Ferrierite compositions for reducing NOx emissions during fluid catalytic cracking

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.

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 particulate NO x  reduction composition having a mean particle size of greater than 45 μm and comprising (i) at least 10 weight percent of ferrierite zeolite, and (ii) from about 5 to about 50 weight percent of an inorganic binder, selected from the group consisting of alumina, silica, silica alumina, alumina phosphate and mixtures thereof; and    b. reducing the amount of NO x  emissions released from the regeneration zone of the FCCU by at least 10% 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 FCC cracking catalyst comprises a Y-type zeolite.  
     
     
         3 . The process of  claim 1  wherein step (b) is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone.  
     
     
         4 . The process of  claim 1  wherein the amount of ferrierite zeolite present in the NO x  reduction composition is at least 30 weight percent of the composition.  
     
     
         5 . The process of  claim 4  wherein the amount of ferrierite zeolite present in the NO x  reduction composition is at least 40 weight percent of the composition.  
     
     
         6 . The process of  claim 5  wherein the amount of ferrierite zeolite present in the NO x  reduction composition is at least 50 weight percent of the composition.  
     
     
         7 . The process of  claim 1  wherein the amount of ferrierite zeolite present in the NO x  reduction composition ranges from about 10 to about 85 weight percent of the composition.  
     
     
         8 . The process of  claim 7  wherein the amount of ferrierite zeolite present in the NO x  reduction composition ranges from about 30 to about 80 weight percent of the composition.  
     
     
         9 . The process of  claim 8  wherein the amount of ferrierite zeolite present in the NO x  reduction composition ranges from about 40 to about 75 weight percent of the composition.  
     
     
         10 . The process of  claim 1  or  3  wherein the ferrierite zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof.  
     
     
         11 . The process of  claim 1  wherein the ferrierite zeolite further comprises at least one stabilizing metal.  
     
     
         12 . The process of  claim 11  wherein the stabilizing metal is a metal selected from the group consisting of Groups IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IIB, IIIA, IVA, VA, the Lanthanide Series of The Periodic Table, Ag and mixtures thereof.  
     
     
         13 . The process of  claim 12  wherein the stabilizing metal is selected from the group consisting of Groups IIIB, IIA, IIB, IIIA and the Lanthanide Series of the Periodic Table, and mixtures thereof.  
     
     
         14 . The process of  claim 13  wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof.  
     
     
         15 . The process of  claim 11  wherein the stabilizing metal is incorporated into the pores of the ferrierite zeolite.  
     
     
         16 . The process of  claim 1  wherein the inorganic binder is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof.  
     
     
         17 . The process of  claim 16  wherein the inorganic binder is alumina.  
     
     
         18 . The process of  claim 17  wherein the alumina is an acid or base peptized alumina.  
     
     
         19 . The process of  claim 17  wherein the alumina is aluminum chlorohydrol.  
     
     
         20 . 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.  
     
     
         21 . The process of  claim 20  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.  
     
     
         22 . The process of  claim 1  wherein the particulate NO x  reduction composition further comprises an additional zeolite other than ferrierite zeolite.  
     
     
         23 . The process of  claim 22  wherein the additional zeolite is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms and a SiO 2  to Al 2 O 3  molar ratio less than about 500.  
     
     
         24 . The process of  claim 23  wherein the SiO 2  to Al 2 O 3  molar ratio is less than 250.  
     
     
         25 . The process of  claim 22  wherein the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61; Offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-35, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite and mixtures thereof.  
     
     
         26 . The process of  claim 25  wherein the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, Offretite, A, ZSM-12 and mixtures thereof.  
     
     
         27 . The process of  claim 22 ,  23  or  25  wherein the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.  
     
     
         28 . The process of  claim 27  wherein the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition.  
     
     
         29 . The process of  claim 1  or  3  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.  
     
     
         30 . The process of  claim 29  wherein the matrix material is present in an amount less than 70 weight percent.  
     
     
         31 . The process of  claim 1  or  3  further comprising recovering the cracking catalyst from said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst.  
     
     
         32 . The process of  claim 31  wherein the cracking catalyst and the particulate NO x  reduction composition are fluidized during contacting said hydrocarbon feedstock.  
     
