High strength SAPO-34 microsphere catalyst, method for preparing same, and method for preparing light olefins using same

Patent metadata

Field	Value
Publication number	US-10112187-B2
Application number	US-201013502496-A
Country	US
Kind code	B2
Filing date	Oct 4, 2010
Priority date	Oct 22, 2009
Publication date	Oct 30, 2018
Grant date	Oct 30, 2018

Abstract

The present invention relates to a high-strength silicoaluminophasphate-34 (SAPO-34) microsphere catalyst, a method for preparing the same, and a method for preparing light olefins by using the same, and when described in more detail, the present invention relates to a method for preparing a SAPO-34 microsphere catalyst, including: spray drying a mixed slurry including a matrix, a binder, an additive, and the like to a SAPO-34 slurry prepared by a hydrothermal synthesizing method using various organic templates such as tetraethylammonium hydroxide (TEAOH), and the like alone or in mixtures to prepare microspheres, and firing the microspheres, and to a SAPO-34 microsphere catalyst for a circulating-fluidized bed reactor, prepared by the preparation method. The SAPO-34 microsphere catalyst of the present invention has excellent reaction activity while having high strength, and thus is appropriate for use in a circulating-fluidized bed reactor requiring high strength of the catalyst. Further, the SAPO-34 microsphere catalyst has a long life-span and excellent conversion rate of C 1 to C 4 oxygen-including compounds (oxygenates), and thus is appropriate for use in the preparation of light olefins such as ethylene, propylene, butene, and the like.

First claim

The invention claimed is:

1. A method for preparing a SAPO-34 microsphere catalyst which is applied to a methanol-to-olefin (MTO) reaction, comprising:
spray drying a mixed slurry comprising 100 parts by weight of a crystallized undried silicoaluminophosphate-34 (SAPO-34) slurry, 50-300 parts by weight of a binder and 0.5-5 parts by weight of an additive to prepare microspheres; and
firing the microspheres, wherein the binder consists of one or more selected from an alumina sol and a silica sol, and wherein the additive consists of one or two or more selected from hydrochloric acid, nitric acid, acetic acid, and formic acid,
wherein the crystallized undried SAPO-34 slurry is prepared by hydrothermally synthesizing a mixed synthetic gel in which a synthetic gel comprising an aluminum phosphate gel, a first organic template and a solvent; and a silica-dissolving solution comprising a silica precursor, a second organic template and a solvent are mixed,
wherein the mixed slurry comprises kaolin as a matrix in range of 13.3-67 parts by weight based on 100 parts by weight of the SAPO-34 slurry,
wherein the solvent comprises one or two selected from water and alcohol in a molar ratio of 10 to 60 based on 1 mole of an alumina precursor (based on Al 2 O 3 ),
wherein the crystallized undried SAPO-34 slurry includes SAPO-34 with average crystal size of less than 1 μm,
wherein the hydrothermal synthesis is performed by putting the mixed synthetic gel into an autoclave, maturing the mixed synthetic gel while being stirred at 20° C. to 120° C. for 0.5 hr to 24 hr and stirring the mixed synthetic gel at 150° C. to 200° C. for 5 hr to 48 hr to perform crystallization,
wherein a molar ratio calculated by the first organic template/the second organic template is 0.5 to 2.0,
wherein the SAPO-34 microsphere catalyst is used in circulating-fluidized bed reactor for preparing light olefins.

2. The method of claim 1 , wherein the aluminum phosphate gel comprises water, an alumina precursor, and phosphoric acid; the first organic template comprises one or more selected from tetraethylammonium hydroxide and diethylamine; and the second organic template comprises one or two or more selected from morpholine, dipropylamine, isopropylamine, diethanolamine, triethylamine, diethylamine, cyclopentylamine, aminomethyl cyclohexane, piperidine, cyclohexylamine, tri-ethyl hydroxyethylamine, and pyridine.

3. The method of claim 1 , wherein the firing is performed at a temperature of 500 to 700° C.

4. The method of claim 1 , wherein the additive is formic acid.

5. The method of claim 1 , wherein the crystallized undried silicoaluminophosphate-34 (SAPO-34) slurry includes 40 wt % of SAPO-34.

