Title of Invention	"A PROCESS OF REDUCING NOX EMISSIONS FROM THE REGENERATION ZONE DURING FCC OF A HYDROCARBON FEEDSTOCK INTO LOWER MOLECULAR WEIGHT COMPONENTS"
Abstract	A process of reducing NOX emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said process consisting of: (i) contacting a hydrocarbon feedstock in a catalytic cracking zone operating at a temperature ranging from 480 °C to 600 °C under fluid catalytic cracking (FCC) conditions with a circulating catalyst inventory of FCC catalytic cracking catalyst comprising a Y-type zeolite and a particulate NOx reduction composition having a mean particle size of greater than 45 (am and comprising (i) at least 30 weight percent of ferrierite zeolite, and (ii) from 5 to 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, aluminum phosphate and mixtures thereof, to produce an effluent comprising cracked products and spent catalyst containing coke and strippable hydrocarbons; (ii) discharging and separating a vapor phase rich in cracked products and a solids rich phase comprising the spent equilibrium cracking catalyst and NOx reduction composition; (iii) removing the vapor phase as product; (iv) stripping the spent FCC cracking catalyst and NOx reduction composition to remove the strippable hydrocarbons; and (v) oxidatively regenerating the spent FCC cracking catalyst and the NOx reduction composition in a regeneration zone operating at a temperature of 600 °C to 800°C to remove the coke from the FCC cracking catalyst and NOx reduction composition and reduce the amount of NOx emissions released from the regeneration zone by at least 10% relative to the amount of NOx emissions released in the absence of the NOx reduction composition; and (vi) recycling the regenerated FCC catalyst and regenerated NOx reduction composition to the cracking zone for further cracking and NOx reduction.

Title of Invention

"A PROCESS OF REDUCING NOX EMISSIONS FROM THE REGENERATION ZONE DURING FCC OF A HYDROCARBON FEEDSTOCK INTO LOWER MOLECULAR WEIGHT COMPONENTS"

Abstract

A process of reducing NOX emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said process consisting of: (i) contacting a hydrocarbon feedstock in a catalytic cracking zone operating at a temperature ranging from 480 °C to 600 °C under fluid catalytic cracking (FCC) conditions with a circulating catalyst inventory of FCC catalytic cracking catalyst comprising a Y-type zeolite and a particulate NOx reduction composition having a mean particle size of greater than 45 (am and comprising (i) at least 30 weight percent of ferrierite zeolite, and (ii) from 5 to 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, aluminum phosphate and mixtures thereof, to produce an effluent comprising cracked products and spent catalyst containing coke and strippable hydrocarbons; (ii) discharging and separating a vapor phase rich in cracked products and a solids rich phase comprising the spent equilibrium cracking catalyst and NOx reduction composition; (iii) removing the vapor phase as product; (iv) stripping the spent FCC cracking catalyst and NOx reduction composition to remove the strippable hydrocarbons; and (v) oxidatively regenerating the spent FCC cracking catalyst and the NOx reduction composition in a regeneration zone operating at a temperature of 600 °C to 800°C to remove the coke from the FCC cracking catalyst and NOx reduction composition and reduce the amount of NOx emissions released from the regeneration zone by at least 10% relative to the amount of NOx emissions released in the absence of the NOx reduction composition; and (vi) recycling the regenerated FCC catalyst and regenerated NOx reduction composition to the cracking zone for further cracking and NOx reduction.

Full Text	[0001] The application is a continuation in part application of U.S. Patent Application Serial No. 10/702,240, filed November 6, 2003. FIELD OF THE INVENTION 10002] The present invention relates to NOx reduction compositions and the method of use thereof to reduce NOx emissions in refinery processes, and specifically in fluid catalytic cracking (FCC) processes. More particularly, the present invention relates to NOx reduction compositions and their method of use to reduce the content of NOx off gases released from a fluid catalytic cracking unit (FCCU) regenerator during the FCC process without a substantial change in hydrocarbon conversion or the yield of valuable cracked products. BACKGROUND OF THE INVENTION [0003] In recent years there has been an increased concern in the United States and elsewhere about air pollution from industrial emissions of noxious oxides of nitrogen, sulfur and carbon. In response to such concerns, government agencies have placed limits on allowable emissions of one or more of these pollutants, and the trend is clearly in the direction of increasingly stringent regulations. [0004] NOx, or oxides of nitrogen, in flue gas streams exiting from fluid catalytic cracking (FCC) regenerators is a pervasive problem. Fluid catalytic cracking units (FCCU) process heavy hydrocarbon feeds containing nitrogen compounds, a portion of which is contained in the coke on the catalyst as it enters the regenerator. Some of this coke-nitrogen is eventually converted into NOx emissions, either in the FCC regenerator or in a downstream CO boiler. Thus, all FCCUs processing nitrogen-containing feeds can have a NOx emissions problem due to catalyst regeneration. [0005] In the FCC process, catalyst particles (inventory) are continuously circulated between a catalytic cracking zone and a catalyst regeneration zone. During regeneration, coke deposited on the cracking catalyst particles in the cracking zone is removed at elevated temperatures by oxidation with oxygen containing gases such as air. The removal of coke deposits restores the activity of the catalyst particles to the point where they can be reused in the cracking reaction. In general, when coke is burned with a deficiency of oxygen, the regenerator .flue gas has a high CO/CC2ratio and a low level of NOx, but when burned with excess oxygen, the flue gas has a high level of NOx and a reduced CO content. Thus, CO and Nx or mixtures of these pollutants are emitted with the flue gas in varying quantities, depending on such factors as unit feed rate, nitrogen content of the feed, regenerator design, mode of operation of the regenerator, and composition of the catalyst inventory. [0006] Various attempts have been made to limit the amount of NOX gases emitted from the FCCU by treating the NOX gases after their formation, e.g., post-treatment of NOX containing gas streams as described. in U.S. Paient Nos. 4,434,347, 4,778,664, 4,735,927, 4,798,813, 4,855,115, 5,413, 699, and 5,547,648. [0007] Another âpproach has been to modify the operation of the regenerator to parţial'bum and then ireal the NO* precursors in the flue gas before they are converted to NOX> e.g., U.S. Patent Nos. 5,173,278, 5,240,690, 5,372,706, 5,413,699, 5,705,053, 5,716,514, and 5,830,346. [0008] Vet another approach has been io modify the operation of the regenerator as to reduce NO„ emissions, e.g., U.S. Patent 5,382,352, or modify the CO combustion promoter used, e.g., U.S. Patents 4,199,435, 4,812,430, and 4,812,431. Enrichment of air with oxygen in a regenerator operating in parţial bum mode has also been suggesied, e.g., U.S. Patent 5,908,804. [0009] Additives have also been used in attempts to deal with NO* emissions. U.S. Patent Nos. 6,379,536, 6,280,607, 6,129,834 and 6J43.167 disclose the use of NOX removal compositions for reducing. NOX emissions from the FCCU regenerator. U.S. Patent Nos. 6,358,881 and 6,165,933 also disclose a NOx reduction composition, which promotes CO combustion during the FCC catalyst regeneration process step while simultaneously reducing the level of NOX emitted during the regeneration step. NOx reduction compositions disclosed by these paients may be used as" an additive which is circulated along with the FCC catalyst inventory, or incorporated as an integral component of the FCC catalyst, [0030] U.S. Paient Nos. 4,973,399 and 4,980,052 disclose reducing emissions of NO, from the regenerator of the FCCU by incorporating into the circulati.ng invemory of cracking catalyst separaie additive particles containing a copper-loaded zeolite. [0011] Many additive compositions heretofore used to control NOX emissions have typ'ically caused a significant decrease in hydrocarbon conversion or the yield of valuable cracked products, e.g., gasoline, light olefins and liquefied petroleum gases (LPGs), while increasing the production of coke. lt is a highly desirable characteristic for N0„ additives added to the FCCU not io affect the -cracked product yields or change the overalî unit conversion, The operation of the FCCU is typically optimized • based on the unit design, feed and catalyst, to produce a slate of cracked produ'cts, and maximize refinery profitability. This product slate is based on the value model of the specific refinery. For exarnple, during the-peak summer driving season-many refiners want to maximize gasoline production, while during the winler season refirîers may want to maximize heating oi] production. In other cases a refinery may find it profitable to produce light olefins products that can be sold in the open.market .or used in an associated petrochemical plant as feedstocks. [0012] When a NO* reduction additive increases coke production, the FCCU may have insufficient air capacity to burn the extra coke and may result in a lower feed thr.oughput in the unit. If the additive increases -the production of low