     
         33 . The process of  claim 1  or  3  further comprising contacting the hydrocarbon feed with at least one additional NO x  reduction composition.  
     
     
         34 . The process of  claim 33  wherein the additional NO x  reduction composition is a non-zeolitic composition.  
     
     
         35 . The process of  claim 34  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.  
     
     
         36 . The process of  claim 33  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.  
     
     
         37 . The process of  claim 33  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.  
     
     
         38 . The process of  claim 33  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.  
     
     
         39 . The process of  claim 38  wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal.  
     
     
         40 . The process of  claim 39  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.  
     
     
         41 . The process of  claim 38  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.  
     
     
         42 . The process of  claim 38  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.  
     
     
         43 . The process of  claim 33  wherein the additional NO x  reduction additive is a zinc based catalyst.  
     
     
         44 . The process of  claim 33  wherein the additional NO x  reduction additive is an antimony based NO x  reduction additive.  
     
     
         45 . The process of  claim 33  wherein the additional NO x  reduction additive is a perovskite-spinel NO x  reduction additive.  
     
     
         46 . The process of  claim 33  wherein the additional NO x  reduction additive is a hydrotalcite containing composition.  
     
     
         47 . The process of  claim 1  wherein the particulate NO x  reduction composition has a mean particle size from about 50 to about 200 μm.  
     
     
         48 . The process of  claim 47  wherein the particulate NO x  reduction composition has a mean particle size from about 55 to about 150 μm.  
     
     
         49 . The process of  claim 1  or  3  wherein the particulate NO x  reduction composition has a Davison attrition index (DI) value of less than 50.  
     
     
         50 . The process of  claim 49  wherein the particulate NO x  reduction composition has a DI value of less than 20.  
     
     
         51 . The process of  claim 49  wherein the particulate NO x  reduction composition has a DI value of less than 15.  
     
     
         52 . The process of  claim 2  wherein the amount of the NO x  reduction composition is that amount sufficient to provide a ratio of ferrierite zeolite to Y-type zeolite in the total catalyst inventory of less than 2.  
     
     
         53 . The process of  claim 33  wherein the additional NO x  reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.  
     
     
         54 . A fluid cracking catalyst (FCC) composition, which composition comprises (a) a FCC cracking component suitable for catalyzing the cracking of hydrocarbons under FCC conditions, and (b) a particulate NO x  reduction composition having a mean particle size of greater than 45 μm and comprising (i) at least 10 weight percent of ferrierite zeolite, and (ii) about 5 to about 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, alumina phosphate, and mixtures thereof.  
     
     
         55 . The catalyst of  claim 54  wherein the FCC cracking component contains a Y-type zeolite.  
     
     
         56 . The catalyst of  claim 55  wherein the NO x  reduction composition is present in an amount sufficient to provide a ratio of ferrierite zeolite to Y-type zeolite of less than 2 in the total catalyst composition.  
     
     
         57 . The catalyst of  claim 54  wherein the amount of ferrierite zeolite present in the NO x  reduction composition is at least 30 weight percent of the composition.  
     
     
         58 . The catalyst of  claim 57  wherein the amount of ferrierite zeolite present in the NO x  reduction composition is at least 40 weight percent of the composition.  
     
     
         59 . The catalyst of  claim 58  wherein the amount of ferrierite zeolite present in the NO x  reduction composition is at least 50 weight percent of the composition.  
     
     
         60 . The catalyst of  claim 54  wherein the amount of ferrierite zeolite present in the NO x  reduction composition ranges from about 10 to about 85 weight percent of the composition.  
     
     
         61 . The catalyst of  claim 60  wherein the amount of ferrierite zeolite present in the NO x  reduction composition ranges from about 30 to about 80 weight percent of the composition.  
     
     
         62 . The catalyst of  claim 61  wherein the amount of ferrierite zeolite present in the NO x  reduction composition ranges from about 40 to about 75 weight percent of the composition.  
     
     
         63 . The catalyst of  claim 54  wherein the ferrierite zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium; alkali-metal and combinations thereof.  
     
     
         64 . The catalyst of  claim 54  wherein the ferrierite zeolite further comprises at least one stabilizing metal.  
     
     
         65 . The catalyst of  claim 64  wherein the stabilizing metal is a metal selected from the group consisting of Groups IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IIB, IIIA, IVA, VA, the Lanthanide Series of The Periodic Table, Ag and mixtures thereof.  
     
