Ferrierite composition for reducing NOx emissions during fluid catalytic cracking

Patent metadata

Field	Value
Publication number	US-9931595-B2
Application number	US-83333610-A
Country	US
Kind code	B2
Filing date	Jul 9, 2010
Priority date	Nov 6, 2003
Publication date	Apr 3, 2018
Grant date	Apr 3, 2018

Abstract

Compositions for reduction of NO x generated during a catalytic cracking process, preferably, a fluid catalytic cracking process, are disclosed. The compositions comprise a fluid catalytic cracking catalyst composition, preferably containing a Y-type zeolite, and a particulate NO x reduction composition containing ferrierite zeolite particles. Preferably, the NO x reduction composition contains ferrierite zeolite particles bound with an inorganic binder. In the alternative, the ferrierite zeolite particles are incorporated into the cracking catalyst as an integral component of the catalyst. NO x reduction compositions in accordance with the invention are very effective for the reduction of NO x emissions released from the regenerator of a fluid catalytic cracking unit operating under FCC process conditions without a substantial change in conversion or yield of cracked products. Processes for the use of the compositions are also disclosed.

First claim

What is claimed is:

1. A process of reducing NO x emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said process comprising
a. contacting a hydrocarbon feedstock during a fluid catalytic cracking (FCC) process wherein NO x emissions are released from a regeneration zone of a fluid catalytic cracking unit (FCCU) operating under FCC conditions with a circulating inventory of a cracking catalyst and a separate particulate NO x reduction composition having a mean particle size of greater than 45 μm and consisting essentially of (i) at least 50 weight percent of ferrierite zeolite based on a total weight of the separate particulate NO x reduction composition, wherein the ferrierite zeolite is stabilized with at least one stabilizing metal selected from the group consisting of Groups IIA, IIIB, and IIIA, but excluding yttrium and lanthanum, and mixtures thereof, (ii) from about 5 to 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, aluminum phosphate and mixtures thereof; and (iii) matrix material; and
b. reducing the amount of NO x emissions released from the regeneration zone of the FCCU as compared to the amount of NO x emissions released in the absence of the particulate NO x reduction composition.

2. The process of claim 1 wherein the cracking catalyst comprises a Y-type zeolite.

3. The process of claim 1 wherein the amount of ferrierite zeolite present in the NO x reduction composition ranges from 50 to about 85 weight percent of the composition.

4. The process of claim 3 wherein the amount of ferrierite zeolite present in the NO x reduction composition ranges from 50 to about 80 weight percent of the composition.

5. The process of claim 4 wherein the amount of ferrierite zeolite present in the NO x reduction composition ranges from 50 to about 75 weight percent of the composition.

6. The process of claim 1 wherein the ferrierite zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof.

7. The process of claim 1 wherein the stabilizing metal is selected from the group consisting of aluminum, magnesium, and mixtures thereof.

8. The process of claim 1 wherein the stabilizing metal is incorporated into the pores of the ferrierite zeolite.

9. The process of claim 1 wherein the inorganic binder is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof.

10. The process of claim 9 wherein the inorganic binder is alumina.

11. The process of claim 10 wherein the alumina is an acid or base peptized alumina.

12. The process of claim 10 wherein the alumina is aluminum chlorohydrol.

13. The process of claim 1 wherein the amount of inorganic binder present in the particulate NO x reduction composition ranges from about 10 to about 30 weight percent of the composition.

14. The process of claim 13 wherein the amount of inorganic binder present in the particulate NO x reduction composition ranges from about 15 to about 25 weight percent of the composition.

15. The process of claim 1 wherein the NO x reduction composition further comprises a matrix material selected from the group consisting of alumina, silica, silica alumina, titania, zirconia, yttria, lanthana, ceria, neodymia, samaria, europia, gadolinia, praseodymia, and mixtures thereof.

16. The process of claim 15 wherein the matrix material is present in an amount less than 70 weight percent.

17. The process of claim 1 further comprising recovering the cracking catalyst from said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst.

18. The process of claim 17 wherein the cracking catalyst and the particulate NO x reduction composition are fluidized during contacting said hydrocarbon feedstock.

19. The process of claim 1 further comprising contacting the hydrocarbon feed with at least one additional NO x reduction composition.

20. The process of claim 19 wherein the additional NO x reduction composition is a non-zeolitic composition.

21. The process of claim 20 wherein the additional NO x reduction composition comprises (1) an acidic metal oxide containing substantially no zeolite; (2) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (3) an oxygen storage metal oxide component; and (4) at least one noble metal component.

22. The process of claim 19 wherein the additional NO x reduction composition is a low NO x , CO combustion promoter composition which comprises (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) palladium.

23. The process of claim 19 wherein the additional NO x reduction composition comprises (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) a transition metal selected from Groups IB and IIB of the Periodic Table, and mixtures thereof.

24. The process of claim 19 wherein the additional NO x reduction composition comprises at least one metal-containing spinel which includes a first metal and a second metal having a valence higher than the valence of said first metal, at least one component of a third metal other than said first and second metals and at least one component of a fourth metal other than said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group VIA metals, the rare-earth metals, the Platinum Group metals and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.

25. The process of claim 24 wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal.

26. The process of claim 25 wherein the third metal component in the metal containing spinel is selected from the group consisting of a Platinum Group metal, the rare-earth metals and mixtures thereof.

27. The process of claim 24 wherein the third metal component is present in an amount in the range of about 0.001 to about 20 weight percent, calculated as elemental third metal.

28. The process of claim 24 wherein said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent, calculated as elemental fourth metal.

29. The process of claim 19 wherein the additional NO x reduction additive is a zinc based catalyst.

30. The process of claim 19 wherein the additional NO x reduction additive is an antimony based NO x reduction additive.

31. The process of claim 19 wherein the additional NO x reduction additive is a perovskite-spinel NO x reduction additive.

32. The process of claim 19 wherein the additional NO x reduction additive is a hydrotalcite containing composition.

33. The process of claim 1 wherein the particulate NO x reduction composition has

Assignees

• Yaluris George
• Ziebarth Michael Scott
• Zhao Xinjin
• Grace W R & Co

Inventors

• Yaluris George
• Ziebarth Michael Scott
• Zhao Xinjin

Classifications

• B01J2229/18

  to introduce other elements into or onto the molecular sieve itself · CPC title

• B01J29/80

  Mixtures of different zeolites · CPC title

• B01D2255/50

  Zeolites · CPC title

• B01J35/0006

  Operations & Transport · mapped topic

• B01J29/65 Primary

  of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively · CPC title