value dry gas, the production of more valuable products may decrease. An incfease in dry gas may exceed the ability of the unit to handle it, thus forcing- a reduction of the amount of feed processed. While an additive that increases ligbt olefins production may be desirable if the refinery values these products and the unit nas the equipment necessary io process the extra light hydrocarbons, the additive may, however, reduce profitability if the refinery's goal is to maximize gasoline production; Light olefins are typically made in the FCCU at the expense of gasoline production. . Eve'n ah. additive which increases unit conversion may be undesirable if it affects product yields, causes the unit io reach an equipment limitation, and/or decreases the amount of feed that can be processed. . . • [0013] Consequently, any change to the FCCU that affects the product slate or changes the ability to process feed at the desired rate can be detrimemal to the refinery profitability. Therefore, there exists a need for NOX control compositions which do not significantly affect produci yields and overall unit conversion. SUMMARY OF THE INVENT10N [0014] ]t has now been discovered that the incorporation of a ferrierite zeolite component with a catalytically cracking caialyst inventory, in particular a cracking catalyst inveniory coniaining an active Y-type zeolite, being circulated throughout a fluid catalytic cracking unit (FCCU) during a fluid catalytic cracking (FCC) process provides superior NO* control performance without substantially changing or affecting the hydrocarbon conversion or the yield of cracked petroleum- products produced during the FCC process. [0015] In accordance with the present invention, novei NOX reduction compositions are provided. Typically, the N0> reduction compositions comprise a particulate composition confa'ining panicles of ferrierite zeolite. The ferrierite zeolite may be added as a separate additive partide to a circulating inventory of the cracking catalyst or incorporated directly into the Y-type zeolite coniaining cracking catalyst as an integral component of the catalyst. In a preferred embodiment of the invention,. the ferrierite zeolite are separate additive particJes bound with an inorganic binder. The binder preferably comprises silica, alumina or silica alumina. Preferably, the ferrierite zeolite is exchanged with hydrogen, ammonium, alkali metal and combinations thereof. The preferred alkali metal is sodium, potassium and combinations thereof. [0016] In one aspect of the invention, nove] ferrierite zeolite-contain'ing NOX reduction compositions are provided which are added to a circulating inventory of the catalytic cracking catalyst as a separate admixture of particJes to reduce NOX emissions released from the FCCU regenerator during th'e FCC process. [0017] In another aspect of the invention, nove] NOX reduction compositions are provided which comprise ferrierite zeolite incorporated as an integral component of the FCC catalyst, preferably coniaining a Y-type zeolite active component. [0018] In yet another aspect of the invention, nove] NOx reduction compositions are provided which compositions reduce NO, emissions from the FCCU regenerator during the FCC process while substantially maintaining hydrocarbon conversion and the yield of cracked petroleum products and minimizing an increase in the production of coke. [0039] It is another aspect of the present invention to provide a process. for the red'uction of the content of NOx in the off gas of the FCCU -regenerator during the FCC process using NOX reduction compositions in accordance with the present invention. [0020] Another aspect of the invention is io provide improved FCC processes for th'e reduction of the content of NO* in the off gases of the FCCU regenerator withoirf substantially affecting hydrocarbon conversion or the yield of petroleum products produced during the FCC process. [0021] These and other aspects of the present invention are described in further detail below. BR1EF DESCRIPT.10N OF THE DRAWINGS [0022] The FJGURE is a graphic representation of the effectiveness-of Additive A and Additive B, prepared in EXAMPLES l and 2, respectively, to reduce NOX emissions from a DCR regenerator versus time on stream, when the addiţives are ® blended with a cornmercially available cracking catalyst (SUPERNOVA -DMR+, obtained from Grace Davison, Columbia, MD), which contains 0.25 weight percent of a platinum promoter, CP-3® (obtained from Grace Davison, Columbia, MD) and which was deactivaied using the Cyclic Propylene Steaming procedura as.described in EXAMPLE 3. DETA1LED DESCRIPT1ON OF THE INVENT1ON [0023] Although severa] nitrogen oxides are known which are relatively stabîe at ambient conditions, for purposes of the present invention, NOX will be used herein to represent nitric oxide, nitrogen dioxide (the principal noxious oxides of nitrogen) as well as ^CXi.NîOs and mixtures thereof. [0024] The present invention encompasses the discovery that the use of ferrierile zeolite containing NOX reduction composilions in combination with a fluid catalytic cracking (FCC) catalyst, preferably a catalyst comprising an active Y-type zeolite, is very effective for the reduction of NOx emissions released from the FCCU regenerator under FCC process conditions without a substanţial change in hydrocarbon feed conversion or the yield of cracked products. The NOx reduction compositions typically comprise a particulate composition containing particles of ferrierite zeolite. In a preferred embodiment of the invention, the ferrierite panicles are bound with an inorganic binder. The nove] ferrierite zeolite-comaining NOX reduction compositions may be added to the circulaiing' inventory of ihe catalytic cracking catalyst as a separate partide additive or incorporaled as an integral component into the cracking catalyst. [0025] For purposes of the present invention, the phrase "a substanţial change in hydrocarbon feed co'nversion or the yield of cracked products" is defined -herein to mean in the alternative, (i) less than a 50% relative change, preferably less than a 30% relative change and most preferably less than a 15% relative change in the yield of LPG (liquefied petrol cum gas) as compared to the baseline yield of the same or substaniially the Same product; or (ii) less than a 30% relative change, preferably less than a 20% relative change and most preferably less than a 30% relative change in the yield of LCO (lighi cycle oils), bottoms and gasoline in combination with LPG as compared to the baseline yield of the same or substantially the same products; or (iii) less than a 10% relative change, preferably less than a 6.5% relative change and most preferably less than a 5% relative change in the hydrocarbon feed conversion as compared to the baseline conversion. The conversion is defined as 100% times (l -bottoms yield - LCO yield). When the NOX reduction composition is used as a separate additive, the baseline is the mean conversion or yield of a product in the FCCU, operating with the same or substantially the same feed and under the same or substaniially the same reacîion and unii conditions, but before the additive .of the present invention is added to the catalyst inventory.' When the NOx reduction composition is inîegrated or incorporated into the cracking catalyst particles to provide an integral NOx reduction catalyst system, a significant change in the hydrocarbon conversion or yield of cracked products is determined using a baseline defined as the mean conversion or yield of a product in the same or substantially the same FCCU operating with the same or substantially the same feed, under the same or substantially the same reaction and unit conditions, and with a cracking catalyst inventory comprising the same or subsiantially the same cracking catalysi composition as that containing the NOX reduction composition, except that the NOX reduction composition is replaced in the cracking catalyst with a matrix component such as kaoJin or other filler. The^percent changes specified above are derived from statistica] analysis of DCR operating data. [0026] Any f emerit e zeolite is useful îo prepare the NOX reduction compositions of the invention. However, it is preferred that the ferrierite zeolite has a surface areâ of at least 100 m2/g. m ore preferably at Jeast 200 m2/g and rnost preferably at least 300 m2/g and a S i Os to Al2Oa molar ratio of less than 500, preferably less than 250, most preferably, less than JOO. In one embodiment of the invention; the ferrierite zeolite-is exchanged wjth a maierial selecied from the group consisting of .hydrogen, ammonium, alkali metal and combinations thereof, prior to incorpdration into .the binder or FCC catajyst. The preferred -alkali metal is one selected from the group t* consisting of sodium, potassium and mixtures thereof. [0027] Optionally, the'ferrierite zeolite may contain stabilizing amounts, e.g., up to about 25 weight percent, of a stabilizing metal (or metal ion), preferably incorporated into. the pores of the zeolite. Suitable stabilizing metals include, but are not limited to, metals selected from the group consisting of Groups ]]A, JJIB, IVB, VB, VIB, V1IB, V]D, 11B, ]]1A, IVA, VA, the Lanthanide Series of The Periodic Table, Ag and mixtures thereof. Preferably, the stabilizing metals are selected from the group consisting of Groups JJJB, ]]A, J1B, 111A and the Lanthanide Series of the Periodic Table, and mixtures thereof, Most preferably, the stabilizing metals are selected from the group consisting of lanthanum, aluminum, magnesium, zinc, and