     
         66 . The catalyst of  claim 65  wherein the stabilizing metal is selected from the group consisting of Groups IIIB, IIA, IIB, IIIA, the Lanthanide Series of the Periodic Table, and mixtures thereof.  
     
     
         67 . The catalyst of  claim 66  wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof.  
     
     
         68 . The catalyst of  claim 64  wherein the stabilizing metal is incorporated into the pores of the ferrierite zeolite.  
     
     
         69 . The catalyst of  claim 54  wherein the inorganic binder in the particulate NO x  reduction composition is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof.  
     
     
         70 . The catalyst of  claim 69  wherein the inorganic binder is alumina.  
     
     
         71 . The catalyst of  claim 70  wherein the inorganic binder is an aluminum chlorohydrol.  
     
     
         72 . The catalyst of  claim 70  wherein the alumina is an acid or base peptized alumina.  
     
     
         73 . The catalyst of  claim 54  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.  
     
     
         74 . The catalyst of  claim 73  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.  
     
     
         75 . The catalyst of  claim 54  wherein the particulate NO x  reduction composition further comprises an additional zeolite other than ferrierite zeolite.  
     
     
         76 . The catalyst of  claim 75  wherein the additional zeolite is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms and a SiO 2  to Al 2 O 3  molar ratio less than about 500.  
     
     
         77 . The catalyst of  claim 76  wherein the SiO 2  to Al 2 O 3  molar ratio is less than 250.  
     
     
         78 . The catalyst of  claim 75  wherein the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-35, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite and mixtures thereof.  
     
     
         79 . The catalyst of  claim 78  wherein the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, Offretite, A, ZSM-12 and mixtures thereof.  
     
     
         80 . The catalyst of  claim 75 ,  76  or  78  wherein the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.  
     
     
         81 . The catalyst of  claim 80  wherein the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition.  
     
     
         82 . The catalyst of  claim 54  wherein the 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.  
     
     
         83 . The catalyst of  claim 82  wherein the matrix material is present in an amount less than 70 weight percent.  
     
     
         84 . The catalyst of  claim 54  further comprising at least one additional NO x  reduction composition.  
     
     
         85 . The catalyst of  claim 84  wherein the additional NO x  reduction composition is a non-zeolitic composition.  
     
     
         86 . The catalyst of  claim 85  wherein the additional NO x  reduction composition comprises (a) an acidic metal oxide containing substantially no zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and, (d) at least one noble metal component.  
     
     
         87 . The catalyst of  claim 84  wherein the additional NO x  reduction composition comprises (a) an acidic metal oxide support; (b) an alkali metal, alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and, (d) a transition metal selected from Groups IB and IIB of the Periodic Table, and mixtures thereof.  
     
     
         88 . The catalyst of  claim 84  wherein the additional NO x  reduction composition is a low NO x , CO combustion promoter composition which comprises (a) an acidic oxide support; (b) an alkali metal, an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) palladium.  
     
     
         89 . The catalyst of  claim 84  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.  
     
     
         90 . The catalyst of  claim 89  wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal.  
     
     
         91 . The catalyst of  claim 89  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.  
     
     
         92 . The catalyst of  claim 89  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.  
     
     
         93 . The catalyst of  claim 89  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.  
     
     
         94 . The catalyst of  claim 84  wherein the additional NO x  reduction additive is a zinc based catalyst.  
     
     
         95 . The catalyst of  claim 84  wherein the additional NO x  reduction additive is an antimony based NO x  reduction additive.  
     
     
         96 . The catalyst of  claim 84  wherein the additional NO x  reduction additive is a perovskite-spinel NO x  reduction additive.  
     
     
         97 . The catalyst of  claim 84  wherein the additional NO x  reduction additive is a hydrotalcite containing composition.  
     
     
         98 . The catalyst of  claim 54  wherein the particulate NO x  reduction composition has a mean particle size from about 50 to about 200 μm.  
     
     
         99 . The catalyst of  claim 98  wherein the particulate NO x  reduction composition has a mean particle size from about 55 to about 150 μm.  
     
     
         100 . The catalyst of  claim 54  wherein the particulate NO x  reduction composition has a Davison attrition index (DI) value of less than 50.  
     
