Sapo-34/zsm-5@kaolin microsphere composite catalytic material and its preparation and use

Patent metadata

Field	Value
Publication number	US-2019224652-A1
Application number	US-201916237857-A
Country	US
Kind code	A1
Filing date	Jan 2, 2019
Priority date	Jan 23, 2018
Publication date	Jul 25, 2019
Grant date	—

Abstract

The present invention relates to a composite catalytic material of SAPO-34/ZSM-5@kaolin microspheres and its preparation and use, the method comprises the steps of: 1) processing kaolin into kaolin microspheres, and baking them to obtain activated kaolin microspheres; 2) mixing the activated kaolin microspheres obtained in step 1), water, a phosphorus source, and a template agent to prepare a gel; 3) mixing the gel obtained in step 2) and a ZSM-5 molecular sieve, and carrying out aging, crystallization, and separation to obtain a composite material of SAPO-34/ZSM-5@kaolin; 4) subjecting the composite material obtained in step 3) to ammonium exchange treatment and baking, to obtain the composite catalytic material of SAPO-34/ZSM-5@kaolin microspheres. The present invention not only greatly shortens the preparation route for the catalyst and reduces the cost of catalyst preparation, but also allows adjustment of the fractions of SAPO-34 and ZSM-5 molecular sieves in the composite material by adjustment of the synthesis conditions.

First claim

What is claimed is:

1 . A method for preparing a composite catalytic material of SAPO-34/ZSM-5@kaolin microspheres, comprising the steps of:
1) processing kaolin into kaolin microspheres, and baking them to obtain activated kaolin microspheres; 2) mixing the activated kaolin microspheres obtained in step 1), water, a phosphorus source, and a template agent, preferably in a molar ratio of (4-6)R:(0.20-0.30)SiO 2 :(0.58-1.85)Al 2 O 3 :(2.0-3.1)P 2 O 5 :(111-222)H 2 O, to prepare a gel, where the R represents the template agent; 3) mixing the gel obtained in step 2) and a ZSM-5 molecular sieve, preferably in a ZSM-5-to-gel mass ratio from 0.042 to 0.066, and carrying out aging, crystallization, and separation to obtain a composite material of SAPO-34/ZSM-5@kaolin; 4) subjecting the composite material obtained in step 3) to ammonium exchange treatment, and baking, to obtain the composite catalytic material of SAPO-34/ZSM-5@kaolin microspheres.

2 . The method according to claim 1 , wherein step 1) comprises
processing kaolin into kaolin microspheres, preferably by spray drying, more preferably by mixing kaolin with water and a binder and then spray-drying the mixture to prepare kaolin microspheres, wherein the binder is preferably selected from one or more of water glass, alumina sol, and silica sol, the mass ratio of the kaolin to the binder is preferably from 1.5 to 2.75, and preferably the kaolin is pulverized and screened before being mixed with water and the binder; and baking the kaolin microspheres to obtain activated kaolin microspheres preferably having a particle size of 80 to 100 μm, preferably at a baking temperature of 650° C. to 900° C., more preferably 750° C. to 800° C., preferably for a baking duration of 1 to 6 h, more preferably 3 to 5 h.

3 . The method according to claim 1 , wherein step 2) comprises
homogeneously mixing the phosphorus source with a part of water first, then adding the template agent and the rest of water, mixing them homogeneously, then adding the activated kaolin microspheres obtained in step 1), and mixing them homogeneously to obtain the gel.

4 . The method according to claim 1 , wherein the template agent is selected from one or more of triethylamine, diethylamine, and tetraethylammonium hydroxide.

5 . The method according to claim 1 , wherein the phosphorus source is phosphoric acid.

6 . The method according to claim 1 , wherein step 3) comprises
mixing the gel obtained in step 2) and a ZSM-5 molecular sieve (preferably a ZSM-5 molecular sieve having not been subjected to template removal) (preferably having a Si/Al molar ratio from 50 to 200, more preferably from 50 to 150); and carrying out aging (preferably at an aging temperature of 40° C. to 90° C., more preferably 70° C.) (preferably for an aging duration of 15 to 60 min, more preferably 30 min), crystallization (preferably at a crystallization temperature of 180° C. to 220° C., more preferably 200° C.) (preferably for a crystallization duration of 24 to 72 h, more preferably 48 h), and separation to obtain the composite material of SAPO-34/ZSM-5@kaolin; (preferably, after the crystallization, performing steps of standing for precipitation, centrifuging, washing, and drying (preferably at a drying temperature of 100° C. to 120° C. for a drying duration of 4 to 12 h) to obtain the composite material of SAPO-34/ZSM-5@kaolin).

7 . The method according to claim 1 , wherein step 4) comprises
subjecting the composite material obtained in step 3) to ammonium exchange treatment in an aqueous solution of ammonium chloride (preferably having a molar concentration of 0.1 to 1 M, more preferably 0.8 M) (preferably by stirring the composite material obtained in step 3) in an aqueous solution of ammonium chloride for 2 to 6 h (more preferably 4 h) at 60° C. to 90° C. (more preferably 80° C.)), drying, and baking, to obtain the composite catalytic material of SAPO-34/ZSM-5@kaolin microspheres.

8 . The method according to claim 1 , wherein in Step 4), the baking temperature is 500° C. to 600° C., and the baking duration is 3 to 6 h.

9 . A composite catalytic material of SAPO-34/ZSM-5@kaolin microspheres prepared by the method according to claim 1 , wherein, based on the relative crystallinity, the relative content of the SAPO-34 molecular sieve is 7 to 15 wt %, and the relative content of the ZSM-5 molecular sieve is 6 to 12 wt %.

10 . A method for producing olefins from methanol, wherein an aqueous solution of methanol (preferably the aqueous solution of methanol has a concentration of 90 to 99 wt %, more preferably 95 wt %) is used as a raw material and the composite catalytic material of SAPO-34/ZSM-5@kaolin microspheres according to claim 9 is used as a catalyst to prepare olefins (preferably at the conditions of normal pressure, a reaction temperature of 400° C. to 500° C. (more preferably 450° C.), and a weight hourly space velocity (WHSV) of 2 to 3 h −1 (more preferably 2.5 h −1 )).

Assignees

• Univ China Petroleum Beijing

Inventors

• Liu Haiyan
• Zhang Lina
• Bao Xiaojun

Classifications

• C01B39/026

  After-treatment · CPC title

• C01B33/40

  Clays · CPC title

• B01J2229/62

  in or on other molecular sieves · CPC title

• B01J37/0045

  Drying a slurry, e.g. spray drying · CPC title

• B01J29/005 Primary

  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 · CPC title