mixtures thereof. The metal may be incorporated into the pores of the ferrierite zeolite by any method known in the art, e.g,, ion exchange, impregnation or the like. For purposes of this invention, the Periodic Table referenced herein above is the Periodic Table as published by the American Chemical Society. [0028] The amount of ferrierite zeolite used in the NOx reduction compositions of the invention will vary depending -upon severa] factors, including but pot limited to, the ' mode of combining the ferrierite zeolite with the catalytic cracking catalyst and the type of cracking catalyst used. In one embodiment of the invention, the NO* reduction compositions of the invention are separate catalyst/additive compositions and comprise a particulele composition formed by binding particles of a ferrierite zeolite with a suitable inoreanic binder. Generally, the amount of ferrierite zeolite present in the particuhite NOX reduction compositions is at least ]0, preferably at least 30, most preferably al least 40 and even more preferably at least 50, weight percent based on the total weight of the composition. Typically, the particulate catalyst/additive composition of the invention contains from about ] O to abouî 85, preferably from about 30 to about 80, most preferably, from about 40 to about 75, weight percent of ferrierite zeolite based on the total weight of the catalyst/additive composilion. [0029] Binder materials useful to prepare the particulate compositions of the invention include any inorganic binder which is capable of binding ferrierite zeolite powder to form particles having properties suitable for use in the FCCU under FCC process conditions. Typical inorganic binder materials useful to prepare compositions in accordance wiih the present invention include, but are not limited to, alumina, silica, silica alumina, aluminum phosphate and the like, and mixtures thereof. Preferably, the binder is selected from the group consisting of alumina, silica, silica alumina. More preferably, the binder comprises alumina. Even more preferably, the binder comprises an acid or base peptized alumina, Most preferably, the binder comprises an alumina sol, e.g., alurninum chlorohydrol. Generally, the amount of ' binder material present in the particular NOX reduction compositions comprises from about 5 to about 50 weight percent, preferably from about 10 to about 30 weight percent, rnost preierably from about 15 to about 25 weight percent, of the NO* reduction composition of the invention. [0030] Additional- materials optionally present in the compositions of the present invention include, but are not limited to, fillers-(e.g., kaolin clay) or matrix materials (e.g., alumina, silica, silica alumina, yttria, lanthana, ceria, neodymia, samaria, europia, gadolinia, litania, zirconia, praseodymia and mixtures thereof). When used, the additional materials are used in an amount which does not significantly adversely affect the performance of the compositions to reduce NOX emissions released from the FCCU regenerator under FCC conditions, the hydrocarbon feed conversion or the product yîeld of ihe cracking catalyst. In general the additional materials will comprise no more than about 70 weight percent of the compositions. It-is preferred, however, that the compositions of the invention consist essentially of ferrierite and an inoreanic binder. [0031] Paniculate NOX reduciion compositions of the invention should have a partide size sufficient io permit the composition to be circulated throughout Ihe FCCU simulianeously with the inventory of cracking catalyst during the FCC process. Typically the composition of the invention wj]] have a mean partide size of greater than 45 \|jm. Preferably, the mean panicle size is from about 50 to about 200 p.m, most preferably from about 55 to about 150 um, even more preferred from about 60 to about 120 (.im. The compositions of the invention typically have a Davison attrition index (DI) value of less than about 50, preferably less than about 20, most preferably less than about 15. •• . [0032] While the present invention is. not limited to any panicular process of ** preparation, typically the particulaie NO* reduction compositions of the invention are prepared by forming an aqueous slurry containing the ferrierite zeolite, opţional zeolite components, the inorganic binder and opţional matrix materials, in an amount sufficient io provide at least 10.0 weight percent of ferrierite zeolite and at least 5.0 weight percent of binder material in the final NOX reduction composition and, thereafter, spray drying the aqueous slurry to form particles.' The spray-dried particles are optionally dried at a- sufficient temperature for a sufficient time to remove volatiles, e.g., at about 90 C to about 320 C for about 0.5 to about 24-hours. In a preferred ernbodiment of the invention, the ferrierite zeolite containing aqueous slurry is rnilled prior io spray-drying io reduce the mean partide size of materials contained in the slurry io 10 um or less, preferably 5 um or less, most preferably 3 (jm or less. The aqueous slurry containing ferrierite zeolite rnay be milled prior to or after incorporation of the binder and/or matrix materials as desired. [0033] The spray-dried composition may be calcined at a temperature and for a time sufficieni to remove volatiles and provide sufficient hardness to the binder for use in the FCCU under FCC process conditions, preferably from about 320°C to about 900°C from about 0.5 to about 6 hours. [0034] Optionally, the dried or calcined composition is washed or exchanged with -an aqueous solution of ammonia or ammonium salt (e.g., ammonium sulfate, nitrate, chloride, carbonate, phosphate and the like), or an inorganic or organic acid (e.g., sulfuric, nitric, phosphoric, hydrochloric, acetic, formic and the like) to reduce the amount of alkaline rnetals, e.g. sodium or potassium, in the finished product. [0035] Participate NOX reduction compositions of the invention are circulated in the form of separate partide addhives along with the rnain cracking catalyst throughout the FCCU. Generally, the catalyst/additive composition is used in an amount of at least 0.1 weight pcrcent of the FCC catalyst inventory. Preferably the amount of the catalyst/additive composition used ranges from about 0.1 to about 75 weight percent, most preferably from about ] to about 50 weight percent of the FCC caîalyst inventory. Separate partide caialyst/additive compositions of the invention may be added to the FCCU in the convenţional manner, e.g., with make-up catalyst to the regenerator or by any oiber convenient method. [0036] In a second embodiment of the invention, the ferrierite zeolite is integrated or incorporated into the cracking catalyst panicles thernselves to provide an integra) NO* reduction catalyst system. In accordance with this embodiment of the invention, the ferrierite zeolite may be added to the catalyst at any stage during catalyst manufacturing prior io spray drying the cracking catalyst slurry to obtain the fluid cracking catalyst, regardless of any additional opţional or required processing steps needed to finish the cracking catalyst preparation. Without intending to limit the incorporation of the ferrierite, and any opţional zeolite components, within the cracking catalyst to any specific method of cracking catalyst manufacturing, typically > the ferrierite zeolite, any additional zeolites, the cracking catalyst zeolite, usually USY or REUSY-type, and any matrix materials are slurried in water. The slurry is milled to reduce the mean partide size of solids in the slurry to less than ]0 pm, preferably to less than 5 um, most preferably less than 3 um. The milled 'slurry is combined with a suitable inorganic binder, i.e., a silica sol binder, and an opţional matrix material, e.g. clay. The resulting slurry is mixed and spray-dried io provide a catalyst material. The spray-dried catalyst is optionally washed using an aqueous solution of ammonium hydroxide, an arnmonium salt, an inorganic or organic acid, and water to remove the undesirable salts. The washed catalyst may be exchanged with a water soluble rare-earth salt, e.g., rare-earţb chlorides, nitrates and the like. [0037] Alternative]y, the ferrierite zeolite, opţional addilional z.eolites, the cracking catalysl zeoJite, any matrix materials, a rare-earth water soluble salt, clay and alumina s o] binder are slurried in water and blended. The slurry is milled'and spray-dried. The spray-dried catalyst is calcined at aboui 250°C to about 900 C. The spray-dried catalyst may then optionally be washed using an aqueous solution of ammonium hydroxide, an ammonium sa]t, ari inorganic or organic acid, and water to remove the undesirable salts. Optionally, ihe catalyst may be exchanged with a water-soluble rare-earth salt after it has been washed, by any of the methods known in the art. [0038] When integrated into the FCC catalyst panicles, the ferrierite zeolite compound lypically represents at least about 0.] weight percent of the FCC catalyst-partide. Preferably, the amoum of the ferrierite zeolite use'd ranges frorn about 0.1. to about 60 weight percent, moşi preferably from about ] to about 40 wejght percent, of the FCC cataJyst particJes. [0039] The integrated FCC catalyst will.typically comprise the ferrierite zeolîte along with the cracking catalyst zeolite, inorganic binder materials and optionally, matrix, fillers, and other additive components such as metals traps (for examp]e, traps for Ni and V) to make up the cracking catalyst. The cracking catalyst