     
         101 . The catalyst of  claim 100  wherein the particulate NO x  reduction composition has a DI value of less than 20.  
     
     
         102 . The catalyst of  claim 101  wherein the particulate NO x  reduction composition has a DI value of less than 15.  
     
     
         103 . The catalyst of  claim 84  wherein the additional NO x  reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals, and mixtures thereof.  
     
     
         104 . A method of reducing NO x  emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said method comprising contacting a hydrocarbon feedstock with a cracking catalyst at elevated temperature whereby lower molecular weight hydrocarbon components are formed, said cracking catalyst comprising the composition of  claim 54 ,  56 ,  64  or  75 .  
     
     
         105 . The method of  claim 104  further comprising recovering the cracking catalyst from said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst.  
     
     
         106 . The method of  claim 105  wherein the cracking catalyst is fluidized during contacting said hydrocarbon feedstock.  
     
     
         107 . The method of  claim 104  wherein the cracking catalyst further comprises an additional NO x  reduction additive composition.  
     
     
         108 . A fluid cracking catalyst comprising (a) a cracking component suitable for catalyzing the cracking of hydrocarbons, (b) at least 0.1 weight percent of ferrierite zeolite and (c) less than 50 weight percent of an inorganic binder material, components (b) and (c) being based oh the total weight of the cracking catalyst.  
     
     
         109 . The cracking catalyst of  claim 108  wherein said catalyst comprises integral particles which contain components (a), (b) and (c).  
     
     
         110 . The cracking catalyst of  claim 108  wherein component (b) comprises from about 0.1 to about 60 wt % of the cracking catalyst.  
     
     
         111 . The cracking catalyst of  claim 110  wherein component (b) comprises from about 1 to about 40 wt % of the cracking catalyst.  
     
     
         112 . The catalyst of  claim 108  further comprising at least one additional NO x  reduction composition.  
     
     
         113 . The catalyst of  claim 112  wherein the additional NO x  reduction composition is a non-zeolitic composition.  
     
     
         114 . The catalyst of  claim 113  wherein the additional NO x  reduction composition comprises (a) an acidic metal oxide containing substantially no zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and (d) at least one noble metal component.  
     
     
         115 . The catalyst of  claim 112  wherein the additional NO x  reduction composition comprises (a) an acidic metal oxide support; (b) an alkali metal, alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and, (d) a transition metal selected from Groups IB and IIB of the Periodic Table, and mixtures thereof.  
     
     
         116 . The catalyst of  claim 112  wherein the additional NO x  reduction composition is a low NO x , CO combustion promoter composition which comprises (a) an acidic oxide support; (b) an alkali metal, an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) palladium.  
     
     
         117 . The catalyst of  claim 112  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.  
     
     
         118 . The catalyst of  claim 117  wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal.  
     
     
         119 . The catalyst of  claim 117  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.  
     
     
         120 . The catalyst of  claim 117  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.  
     
     
         121 . The catalyst of  claim 117  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.  
     
     
         122 . The catalyst of  claim 112  wherein the additional NO x  reduction additive is a zinc based catalyst.  
     
     
         123 . The catalyst of  claim 112  wherein the additional NO x  reduction additive is an antimony based NO x  reduction additive.  
     
     
         124 . The catalyst of  claim 112  wherein the additional NO x  reduction additive is a perovskite-spinel NO x  reduction additive.  
     
     
         125 . The catalyst of  claim 112  wherein the additional NO x  reduction additive is a hydrotalcite containing composition.  
     
     
         126 . A method 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 the FCCU operating under FCC conditions with the cracking catalyst composition of  claim 108;  and (b) reducing the amount of NO x  emissions released from the regeneration zone of the FCCU by at least 10 percent as compared to the amount of NO x  emissions released in the absence of the NO x  reduction composition.  
     
     
         127 . The method of  claim 126  wherein step (b) is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained during the FCC process as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone.  
     
     
         128 . The method of  claim 126  or  127  wherein the amount of ferrierite zeolite present in the cracking catalyst composition comprises at least about 0.1 wt % of the cracking catalyst composition.  
     
     
         129 . The method of  claim 126  or  127  wherein the amount of ferrierite zeolite present in the cracking catalyst composition ranges from about 0.1 to about 60 wt % of the cracking catalyst composition.  
     
