Method of producing FCC catalysts with reduced attrition rates

Patent metadata

Field	Value
Publication number	US-9682366-B2
Application number	US-201615196241-A
Country	US
Kind code	B2
Filing date	Jun 29, 2016
Priority date	Jun 17, 2013
Publication date	Jun 20, 2017
Grant date	Jun 20, 2017

Abstract

FCC catalysts having improved attrition resistance are provided by mixing a cationic polyelectrolyte with either zeolite crystals or a zeolite-forming nutrient and/or a matrix material, prior to or during formation of a catalyst microsphere.

First claim

The invention claimed is:

1. An FCC zeolite-containing catalyst microsphere, the microsphere comprising zeolite, the microsphere having been formed from a slurry comprising a matrix and at least one of a zeolite-forming nutrient or zeolite crystals, the slurry having been mixed with, prior to or during formation of the microsphere, a cationic polyelectrolyte in an amount from 0.005 to 0.5 wt. % relative to a total weight of the matrix and the zeolite-forming nutrient or the zeolite crystals in the slurry, wherein the FCC zeolite-containing catalyst microsphere comprises a macroporous structure having a macropore volume in the pore range of 600 to 20,000 Å of about 0.07 cc/gm or more mercury intrusion.

2. The catalyst of claim 1 , wherein the microsphere is 20 to 200 micrometers in diameter.

3. The catalyst of claim 1 , wherein the microsphere is formed from the zeolite-forming nutrient and the matrix, and wherein the zeolite is formed in situ.

4. The catalyst of claim 3 , wherein the zeolite-forming nutrient is metakaolin.

5. The catalyst of claim 4 , wherein the matrix is formed from kaolin that has been calcined through its exotherm.

6. The catalyst of claim 1 , wherein the cationic polyelectrolyte is selected from the group consisting of polyamines, quaternary ammonium salts, diallyl ammonium polymer salts, and dimethyl diallyl ammonium chloride.

7. The catalyst of claim 1 , wherein the microsphere has a total pore volume ranging from about than 0.2381 cc/g to about 0.390 cc/g.

8. The catalyst of claim 6 , wherein the polyamine is mixed with the zeolite-forming nutrient and the matrix.

9. The catalyst of claim 6 , wherein the polyamine is mixed with the zeolite-forming nutrient and the matrix in an amount of from about 0.025 to 0.1 wt. %, relative to a total weight of the matrix and the zeolite-forming nutrient.

10. The method of claim 6 , wherein the polyamine has a molecular weight of between 10,000 and 1,000,000.

11. A method of producing an FCC catalyst microsphere, the method comprising:
forming a slurry comprising a matrix and zeolite crystals or kaolin;
mixing with the slurry a cationic polyelectrolyte such that the cationic polyelectrolyte is present in the slurry in an amount from 0.005 to 0.5 wt. % relative to a total weight of the matrix and the zeolite crystals or kaolin in the slurry; and
spray drying the slurry into microspheres,
wherein the microsphere comprises a macroporous structure having a macropore volume in the pore range of 600 to 20,000 Å of about 0.07 cc/g or more mercury intrusion.

12. The method of claim 11 , wherein the catalyst microsphere is 20 to 200 micrometers in diameter.

13. The method of claim 11 , wherein the matrix is kaolin calcined through the exotherm.

14. The method of claim 11 , wherein the cationic polyelectrolyte is a polyamine, and wherein the polyamine has a molecular weight of between 10,000 and 1,000,000.

15. The method of claim 11 , wherein the cationic polyelectrolyte is present in the slurry in an amount from 0.025 to 0.1 wt. % relative to a total weight of the matrix and the zeolite crystals or kaolin in the slurry.

16. The method of claim 11 , wherein the slurry contains hydrous kaolin and/or metakaolin, and the microspheres are reacted with a silicate to form zeolite crystals in situ.

17. The method of claim 11 , wherein said matrix is kaolin calcined through the exotherm and is formed from an ultrafine hydrous kaolin having at least 90 wt. % of the particles less than 2 microns.

18. The method of claim 11 , further comprising:
reacting the microspheres with a silicate to form catalyst microspheres containing zeolite crystals formed in situ.

19. The method of claim 11 , wherein the kaolin comprises one or more of hydrous kaolin or metakaolin.

20. The catalyst of claim 5 , wherein the microsphere comprises 25 parts to 75 parts kaolin calcined through the exotherm and 75 parts to 25 parts metakaolin.

Assignees

• Basf Corp

Inventors

• Sigman Michael
• Willis Mitchell
• Folmar Kenneth

Classifications

• B01J2235/15

  X-ray diffraction · CPC title

• B01J35/77

  Compounds characterised by their crystallite size · CPC title

• B01J35/70

  characterised by their crystalline properties, e.g. semi-crystalline (catalysts comprising carbon B01J21/18; molecular sieves B01J29/00) · CPC title

• B01J35/45

  Nanoparticles · CPC title

• B01J35/38

  Abrasion or attrition resistance · CPC title