6. A SAPO-34 microsphere catalyst prepared by the method of any one selected from claims 1 , 2 , and 3 .

7. A method for preparing a SAPO-34 microsphere catalyst which is applied to a methanol-to-olefin (MTO) reaction, comprising:
spray drying a mixed slurry comprising 100 parts by weight of a crystallized undried silicoaluminophosphate-34 (SAPO-34) slurry, 50-300 parts by weight of a binder and 0.5-5 parts by weight of an additive to prepare microspheres; and
firing the microspheres at a temperature of 500 to 700° C., wherein the binder consists of one or more selected from an alumina sol and a silica sol, and wherein the additive comprises formic acid,
wherein the crystallized undried SAPO-34 slurry is prepared by hydrothermally synthesizing a mixed synthetic gel in which a synthetic gel comprising an aluminum phosphate gel, a first organic template and a solvent; and a silica-dissolving solution comprising a silica precursor, a second organic template and a solvent are mixed,
wherein the mixed slurry comprises kaolin as a matrix in range of 13.3-67 parts by weight based on 100 parts of the SAPO-34 slurry,
wherein the solvent comprises one or two selected from water and alcohol in a molar ratio of 10 to 60 based on 1 mole of an alumina precursor (based on Al 2 O 3 ),
wherein the hydrothermal synthesis is performed by putting the mixed synthetic gel into an autoclave, maturing the mixed synthetic gel while being stirred at 20 to 120° C. for 0.5 to 24 hr, and stirring the mixed synthetic gel at 150 to 200° C. for 5 to 48 hr to perform crystallization, and
wherein the crystallized undried silicoaluminophosphate-34 (SAPO-34) slurry includes 40 wt % of SAPO-34,
wherein the crystallized undried SAPO-34 slurry includes SAPO-34 with average crystal size of less than 1 μm,
wherein the hydrothermal synthesis is performed by putting the mixed synthetic gel into an autoclave, maturing the mixed synthetic gel while being stirred at 20° C. to 120° C. for 0.5 hr to 24 hr and stirring the mixed synthetic gel at 150° C. to 200° C. for 5 hr to 48 hr to perform crystallization,
wherein a molar ratio calculated by the first organic template/the second organic template is 0.5 to 2.0,
wherein the SAPO-34 microsphere catalyst is used in circulating-fluidized bed reactor for preparing light olefins.

8. A method for preparing a silicoaluminophosphate (SAPO) microsphere catalyst, the method comprising:
mixing together an aluminum precursor, phosphoric acid, water and a first organic template to prepare a synthetic gel;
dissolving a silica precursor into second organic template to prepare a silica-dissolved solution;
stirring together the silica-dissolved solution with the synthetic gel to prepare a mixed synthetic gel;
autoclaving the mixed synthetic gel at a between 150° C. to 200° C. to obtain a crystallized SAPO slurry;
spray drying a mixture of the SAPO slurry, a binder, an additive, and a matrix to prepare a spray dried product; and
firing the spray dried product to prepare the SAPO microsphere catalyst,
wherein the spray drying a mixed slurry comprising 100 parts by weight of the SAPO slurry, 50-300 parts by weight of the binder, 13.3-67 parts by weight of the matrix and 0.5-5 parts by weight of the additive,
wherein the SAPO microsphere catalyst is used in circulating-fluidized bed reactor for preparing light olefins.

9. The method of claim 8 wherein the alumina precursor is selected from the group consisting of aluminum alkoxide, pseudoboehmite, and aluminum isopropoxide.

10. The method of claim 8 , wherein the first organic template is selected from the group consisting of tetraethylammonium hydroxide and diethylamine.

11. The method of claim 8 , wherein the second organic template is selected from the group consisting of morpholine, dipropylamine, isopropylamine, diethanolamine, triethylamine, diethylamine, cyclopentylamine, aminomethyl cyclohexane, piperidine, cyclohexylamine, tri-ethyl hydroxyethylamine, and pyridine.

12. The method of claim 8 , wherein the silica precursor is selected from the group consisting of water glass, silica sol, and fumed silica.

13. The method of claim 8 , wherein the binder is selected from the group consisting of an alumina sol, a silica sol, and poly aluminum chloride.

14. The method of claim 8 , wherein the additive is selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, and formic acid.

15. The method of claim 8 , wherein the matrix is selected from the group consisting of kaolin, bentonite, montmorillonite, china clay, and boehmite.

16. The method of claim 8 , wherein the firing is performed between 500° C. and 700° C.

Assignees

• Chae Ho Jeong
• Jeong Soon Yong
• Kim Chul Ung
• Jeong Kwang Eun
• Kim Tae Wan
• Korea Res Inst Chemical Tech

Inventors

• Chae Ho Jeong
• Jeong Soon Yong
• Kim Chul Ung
• Jeong Kwang Eun
• Kim Tae Wan

Classifications

• C10G2400/20

  C2-C4 olefins · CPC title

• C10G11/18

  according to the "fluidised-bed" technique · CPC title

• C10G3/00

  Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids (production from non-melting solid oxygen-containing carbonaceous materials C10G1/00) · CPC title

• B01J37/0045

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

• C07C1/20

  starting from organic compounds containing only oxygen atoms as heteroatoms · CPC title