     
         130 . The method of  claim 129  wherein the amount of ferrierite zeolite present in the cracking catalyst composition ranges from about 1 to about 40 wt % of the cracking catalyst composition.  
     
     
         131 . The method of  claim 126  or  127  wherein the ferrierite zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof.  
     
     
         132 . The method of  claim 126  or  127  wherein the ferrierite zeolite further comprises at least one stabilizing metal.  
     
     
         133 . The method of  claim 132  wherein the stabilizing metal is a metal selected from the group consisting of Groups IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IIB, IIIA, IVA, VA the Lanthanide Series of The Periodic Table, Ag and mixtures thereof.  
     
     
         134 . The method of  claim 133  wherein the stabilizing metal is selected from the group consisting of Groups IIIB, IIA, IIB, IIIA and the Lanthanide Series of the Periodic Table, and mixtures thereof.  
     
     
         135 . The method of  claim 134  wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof.  
     
     
         136 . The method of  claim 132  wherein the stabilizing metal is incorporated into the pores of the ferrierite zeolite.  
     
     
         137 . The method of  claim 126  or  127  further comprising recovering the cracking catalyst and treating the used catalyst in a regeneration zone to regenerate said catalyst.  
     
     
         138 . The method of  claim 126  or  127  wherein the cracking catalyst is fluidized during contacting said hydrocarbon feedstock.  
     
     
         139 . The method of  claim 126  further comprising contacting the hydrocarbon feed with at least one additional NO x  reduction additive composition.  
     
     
         140 . The method of  claim 139  wherein the additional NO x  reduction additive composition is a non-zeolitic composition.  
     
     
         141 . The method of  claim 140  wherein the additional NO x  reduction additive composition comprises (a) an acidic metal oxide containing substantially no zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and (d) at least one noble metal component.  
     
     
         142 . The method of  claim 139  wherein the NO x  reduction additive composition is a low NO x , CO combustion promoter composition which comprises (a) an acidic oxide support; (b) an alkali metal and/or alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) palladium.  
     
     
         143 . The method of  claim 139  wherein the additional NO x  reduction additive 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.  
     
     
         144 . The method of  claim 143  wherein the metal-containing spinel comprises magnesium as said first metal and aluminum as said second metal.  
     
     
         145 . The method of  claim 143  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.  
     
     
         146 . The method of  claim 143  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.  
     
     
         147 . The method of  claim 143  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.  
     
     
         148 . The method of  claim 139  wherein the additional NO x  reduction additive composition comprises (a) an acidic oxide support; (b) an alkali metal and/or alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) a transition metal selected from the Groups IB and IIB of the Periodic Table.  
     
     
         149 . The method of  claim 139  wherein the additional NO x  reduction additive composition is a zinc based catalyst.  
     
     
         150 . The method of  claim 139  wherein the additional NO x  reduction additive composition is an antimony based NO x  reduction additive.  
     
     
         151 . The method of  claim 139  wherein the additional NO x  reduction additive composition is a perovskite-spinel NO x  reduction additive.  
     
     
         152 . The method of  claim 139  wherein the additional, NO x  reduction additive composition is a hydrotalcite containing composition.  
     
     
         153 . The cracking catalyst of  claim 108  wherein component (a) comprises a Y-type zeolite and component (b) is present in an amount sufficient to provide a ratio of ferrierite to Y-type zeolite of less than 2 in the total catalyst.  
     
     
         154 . The cracking catalyst of  claim 108  wherein component (b) further comprises at least one stabilizing metal.  
     
     
         155 . The cracking catalyst of  claim 154  wherein the stabilizing metal is a metal selected from the group consisting of Groups IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IIB, IIIA, IVA, VA, the Lanthanide Series of The Periodic Table, Ag and mixtures thereof.  
     
     
         156 . The cracking catalyst of  claim 155  wherein the stabilizing metal is selected from the group consisting of Groups IIIB, IIA, IIB, IIIA, the Lanthanide Series of the Periodic Table, and mixtures thereof.  
     
     
         157 . The cracking catalyst of  claim 156  wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof.  
     
     
         158 . The cracking catalyst of  claim 154  wherein the stabilizing metal is incorporated into the pores of component (b).  
     
