SAPO-11 molecular sieve, preparation method thereof, and use thereof in hydrocarbon isomerization

Patent metadata

Field	Value
Publication number	US-10258974-B2
Application number	US-201815882718-A
Country	US
Kind code	B2
Filing date	Jan 29, 2018
Priority date	Mar 14, 2017
Publication date	Apr 16, 2019
Grant date	Apr 16, 2019

Abstract

A SAPO-11 molecular sieve, preparation method thereof and use thereof in the isomerization of hydrocarbons is disclosed. The preparation method includes dissolving an aluminum source in ethylene glycol, and stirring to give a solution A; adding a structure-directing agent and a phosphorus source to the solution A, and stirring to give a solution B; adding a silicon source to the solution B, and stirring to give a solution C; transferring the solution C to a supercritical CO2 reactor, and introducing CO2 into the reactor to increase the pressure in the reactor; heating the supercritical CO2 reactor to the reaction temperature for crystallization; and after crystallization, lowering the temperature of the supercritical CO2 reactor, removing the solution from the reactor, separating the product, drying and calcining to obtain the SAPO-11 molecular sieve. A hydrocarbon isomerization catalyst can be obtained by molding the molecular sieve, loading a metal component, drying and calcining.

First claim

What is claimed is:

1. A method for preparing a SAPO-11 molecular sieve, comprising the steps of:
(1) dissolving an aluminum source in ethylene glycol, and stirring to give a solution A;
(2) adding a structure-directing agent and a phosphorus source to the solution A in step (1), and stirring to give a solution B;
(3) adding a silicon source to the solution B in step (2), and stirring to give a solution C;
(4) transferring the solution C in step (3) to a supercritical CO 2 reactor, and introducing CO 2 into the reactor to increase the pressure in the reactor;
(5) heating the supercritical CO 2 reactor to the reaction temperature for crystallization; and
(6) after the completion of crystallization, lowering the temperature of the supercritical CO 2 reactor, removing the solution from the reactor, separating the product, drying and calcining to obtain the SAPO-11 molecular sieve.

2. The method of claim 1 , wherein in step (2) the structure-directing agent comprises di-n-propylamine and/or diisopropylamine;
preferably, in step (2), the phosphorus source comprises phosphoric acid;
preferably, in step (2), the stirring is carried out at a temperature of 10 to 50° C. for 0.5 to 3 h.

3. The method of claim 1 , wherein in step (3) the silicon source comprises one or more of silica sol, ethyl orthosilicate, and propyl orthosilicate;
preferably, in step (3), the stirring is carried out at a temperature of 10 to 50° C. for 0.5 to 3 h.

4. The method of claim 1 , wherein the molar ratio of the aluminum source, silicon source, phosphorus source, structure-directing agent, and ethylene glycol is 0.5 to 1.5:0.1 to 0.3:1 to 3:1.5 to 5:20 to 50.

5. The method of claim 1 , wherein in step (4) CO 2 is introduced into the reactor such that the pressure in the reactor is increased to 40 to 75 bar.

6. The method of claim 1 , wherein in step (5) the reaction temperature in the super critical CO 2 reactor is 150 to 250° C.; preferably, the crystallization time is 50 to 200 h.

7. The method of claim 1 , wherein in step (6), the calcination is carried out at a temperature of 500 to 700° C. for 4 to 8 h;
preferably, in step (6), after the completion of crystallization, the temperature of the supercritical CO 2 reactor is lowered to 10 to 50° C.;
preferably, in step (6), the drying is carried out at a temperature of 80 to 150° C. for 8 to 24 h.

8. The method of claim 1 , wherein in step (1) the aluminum source comprises aluminum isopropoxide and/or pseudo-boehmite.

9. The method of claim 1 , wherein in step (1) the stirring is carried out at a temperature of 10 to 50° C. for 0.5 to 3 h.

Assignees

• Univ China Petroleum Beijing

Inventors

• Fan Yu
• Han Shanlei
• Wen Chenglong
• Wang Shihua

Classifications

• B01J37/04

  Mixing {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J37/0018

  Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat) · CPC title

• C07C2529/85

  Silicoaluminophosphates (SAPO compounds) · CPC title

• Y02P20/544

  Cross-Sectional Technologies · mapped topic

• B01J23/883

  and nickel · CPC title