zeolite, usually a Y, USY or REUSY-type, provides the majority of the cracking activity and is typically present in a range from about 10 io about 75, preferably from about 15 to about 60 and most preferably from about 20 to about 50 weight percent based on the total weight of the composition. Inorganic binder materials useful to prepare integrated catalyst cornpositions in accordance with the present invention include, any inorganic materia] capable of bmding the components of the integrated catalyst to form particles having propenies suitable for use in the FCCU under FCC process conditions. Typically, the inorganic binder materials include, but are .not limited to, alumina, silica, silica alumina, aluminum phosphate and the like, and mixtures thereof. Preferably, the binder is selected from the group consisting of alumina, silica, silica alumina. Generally, the amount of binder material .present in the integrated catalyst composition is less than 50 weight percent, based on the total weight of the catalyst composition. Preferably, the amount of binder materia] present in the integrated catalyst composition ranges from about 5 to about 45 weight percent, most preferably from about J O to about 30 weight percent and even more preferably from about 15 to about 25 weight percent, based on the total weight of the composition. [0040] The matrix maierials optionally present in the integrated catalyst cornpositions of the presenl invention include, but are not limited to alumina, silica alumina, rare earth oxides such as lanthana, transition metal oxides such as titania, zirconia, and manganese oxide, Group 11A oxides such as magnesium and barium oxides, clays such as kaolin, and mixtures thereof. The matrix.or fillers may be present in the integra] catajyst in' the amouni of less than 50 weight percent based on the total weight of the composition. Preferably, the matrix and fillers, if any, are present in an amount ranging from about ] io about 45 weight present based on the total weight of the catalyst composition. [0041] The partide size and attrition propenies of the integral catalyst affect fluidization propenies in the unit and determine how well the catalyst is relained in the commercia] FCC unit. The iniegral catalyst composition of the invention typically has a mean partide size of about 45 to about 200um, more preferabJy from about 50unrto about J50fjm. The attrition propenies of the integral catalyst, as measured by the Davison A'tirition Index (DI), have.a Dl value of less'than 50, more preferably less than 20 and most preferably less than 15. [0042] In a preferred embodiment of the invention, the FCC cracking catalyst contains a Y-type zeolite. The ferrierite zeolite may be added as a separate additive partide to a circulating inventory of the cracking catalyst or incorporated directly into the Y-type zeoliîe containing cracking catalyst as an integra] component of the catalyst. In either case, it is preferred that ferrierite zeolite is present in the final composition in an amount sufficient to provide in the total catalyst inventory a ratio of ferrierite zeolite to Y-type zeolite of less than 2, preferably less than J. [0043] ]t is also wjtbin the scope of the invention-to include additional zeolite components in the ferrierite zeolite containing NO* reduction compositions of the invention. The additional zeolite component may be any zeolite which does not adversely affect the NO* reduction performance or căuşe a substanţial change in hydrocarbon conversion or cracked product yields during the FCC process. Preferably, the addilional zeolite component is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms with a SiO? to AlsO.i molar ratio of less than about 500, preferably less than 250. Preferably, the additional zeolite component is a zeolite selected from the group consisting of ZSM-5, ZSM-]], beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-32, ZSM-23, ZSM-18, ZSM-22, ZSM-35, ZSM-57, ZSM-61, ZK-5, Nai Nu-87, Cit-], SSZ-35, SSZ-48, SSZ-44, SSZ-23, Dachiardiie, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite or mixtures thereof. Most preferably the addilional zeolite component is selecied from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenhe, MC3V1-56, Zeo]ite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, Offretite, A, ZSM-12 and mixtures thereof. The additional zeolite component is used in any arriounî ihat does not significantly adversely affect the performance of the NOX reduction compositions to reduce NOX emissions and substantialjy maintain the hydrocarbon conversion or the product yields of the cracking catalyst relative to the use of the cracking catalyst without the catalyst/additive composition. Typic'ally, the t* additiona] zeolhe component is used in an amount ranging from about l to about 80, preferably from about '10 to about 70, weight percent of the catalyst/additive composition. Where the NO* reduction composition is used as an integra] component of the catalyst, the additional zeolite component is preferably used in an amount ranging from about 01 io about 60, moşi preferably from about 1-to about 40, weight percent of the catalyst composition. [0044] Somewhat briefly, the FCC process involves the cracking of heavy hydrocarbon feedstocks to lighter products by contact of the feedstock in a cyclic cataJyst recircuJalion crack'ing process with a circulating fluidizable cracking catalyst inventory consisting of panicles having a mean size ranging from.about 50 to about 150 pm, preferably from about 60 to about 120 um. The catalytic cracking of these relatively high molecular weight hydrocarbon feedstocks results in the production of a hydrocarbon product of lower molecular weight. The significant sieps in the cyclic FCC process are: (i). tbe feed is catalytically cracked in a catalytic cracking zone, hormally a riser cracking zone, operating at catalytic cracking conditions by contactîng feed with a source of hoţ, regenerated cracking catalyst to produce an effluent comprising cracked products and spent catalyst • containing coke and strippable hydrocarbons; (ii) the effjuent is discharged and separated, normally. in one or more cyclones, into a vapor phase rich in cracked product and a solids n eh phase comprising the spent catalyst; (iii) Lhe vapor phase is removed as product and fractionated in the FCC main column and its associated .side columns to form gas and liquid cracking products including gasoline; (iv) the spent catalyst is stripped, usually with steam, to remove occluded hydrocarbons from the catalyst, after which the stripped catalyst is oxidatively regenerated in a catalyst • regeneration zone to produce hoţ, regenerated catalyst which is then recycled to the cracking zone for cracking further . quantities of feed. [0045] Convenţional FCC catatysts include, for example, zeolite based catalysts with a faujasite cracking component as described in the seminal review by Venuto and Habib, Fluid Caialyiic Cracking with Zeoliie Caialysis, Marcel Dekker, New York 1979, ISBN 0-8247-6870-1, as well as in numerous other sources such as Sadeghbeigi, Fluid Caialytic Cracking Handbook, Gulf Publ. Co. Houston, 1995, ISBN 0-88415-290-1. Preferably, the FCC catalyst is a catalyst comprising a Y-t.ype zeolite active cracking component. In a particulari)' preferred embodiment of the invention, the FCC catalysts consist of a binder, usually silica, alumina, or silica alumina, a Y-type zeolite active component, one or more matrix aluminas and/or silica aluminas, and fillers such as kaolin clay. The Y-type zeolite may be present in one or more forms and may have been ultra stabilized and/or treated with stabilizing cations such as any of the rare-earths. [0046] Typical FCC processes are conducied at reaction temperatures of 480°C to 600°C with catalyst regeneration temperatures of 600 C to 800 C. As it is well known in the an, the catalysî regeneration zone may consist of a single or multiple reactor vessels. The compositions of ihe invention may be used in FCC processing of any ţypical hydrocarbon feedstock. Suitable feedstocks include petroleum distillates or residuals of crude oils, which when catalytically cracked, provide either a gasoline or a gas oii product. Synthetic feeds having boiling points of about 204°C to about 816°C, such as oii from coal, tar sands or shale oii, can also be included. [0047] In order to remove coke from the catalyst, oxygen or ajr is added to the reeeneration zone. This is performed by a suitable sparging device in the bonom of he regeneration] zone, or if desired, additional oxygen is added to the dilute or dense phase of the regeneration zone. [0048] NO„ reduction compositions in accordance with the invention dramatically reduce, i.e., by at least 10%, preferably at least 20%, the emissions of NOx in the FCCU regenerator effluent during the catalyst regeneration, while substantially maintaining the hydrocarbon feed conversion or the yield of cracked products, e.