight, a total pore volume of about 0.36 mL/g to about 0.48 mL/g, a percentage of a 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 20% to about 40%, a lattice constant of about 2.440 nm to about 2.455 nm, a percentage of the non-framework aluminum content to the total aluminum content of the modified Y-type molecular sieve of no more than about 10%, a lattice collapse temperature of not lower than about 1060° C., and a ratio of Brønsted acid to Lewis acid in a total acid content of the modified Y-type molecular sieve of no less than about 3.5, as determined by pyridine adsorption infrared spectroscopy at 200° C., and
wherein the modified Y-type molecular sieve has a framework structure of zeolite Y.

2. 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 28% to about 38%.

3. The modified Y-type molecular sieve according to claim 1 , wherein the modified Y-type molecular sieve has a percentage of the non-framework aluminum content to the total aluminum content of about 5% to about 9.5% by weight, and a framework silica-alumina ratio of about 7 to about 14 calculated on the basis of SiO 2 /Al 2 O 3 molar ratio.

4. The modified Y-type molecular sieve according to claim 1 , wherein the modified Y-type molecular sieve has a lattice collapse temperature of about 1060° C. to about 1085° C.

5. The modified Y-type molecular sieve according to claim 1 , wherein the ratio of Brönsted acid to Lewis acid in the total acid content of the modified Y-type molecular sieve is about 3.5 to about 6, as determined by pyridine adsorption infrared spectroscopy at 200° C.

6. The modified Y-type molecular sieve according to claim 1 , wherein the modified Y-type molecular sieve has a relative crystallinity of about 70% to about 80%, and, after being aged at 800° C. under atmospheric pressure in a 100% steam atmosphere for 17 hours, the modified Y-type molecular sieve shows a relative crystallinity retention of about 38% or more.

7. 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 phosphorus content of about 0.1% to about 6% by weight on the basis of P 2 O 5 , a sodium oxide content of about 0.05% to about 0.3% by weight, a lattice constant of 2.442-2.451 nm, and a framework silica-alumina ratio of about 8.5-12.6 calculated on the basis of SiO 2 /Al 2 O 3 molar ratio.

8. 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 5.5% to about 10% by weight, a sodium oxide content of about 0.15% to about 0.3% by weight, 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 20-38%, a lattice constant of 2.442-2.453 nm, and a framework silica-alumina ratio of about 7.8-12.6 calculated on the basis of SiO 2 /Al 2 O 3 molar ratio.

9. The modified Y-type molecular sieve according to claim 1 , wherein the percentage of the pore volume of secondary pores having a pore size of 8-100 nm to the total pore volume of secondary pores having a pore size of 2-100 nm of the modified Y-type molecular sieve is about 40-80%.

10. A method for the preparation of a 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 Y-type molecular sieve containing rare earth elements and having a reduced sodium oxide content;
(2) calcining the Y-type molecular sieve obtained in the step (1) at a temperature of about 350° C. to about 520° C. in an atmosphere containing about 30 vol % to about 90 vol % of steam for a time of 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 at a weight ratio of SiCl 4 to the Y-type molecular sieve on a dry basis ranging from about 0.1:1 to about 0.7:1 and a reaction temperature of about 200° C. to 650° C. for a reaction time of about 10 minutes to about 5 hours to obtain a gas phase ultra-stabilized Y-type molecular sieve;
(4) contacting the ultra-stabilized Y-type molecular sieve obtained in the step (3) with an acid solution; and
(5) optionally contacting the acid-treated Y-type molecular sieve obtained in the step (4) to with a phosphorus compound.

11. The method according to claim 10 , wherein the Y-type molecular sieve 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 9.0% by weight.

12. The method according to claim 10 , 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: NaY molecular sieve:rare earth salt:H 2 O weight ratio of about 1:0.01-0.18:5-20, an ion-exchange temperature of about 15-95° C., and an ion-exchange time of about 30-120 minutes.

13. The method according to claim 10 , wherein, in the step (2), the calcination temperature is about 380-480° C., the calcination atmosphere contains about 40-80 vol % steam, and the calcination time is about 5-6 hours.

14. The method according to claim 10 , 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.

15. The method according to claim 10 , wherein the step (4) comprises first contacting with an inorganic acid having a medium or higher strength; and then contacting with an organic acid,
wherein the contacting with the inorganic acid having a medium or higher strength is carried out under the following conditions: a weight ratio of the inorganic acid to the molecular sieve of about 0.01-0.05:1, a weight ratio of water to the molecular sieve of about 5-20:1, a contact time of about 60-120 minutes, and a contact temperature of about 90-98° C.; and
the contacting with the organic acid is carried out under the following conditions: a weight ratio of the organic acid to the molecular sieve of about 0.02-0.10:1, a weight ratio of water to the molecular sieve of about 5-20:1, a contact time of about 60-120 minutes and a contact temperature of about 90-98° C.

16. The method according to claim 15 , wherein the organic acid is one or more selected from the group consisting of oxalic acid, malonic acid, succinic acid, methyl succinic acid, malic acid, tartaric acid, citric acid, and salicylic acid, and the inorganic acid having a medium or higher strength is one or more selected from the group consisting of phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid.

17. The method according to claim 10 , comprising carrying out the step (5) by contacting the acid-treated Y-type molecular sieve obtained in the step (4) with an exchange liquid containing a phosphorus compound to conduct an ion-exchange reaction at about 15-100° C

Assignees

• China Petroleum & Chem Corp
• Sinopec Res Inst Petroleum

Inventors

• Zhou Lingping
• Zhang Weilin
• Xu Mingde
• Chen Zhenyu
• Tian Huiping
• Zhu Yuxia

Classifications

• C10G11/05 Primary

  Crystalline alumino-silicates, e.g. molecular sieves · CPC title

• B01J29/088 Primary

  Y-type faujasite · CPC title

• B01J29/085

  containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead · CPC title

• C10G2400/04

  Diesel oil · CPC title

• C10G2300/302

  Viscosity · CPC title