     
         159 . The cracking catalyst of  claim 112  wherein the additional NO x  reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.  
     
     
         160 . The cracking catalyst of  claim 108  further comprising an additional zeolite other than ferrierite zeolite.  
     
     
         161 . The cracking catalyst of  claim 160  wherein the additional zeolite is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms and a SiO 2  to Al 2 O 3  molar ratio less than about 500.  
     
     
         162 . The cracking catalyst of  claim 161  wherein the SiO 2  to Al 2 O 3  molar ratio is less than 250.  
     
     
         163 . The cracking catalyst of  claim 160  wherein the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-35, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite and mixtures thereof.  
     
     
         164 . The cracking catalyst of  claim 163  wherein the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, Offretite, A, ZSM-12 and mixtures thereof.  
     
     
         165 . The cracking catalyst of  claim 160 ,  161  or  163  wherein the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.  
     
     
         166 . The cracking catalyst of  claim 165  wherein the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition.  
     
     
         167 . The method of  claim 139  wherein the additional NO x  reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.  
     
     
         168 . The process of  claim 2  wherein step (b) is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone.  
     
     
         169 . The cracking catalyst of  claim 108  wherein component (c) comprises from about 1 to about 45 weight percent of the cracking catalyst.  
     
     
         170 . The method of  claim 126  wherein the cracking catalyst further comprises an additional zeolite other than ferrierite zeolite.  
     
     
         171 . The process of  claim 170  wherein the additional zeolite is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms and a SiO 2  to Al 2 O 3  molar ratio less than about 500.  
     
     
         172 . The process of  claim 171  wherein the SiO 2  to Al 2 O 3  molar ratio is less than 250.  
     
     
         173 . The process of  claim 170  wherein the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-35, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite and mixtures thereof.  
     
     
         174 . The process of  claim 173  wherein the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, Offretite, A, ZSM-12 and mixtures thereof.  
     
     
         175 . The process of  claim 170 ,  171  or  173  wherein the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.  
     
     
         176 . The process of  claim 175  wherein the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition  
     
     
         177 . The catalyst of  claim 108  wherein the ferrierite zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof.  
     
     
         178 . The method of  claim 126  wherein the cracking catalyst composition comprises a Y-type zeolite as component (a) and component (b) is present in an amount sufficient to provide a ratio of ferrierite to Y-type zeolite of less than 2 in the total catalyst composition.  
     
     
         179 . The method of  claim 104  wherein the reduction of NO x  emissions is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone.  
     
     
         180 . The method of  claim 107  wherein the additional NO x  reduction additive composition is a non-zeolitic composition.  
     
     
         181 . The method of  claim 107  wherein the NO x  reduction additive composition is a low NO x , CO combustion promoter composition which comprises (a) an acidic oxide support; (b) an alkali metal and/or alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) palladium.  
     
     
         182 . The method of  claim 107  wherein the additional NO x  reduction additive 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.  
     
     
         183 . The method of  claim 182  wherein the metal-containing spinel comprises magnesium as said first metal and aluminum as said second metal.  
     
     
         184 . The method of  claim 182  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.  
     
     
         185 . The method of  claim 182  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.  
     
     
         186 . The method of  claim 182  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.  
     
     
         187 . The method of  claim 107  wherein the additional NO x  reduction additive composition comprises (a) an acidic oxide support; (b) an alkali metal and/or alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) a transition metal selected from the Groups IB and IIB of the Periodic Table.  
     
     
         188 . The method of  claim 107  wherein the additional NO x  reduction additive composition is a zinc based catalyst.  
     
     
         189 . The method of  claim 107  wherein the additional NO x  reduction additive composition is an antimony based NO x  reduction additive.  
     
     
         190 . The method of  claim 107  wherein the additional NO x  reduction additive composition is a perovskite-spinel NO x  reduction additive.  
     
     
         191 . The method of  claim 107  wherein the additional NO x  reduction additive composition is a hydrotalcite containing composition.  
     
     
         192 . The method of  claim 107  wherein the additional NO x  reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.  
     
     
         193 . The method of  claim 180  wherein the additional NO x  reduction additive composition comprises (a) an acidic metal oxide containing substantially no zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and (d) at least one noble metal component.