-g., • gasoline and lignt olefins, obtained from the cracking catalyst. In some casfes, NOX reduction of 90% or greater is readily achievable using the compositions and.method of the inventJon without significantly affecting the cracked products yields or feed conversion. However, as will be understood by one skilled in the catalyst' art, the â* extent of NOX reduction will depend on such factors as, for example, the composition and amount of the additive utilized; the design and the manner in which the catalytic cracking unit is operated, including but not limited to oxygen level and distribution of air in the regenerator, catalyst bed depth in the regenerator, stripper operation and regenerator lemperalure, the properties of the hydrocarbon feedstock cracked, and the presence of other catalytic additives that may affect the chemistry and operation of the regenerator. Thus, since each FCCU is different in some or al l of these respects, the effectiveness of the process of the invenlion may be expected to vary from unit to unit. NO* reduclioii compositions of the invention also prevent a significant increase in Ihe production of coke during the FCC process. [0049] lt is also within the scope of the invenlion that NOX reduction compositions of the invention may be used alone or in combination with one or more additional NOX reduction component to achieve NOx reduction more efficiently than the use of either of the compositions alone. Preferably, the additiorial NOX reduction component is â non-zeolitic materia], that is, a material that comains no or substantially no (i.e., less than 5 weight percent, preferably less than l weight percent) zeolite. [0050] One such class of non-zeolitic maierials suitable for use in combination with the NOX reduction compositions of the invention include noble metal containing NO* reduction compositions such as disclosed and described in U.S. Patent No. 6,660,683 the entire disclosure of which is herein incorporated by reference. Compositions in this class will typically comprise a particulate mixture of (•]) an acidic metal oxide containing substantially no zeolite (preferably containing silica and alumina, most preferably containing al least l weight percent alumina); (2) an alkali metal (at least 0.5 weighî percent, preferably about l to about 15 weight percent), an alkaline earth metal (at least 0.5 weight percent, preferably about 0.5 to about 50 weight percent) and rnixtures thereof; (3) al least 0.] weight percent of an oxygen storage metal oxide component (preferably ceria); and (4) at least 0.1 ppm of a nobîe metal component (preferably Pt, Pd, Rh, Ir,- Os, Ru, Re and rnixtures thereof). Preferred compositions in this class of materials comprise (1) an acidic oxide containing at least 50 weight percent alumina and substantially no zeolite; (2) at least 0.5 weight percent of.an alkali metal and/or an alkaline earth metal or rnixtures thereof; (3) about l to about 25 weight percent of an oxygen siorage capable transition metal oxide or a rare-earth (preferably, ceria); and (4) at least 0.1 ppm of a noble metal selected from the group consisting of Pt, Rh, Ir, and a combination thereof, all percentages being based on the total weight of the oxidative cătaiyst/additive cbmposhion. [0051] Another class of non-zeolitic materials suitable for use in combination with the NOX reduction compositions of the invention include a low NOx, CO combustion promoier as disclosed and described in U.S. Patent Nos.' 6,165,933 and 6,358,881, the entire disdosure of these patents being herein incorporated by reference. Typically, the low NO CO combustion promoier compositions comprise (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or rnixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) palladium... The acidic oxide suppon preferably contains silica alumina. Ceria is the preferred oxygen storage oxide. Preferably, the NOX reduction composition comprises (1) an acidic metal oxide suppon containing at least 50 weight percent alumina; (2) about 1-10 • parts by weight, measured as metal oxide, of at least one alkali metal, alkaline earth metal or rnixtures thereof; (3) at least l part by weight of CeOs; and (4) about 0.01-5.0 parts by weight of Pd, all of said parts by weight of components (2) - (4) being per J 00 parts by weight ofsaid acidic metal oxide support material. [0052] Yet another class of non-zeolitic materials suitable for use in combination with the NOX reduction compositions of the invention include NOX reduction composilions as disclosed and described in U.S. Patent Nos. 6,280,607 Bl, 6,143,167, 6,379,536 and 6,129,834, the entire disclosure of these patents being herein incorporated by reference. In general, the NO* reduction compositions comprise (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 1B and 31B of the Periodic Table. Preferably, the acidic oxide support contains at least 50 weight percent alumina.and preferably contains silica alumina. Ceria is the preferred oxygen storage oxide. In a -preferred embodiment of the invention, the NO* reduction compositions comprise (1) an acidic oxide support containing at least 50 weight percent alumina; (2)']-]0 weight percent, measured as the metal oxide, of an alkali meta], an alkaline earth metal or mixtures thereof; (3) at least l weight percent CeC>2; and (4) 0.01-5.0 parts weight percent of a transition metal, measured as metal oxide, of Cu or Ag, al] parts by weight of '* components (2) - (4) being per 100 parts by weight of said acidic oxide support. [0053] Another class of non-zeolitic. NO„ reduction material suitable for .use in combination with the NOX reduction compositions of the invention include magnesium-aluminum spinel based additives heretofore being-usefuî for the removal of sulfur oxides from a FCC regenerator. Exemplary patents which disclose and describe this type of materials include U.S. Patent Nos. 4,963,520, 4,957,892, 4,957,718, 4,790,982, 4,471,070, 4,472,532, 4,476,245, 4,728,635, 4,830,840, 4,904,627, 4,428,827, 5,371,055, 4,495,304, 4,642^178, 4,469,589,- 4,758,418, 4,522,937, 4,472,267 and 4,495,305 the entire disclosure of said patents beingherein incorporated by reference. Preferably, compositions in this class comprise 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 selecîed from the group consisting of Group 1B metals, Group 1IB 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. ţin, bismuth, molybdenum, antimon-y, vanadium and mixiures thereof. Preferably, the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal, and the atomic' ratio of magnesium to aluminum in said spinel is at least about 0.17. The third metal in the spinel preferably comprises a metal selected from the group consisting of the P]atinum Group metals, the rare-eanh melals and mixtures thereof. The third. metal component is preferably present in an amount in the.range of about 0.001 to about 20 weigbt percent, calculated as elemental third metal, and 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. [0054] Other non-zeolitic materials useful in combination with the NOX reduction additives of tne invention mcJude, but are not limited to, zinc based catalysts such as disclosed and described in U.S. Patent No. 5,002,654; antimony based NOX reduction additives such as described and disclosed in U.S. Patent No. 4,988,432; perovskite- spinel NO* reduction additives such as described and disclosed in U.S. Patent Nos. 5,364,517 and 5,565,181; hydrotalcite catalyst and additive compositions such as described and di'sclosed, for example, in U.S. Patent Nos. 4,889,615, 4,946,581, 4,952,382, 5,114,691, 5,114,898, 6,479,421 Bl and PCT International Publication No. WO 95/03876; and low NO* promoter additive compositions such as described, for example in U.S. Patent No. 4,290,878; the entire disclosure of each.patent being herein incorporaied by reference. [0055] It is aJso vvithin the scope of the invention to use the NOX reduction compositions of the invention in combinalion with NOX removal compositions as disclosed and described in PCT International Publication Number WO 03/046112 Al and PCT International Publication No. WO 2004/033091 Al, the entire disclosures of which are herein incorporated by reference. Such NO, removal composition generally comprises (i) an acidic oxide support, (ii) cerium oxide, (iii) a lanthanide oxide other than ceri a and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and 11B of the Periodic Table, noble metals, and mixtures thereof. [0056] When used, the additional non-zeolitic NOX reduction compositions are used in an amount sufficient toprovide increased NOX reduction when compare'd to the use of the ferrierite NOX reduction compositions alone. Typically, the additional non-zeolitic compositions are used in an amounl up to about 50 weight percent of the FCC catalyst inventory. Preferably, the non-zeolitic composition is used in an amount up to about 30 weight percent, moşi preferably up io about l O weight percent of the FCC catalyst inveniory. The additional NO* reduction composition may be blended with the FCC catalysl inventory as. a separate partide additive. A]temativ.e]y, the additional NOx reduction composition may be incorporated into the FCC catalyst as an integral component of the catalyst. [0057] h is aJso contemplated within the scope of the present invention that MOX reduction compositions in accordance wiih the present invention may be used in combination wjth other additives conventionally used in the FCC process, e.g., SOX reduction additives, gasoline-sulfur reduction additives, CO combustion prdmoters, additives for the production of light olefins, and the like. [0058] The scope of the invention is not-in any way imended to be' limited by the examples set forth below. The examples include the preparation of catalyst/âdditives ' useful in the process of the invention and the evaluation of the invention process to reduce NOX in a catolytic cracking environment. The examples-are given as specific illustrations of the daimed invention. Jt should be understood, however, that the invention is not limiied to the specific details set forth in the examples. [0059] AII parts and percentages in the examples, as well as the remainder of the specification which refers to solid compositions or concentrations, are by weight unless otherwise specified. Concentrations of gaseous 'mixtures are by volume unless otherwise specified. [0060] Further, any range of numbers recited in the specification or claims, such as that representing a panicular set of propenies, units of measure, conditioris, physical states or percentages, is imended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited. EXAMPLES EXAMPLE l [0061] A composition comprising 40% ferrierite, 40% clay and 20% silica sol (Additive A) was prepared as follows. An aqueous slurry containing 29% ferrierite (SiO2/Al2O3 = 20) was milled in a Drais mill to an average partide size of less th'an 2.5 um. The milled ferrierite slurry (4160g) was combined with 1200g Natka clay (dry basis) and 6000g silica sol binder (10% solids). The silica sol binder was prepared from sodium silicate and acid alum. The catalyst slurry was then spray-dried in a Bowen spray drier. The resuhing spray-dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a Na„O level of less than 0.1 weight percent. The properties of the additive are shown in Table ] below. EXAMPLE 2 [0062] A composition comprising 75% ferrierite and 25% alumina sol' (Additive B) was prepared as follows. An aqueous slurry was prepared which contained 2174g of aluminum chJorohydrol solution (23%- solids), 1500g (dry basis) of. ferrierite (SiO2/Al2O3 = 20, NaoO -f K^O EXAMELE3 . [0063] Additives A and B were evaluated for their ability to reduce NO emissions from a FCCU using the Davison Circulating Riser (DCR). The description of the DCR has been published in the following papers: G. W. Young, G. D. Weatherbee, and S. W. Davey, "Simulating Commercia] FCCU Yields' With The Davison Circulating Riser (DCR) Pitoî Plant "Unit," National Petroleum Refiners_Association (NPRA) Paper AM88-52; G. W. Young, "Realistic Assessment of FCC Catalyst Performance in the Laboratory," in Fluid Catalytic Cracking: Science and Technology, J. S. Magee and M. M. Muche]], Jr. Eds. Studies in Surface Science and Catalysis Volume 76, p. 257, Elsevier Science Publishers B.V., Amsterdam 1993, ISBN 0-444-89037-R. [0064] The DCR was started up by charging the unit with approximately 1800g of a ® commercially available cracking catalyst, SUPERNOVA -DMR+, obtained from Grace Davison. hydrothermally deactivated in a fluidiz,ed bed reactor with 100% steam for 4 hours at 816'C. (Table Removed) [0066] The DCR was operated with l % excess 02 in the regenerator, and with the regenerator operaiing at 705 C. After the unit stabilized the baseline NO* emissions data were collected using an on-line Lear-Siegler SO,/NOX Analyzer (SM8100A). Subsequently, lOOg of catalyst were injected into the DCR consisting of 4.75g of a commercial sample of a Pt-based combustion promoter, CP-3® (obtained'from Grace Davison), which hâd been deactivated for 20 hours at 788°C without any added Ni or V using the Cyclic Propylene Steaming method (CPS) and 95.25 grams of hydrothermally deactivated SUPERNOVA®-DMR+. The description of the CPS method has been published in L.T. BoocL T.F. Peni. and J.A Rudesill, "Contaminant-Metal Deactivation and Metal-Dehydrogenation Effects During Cyclic Propylene Sieaming of Fluid Catalytic Cracking CaîaJysts," Deactivation and Testing of Hydrocarbon Processing Catalysts, ACS Symposium Series 634, p. 171 (1996), ISBN 0-8412-3411-6. [0067] After the unii was again stabilized, the NO* emissions data were collected. Thereafter, 0.525g of the CO promoter wjth 2]0g of Additive A, or ]05g of the same sieamed deactivated cracking cata]yst originally loaded into the DCR with I05g-of Additive B was added to the DCR; The resuhs are recorded in Table 3 beJow." TOS is lime on stream from the lime of adding Pt CO combuslion promoter ,to the unit. As shown in that table and the FJGURE, Additives A and B are effective in-reducing NOX emissions from the DCR regenerator. [0068] Table 4 shows the conversion and product yields with and without the compositjon of this invention. In Table 4 the means of conversion and cracked product yields were calculated using a sample of 7 baseh'ne DCR tests. Aş shbwn in Table 4, when acconnting for the expected variation from-experiment to experiment, both Additives A and B are especially effective in decreasing NOX emissions without signifi'cantly affecting the cracked products yields. In' particular, both overall conversion and gasoline yield do not change.substantialîy, even though the FCC feedstock used in these experiments is a high nitrogen feed. EXAMPLE 4 [0069] A composition comprising 65% ferrierite, 20% Alumina Sol and 15% kaolin clay (ADDITJVE C) was prepared as follows: An aqueous slurry was prepared which comained 40.3 Ibs of alurninurrr chlorohydrol solution (23% solids), 29.3 Ibs (dry basis) of ferrierite (SiO2/AI203 = 36, Na20 -f K20 and 32.5 Ibs additional water, enough to make a slurry which contained about 40% solids. The slurry was milled in a Drais mill to an average partide size of less' than 2.5 um and then spray-dried in a Bowen Engineering spray drier. The spray-dried product was calcined for 60 minutes at ]]009F. The properties of the catalyst are shown in Table 5 below. (Table Removed) EXAMPLE 5 [0070] A paniculaie NO* reduction composition (Additive D) was prepared as follows: A slurry was prepared from an aqueous slurry having 20% solids of a peptizable alumina (Versal 700 alumina powder obtained from La Roche Industries Inc., 99% A^Oa, 30% moisture). The alumina slurry was prepared using 31.6 Ibs of the alumina. To the alumina slurry 3.87 Ibs of an aqueous sodium hydroxide'solution (50% NaOH) was added. Next, 10.4 Ibs of cerium carbonate crystals .(obtained from Rhone Poulenc, Inc., 96% CeOj, 4% La203, 50% moisture) was added to the'slurry. The slurry was diluted with a sufficient amount of water to bring .the solids »» conceniration of the slurry to 12%. Finally, 3.38 Ibs of ion exchanged silica sol of Nalco 1140 (obtained from Nalco Chemicals Co.) was added to the slurry. The mixture was agilated to assure good mixing and then milled in a stirred media mi]] to reduce agglomerates to substantially less than 10 pm. The milled mixture was then spray-dried to form approximately 70 um microspheres and thereafter calcined at approximately 650°C to remove volatiles. The resuhing material was impregnated with an aqueous solution of a Cu containing salt (e.g., CuSO^) to achieve about 2% Cu on the final product, and was flash dried. The final product hâd the following analysis (dry basis): 7.8% SiO2, 7.1% Na2O, 18.5% Ce02, 60.2% A12O3,1.9% Cu and BET surface area of 111 m2/g. EXAMPLE 6 [0073] Additive C and a blend of Additives C and D consisting of 75% Additiye C and 25% Additive D where tested in the DCR with a feedstock having the properties shown in Table 6. The unit was loaded with I995g of an equilibrium cracking caialyst (ECAT) having the properties as shown in Table 7 below, and 5g' of the. commercially available CO combustion promoter CP-3®,-which hâd been deactivated for 20 hours at 788°C without any added Ni or V using the CPS method. After the unit was stabilized, the baseline NO* emissions data were collected. Subsequently, 42g of Additive C or the blend of Additive C and D were injected into the unit alo'ng with 0.25g of the combustion promoter, and ]57.75g of the equilibrium catalyst. The results are shown in Table 8 below. TOS is time on stream from the time of adding the Pt CO combustion promoter to the unit. As this Table shows, both Additive C and the blend of Additives C and D are effective in decreasing NO, emissions in the DCR unit regenerator. However, the blend of Additives C and D when used in the catalyst inventory in the same amount as Additive C alone is more effective in reducing NOX than Additive C . (Table Removed) We claim: 1. A process of reducing NOX emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said process consisting of: (i) contacting a hydrocarbon feedstock in a catalytic cracking zone operating at a temperature ranging from 480 °C to 600 °C under fluid catalytic cracking (FCC) conditions with a circulating catalyst inventory of FCC catalytic cracking catalyst comprising a Y-type zeolite and a particulate NOx reduction composition having a mean particle size of greater than 45 µm and comprising (i) at least 30 weight percent of ferrierite zeolite, and (ii) from 5 to 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, aluminum phosphate and mixtures thereof, to produce an effluent comprising cracked products and spent catalyst containing coke and strippable hydrocarbons; (ii) discharging and separating a vapor phase rich in cracked products and a solids rich phase comprising the spent equilibrium cracking catalyst and NOx reduction composition; (iii) removing the vapor phase as product; (iv) stripping the spent FCC cracking catalyst and NOx reduction composition to remove the strippable hydrocarbons; and (v) oxidatively regenerating the spent FCC cracking catalyst and the NOx reduction composition in a regeneration zone operating at a temperature of 600 °C to 800°C to remove the coke from the FCC cracking catalyst and NOx reduction composition and reduce the amount of NOx emissions released from the regeneration zone by at least 10% relative to the amount of NOx emissions released In the absenee of the NOx redustion composition; and (vi) recycling the regenerated FCC catalyst and regenerated NOX reduction composition to the cracking zone for further cracking and NOx reduction. 2. The process as claimed in claim 1 wherein step (v) 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. 3. The process as claimed in claim 1 wherein the amount of ferrierite zeolite present in the NOx reduction composition is at least 40 weight percent of the composition. 4. The process as claimed in claim 3 wherein the amount of ferrierite zeolite present in the NOx reduction composition is at least 50 weight percent of the composition. 5. The process as claimed in claim 1 wherein the amount of ferrierite zeolite present in the NOx reduction composition ranges from 30 to 80 weight-percent of the composition. 6. The process as claimed in claim 5 wherein the amount of ferrierite zeolite present in the NOx reduction composition ranges from 40 to 75 weight percent of the composition. 7. The process as claimed in claim 1 or 2 wherein the ferierite zeolite is exchanged with a cation selected from the - group consisting of hydrogen, ammonium, alkali metal and combinations thereof. 8. The process as claimed in claim 1 wherein the ferrierite zeolite further comprises at least one stabilizing metal. 9. The proceses as claimed in claim 8 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. 10. The process as claimed in claim 9 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. 11. The process as claimed in claim 10 wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof. 12. The process as claimed in claim 8 wherein the stabilizing metal is incorporated into the pores of the ferrierite zeolite. 13. The process as claimed in claim 1 wherein the inorganic binder is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof. 14. The process as claimed in claim 13 wherein the inorganic binder is alumina. 15. The process as claimed in claim 14 wherein the alumina is an acid or base peptized alumina. 16. The process as claimed in claim 14 wherein the alumina is aluminum chlorohydrol. 17. The process as claimed in claim 1 wherein the amount of inorganic binder present in the particulate NOx reduction composition ranges from 10 to 30 weight percent of the composition. 18. The process as claimed in claim 17 wherein the amount of inorganic binder present in the particulate NOx reduction composition ranges from 15 to 25 weight percent of the composition. 19. The process as claimed in claim 1 wherein the particulate NO* reduction composition further comprises an additional zeolite other than ferrierite zeolite, 20. The process as claimed in claim 19 wherein the additional zeolite is a zeolite having a pore size ranging from 3 to 7.2 Angstroms and a SiO2 to Al2O3 molar ratio less than 500. 21. The process as claimed in claim 20 wherein the SiO2 to Al2O3 molar ratio is less than 250. 22. The process as claimed in claim 19 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, Loydarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite and mixtures thereof. 23. The process as claimed in 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, Offretite, A, ZSM-12 and mixtures thereof. 24. The process as claimed in claim 19, 20 or 22 wherein the additional zeolite is present in an amount ranging from 1 to 80 weight percent of the composition. 25. The process as claimed in claim 24 wherein the additional zeolite is present in an amount ranging from 10 to 70 weight percent of the composition. 26. The process as claimed in claim 1 or 2 wherein the NOx 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. 27. The process as claimed in claim 26 wherein the matrix material is present in an amount less than 70 weight percent. 28. The process as claimed in claim 1 or 2 further comprising recovering the cracking catalyst from said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst 29. The process as claimed in claim 28 wherein the cracking catalyst and the particulate NOx reduction composition are fluidized during contacting said hydrocarbon feedstock. 30. The process as claimed in claim 1 or 2 further comprising contacting the hydrocarbon feed with at least one additional NOx reduction composition. 31. The process as claimed in claim 30 wherein the additional NOx reduction composition is a non-zeolitic composition. 32. The process as claimed in claim 31 wherein the additional NOx reduction, composition comprises (1) an acidic metal oxide; (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. .; 33. The process as claimed in claim 30 wherein the additional NOx reduction composition is a low NOx, 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. 34. The process as claimed in claim 30 wherein the additional NOx 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. 35. The process as claimed in claim 30 wherein the additional NOx 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. 36. The process as claimed in claim 35 wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal. 37. The process as claimed in claim 36 wherein the third metal component in the metal containing spinel is selected from the grpup consisting of a Platinum Group metal, the rare-earth metals and mixtures thereof. 38. The process as claimed in claim 35 wherein the third metal component is present in an amount in the range of 0.001 to 20 weight percent, calculated as elemental third metal. 39. The process as claimed in claim 35 wherein said fourth metal component is present in an amount in the range of 0.001 to 10 weight percent, calculated as elemental fourth metal. 40. The process as claimed in claim 30 wherein the additional NOx reduction additive is a zinc based catalyst. 41. The process as claimed in claim 30 wherein the additional NOx reduction additive is an antimony based NOx reduction additive. 42. The process as claimed in claim 30 wherein the additional NOx reduction additive is a perovskite-spinel NOx reduction additive. 43. The process as claimed in claim 30 wherein the additional NOx reduction additive is a hydrotalcite containing composition. 44. The process as claimed in claim 1 wherein the particulate NOx reduction composition has a mean particle size from 50 to 200 urn. 45. The process as claimed in claim 44 wherein the particulate NOx reduction composition has a mean particle size from 55 to 150um. 46. The process as claimed in claim 1 wherein the amount of the NOx 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. 47. The process as claimed in claim 30 wherein the additional NOx 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.

Full Text

[0001] The application is a continuation in part application of U.S. Patent Application
Serial No. 10/702,240, filed November 6, 2003.
FIELD OF THE INVENTION
10002] The present invention relates to NOx reduction compositions and the method of use thereof to reduce NOx emissions in refinery processes, and specifically in fluid catalytic cracking (FCC) processes. More particularly, the present invention relates to NOx reduction compositions and their method of use to reduce the content of NOx off gases released from a fluid catalytic cracking unit (FCCU) regenerator during the FCC process without a substantial change in hydrocarbon conversion or the yield of valuable cracked products.
BACKGROUND OF THE INVENTION
[0003] In recent years there has been an increased concern in the United States and elsewhere about air pollution from industrial emissions of noxious oxides of nitrogen, sulfur and carbon. In response to such concerns, government agencies have placed limits on allowable emissions of one or more of these pollutants, and the trend is clearly in the direction of increasingly stringent regulations.
[0004] NOx, or oxides of nitrogen, in flue gas streams exiting from fluid catalytic cracking (FCC) regenerators is a pervasive problem. Fluid catalytic cracking units (FCCU) process heavy hydrocarbon feeds containing nitrogen compounds, a portion of which is contained in the coke on the catalyst as it enters the regenerator. Some of this coke-nitrogen is eventually converted into NOx emissions, either in the FCC regenerator or in a downstream CO boiler. Thus, all FCCUs processing nitrogen-containing feeds can have a NOx emissions problem due to catalyst regeneration.
[0005] In the FCC process, catalyst particles (inventory) are continuously circulated between a catalytic cracking zone and a catalyst regeneration zone. During regeneration, coke deposited on the cracking catalyst particles in the cracking zone is removed at elevated temperatures by oxidation with oxygen containing gases such as air. The removal of coke deposits restores the activity of the catalyst particles to the point where they can be reused in the cracking reaction. In general, when coke is burned with a deficiency of oxygen, the regenerator .flue gas has a high CO/CC2ratio and a low level of NOx, but when burned with excess oxygen, the flue gas has a high level of NOx and a reduced CO content. Thus, CO and Nx or mixtures of these pollutants are emitted with the flue gas in varying quantities, depending on such factors as unit feed rate, nitrogen content of the feed, regenerator design, mode of operation of the regenerator, and composition of the catalyst inventory. [0006] Various attempts have been made to limit the amount of NOX gases emitted from the FCCU by treating the NOX gases after their formation, e.g., post-treatment of NOX containing gas streams as described. in U.S. Paient Nos. 4,434,347, 4,778,664, 4,735,927, 4,798,813, 4,855,115, 5,413, 699, and 5,547,648.
[0007] Another âpproach has been to modify the operation of the regenerator to parţial'bum and then ireal the NO* precursors in the flue gas before they are converted to NOX> e.g., U.S. Patent Nos. 5,173,278, 5,240,690, 5,372,706, 5,413,699, 5,705,053, 5,716,514, and 5,830,346.
[0008] Vet another approach has been io modify the operation of the regenerator as to reduce NO„ emissions, e.g., U.S. Patent 5,382,352, or modify the CO combustion promoter used, e.g., U.S. Patents 4,199,435, 4,812,430, and 4,812,431. Enrichment of air with oxygen in a regenerator operating in parţial bum mode has also been suggesied, e.g., U.S. Patent 5,908,804.
[0009] Additives have also been used in attempts to deal with NO* emissions. U.S. Patent Nos. 6,379,536, 6,280,607, 6,129,834 and 6J43.167 disclose the use of NOX removal compositions for reducing. NOX emissions from the FCCU regenerator. U.S. Patent Nos. 6,358,881 and 6,165,933 also disclose a NOx reduction composition, which promotes CO combustion during the FCC catalyst regeneration process step while simultaneously reducing the level of NOX emitted during the regeneration step. NOx reduction compositions disclosed by these paients may be used as" an additive which is circulated along with the FCC catalyst inventory, or incorporated as an integral component of the FCC catalyst,
[0030] U.S. Paient Nos. 4,973,399 and 4,980,052 disclose reducing emissions of NO, from the regenerator of the FCCU by incorporating into the circulati.ng invemory of cracking catalyst separaie additive particles containing a copper-loaded zeolite.
[0011] Many additive compositions heretofore used to control NOX emissions have typ'ically caused a significant decrease in hydrocarbon conversion or the yield of valuable cracked products, e.g., gasoline, light olefins and liquefied petroleum gases (LPGs), while increasing the production of coke. lt is a highly desirable characteristic for N0„ additives added to the FCCU not io affect the -cracked product yields or change the overalî unit conversion, The operation of the FCCU is typically optimized • based on the unit design, feed and catalyst, to produce a slate of cracked produ'cts, and maximize refinery profitability. This product slate is based on the value model of the specific refinery. For exarnple, during the-peak summer driving season-many refiners want to maximize gasoline production, while during the winler season refirîers may want to maximize heating oi] production. In other cases a refinery may find it profitable to produce light olefins products that can be sold in the open.market .or used in an associated petrochemical plant as feedstocks.
[0012] When a NO* reduction additive increases coke production, the FCCU may
have insufficient air capacity to burn the extra coke and may result in a lower feed
thr.oughput in the unit. If the additive increases -the production of low value dry gas,
the production of more valuable products may decrease. An incfease in dry gas may
exceed the ability of the unit to handle it, thus forcing- a reduction of the amount of
feed processed. While an additive that increases ligbt olefins production may be
desirable if the refinery values these products and the unit nas the equipment
necessary io process the extra light hydrocarbons, the additive may, however, reduce
profitability if the refinery's goal is to maximize gasoline production; Light olefins
are typically made in the FCCU at the expense of gasoline production. . Eve'n ah.
additive which increases unit conversion may be undesirable if it affects product
yields, causes the unit io reach an equipment limitation, and/or decreases the amount
of feed that can be processed. . . •
[0013] Consequently, any change to the FCCU that affects the product slate or changes the ability to process feed at the desired rate can be detrimemal to the refinery profitability. Therefore, there exists a need for NOX control compositions which do not significantly affect produci yields and overall unit conversion.
SUMMARY OF THE INVENT10N
[0014] ]t has now been discovered that the incorporation of a ferrierite zeolite component with a catalytically cracking caialyst inventory, in particular a cracking catalyst inveniory coniaining an active Y-type zeolite, being circulated throughout a fluid catalytic cracking unit (FCCU) during a fluid catalytic cracking (FCC) process provides superior NO* control performance without substantially changing or affecting the hydrocarbon conversion or the yield of cracked petroleum- products produced during the FCC process.
[0015] In accordance with the present invention, novei NOX reduction compositions are provided. Typically, the N0> reduction compositions comprise a particulate composition confa'ining panicles of ferrierite zeolite. The ferrierite zeolite may be added as a separate additive partide to a circulating inventory of the cracking catalyst or incorporated directly into the Y-type zeolite coniaining cracking catalyst as an integral component of the catalyst. In a preferred embodiment of the invention,. the ferrierite zeolite are separate additive particJes bound with an inorganic binder. The binder preferably comprises silica, alumina or silica alumina. Preferably, the ferrierite zeolite is exchanged with hydrogen, ammonium, alkali metal and combinations thereof. The preferred alkali metal is sodium, potassium and combinations thereof. [0016] In one aspect of the invention, nove] ferrierite zeolite-contain'ing NOX reduction compositions are provided which are added to a circulating inventory of the catalytic cracking catalyst as a separate admixture of particJes to reduce NOX emissions released from the FCCU regenerator during th'e FCC process. [0017] In another aspect of the invention, nove] NOX reduction compositions are provided which comprise ferrierite zeolite incorporated as an integral component of the FCC catalyst, preferably coniaining a Y-type zeolite active component. [0018] In yet another aspect of the invention, nove] NOx reduction compositions are provided which compositions reduce NO, emissions from the FCCU regenerator during the FCC process while substantially maintaining hydrocarbon conversion and the yield of cracked petroleum products and minimizing an increase in the production of coke.
[0039] It is another aspect of the present invention to provide a process. for the
red'uction of the content of NOx in the off gas of the FCCU -regenerator during the
FCC process using NOX reduction compositions in accordance with the present
invention.
[0020] Another aspect of the invention is io provide improved FCC processes for th'e
reduction of the content of NO* in the off gases of the FCCU regenerator withoirf
substantially affecting hydrocarbon conversion or the yield of petroleum products
produced during the FCC process.
[0021] These and other aspects of the present invention are described in further detail
below.
BR1EF DESCRIPT.10N OF THE DRAWINGS
[0022] The FJGURE is a graphic representation of the effectiveness-of Additive A
and Additive B, prepared in EXAMPLES l and 2, respectively, to reduce NOX
emissions from a DCR regenerator versus time on stream, when the addiţives are
® blended with a cornmercially available cracking catalyst (SUPERNOVA -DMR+,
obtained from Grace Davison, Columbia, MD), which contains 0.25 weight percent of a platinum promoter, CP-3® (obtained from Grace Davison, Columbia, MD) and which was deactivaied using the Cyclic Propylene Steaming procedura as.described in EXAMPLE 3.
DETA1LED DESCRIPT1ON OF THE INVENT1ON
[0023] Although severa] nitrogen oxides are known which are relatively stabîe at
ambient conditions, for purposes of the present invention, NOX will be used herein to
represent nitric oxide, nitrogen dioxide (the principal noxious oxides of nitrogen) as
well as ^CXi.NîOs and mixtures thereof.
[0024] The present invention encompasses the discovery that the use of ferrierile
zeolite containing NOX reduction composilions in combination with a fluid catalytic
cracking (FCC) catalyst, preferably a catalyst comprising an active Y-type zeolite, is
very effective for the reduction of NOx emissions released from the FCCU regenerator
under FCC process conditions without a substanţial change in hydrocarbon feed
conversion or the yield of cracked products. The NOx reduction compositions
typically comprise a particulate composition containing particles of ferrierite zeolite. In a preferred embodiment of the invention, the ferrierite panicles are bound with an inorganic binder. The nove] ferrierite zeolite-comaining NOX reduction compositions may be added to the circulaiing' inventory of ihe catalytic cracking catalyst as a separate partide additive or incorporaled as an integral component into the cracking catalyst.
[0025] For purposes of the present invention, the phrase "a substanţial change in hydrocarbon feed co'nversion or the yield of cracked products" is defined -herein to mean in the alternative, (i) less than a 50% relative change, preferably less than a 30% relative change and most preferably less than a 15% relative change in the yield of LPG (liquefied petrol cum gas) as compared to the baseline yield of the same or substaniially the Same product; or (ii) less than a 30% relative change, preferably less than a 20% relative change and most preferably less than a 30% relative change in the yield of LCO (lighi cycle oils), bottoms and gasoline in combination with LPG as compared to the baseline yield of the same or substantially the same products; or (iii) less than a 10% relative change, preferably less than a 6.5% relative change and most preferably less than a 5% relative change in the hydrocarbon feed conversion as compared to the baseline conversion. The conversion is defined as 100% times (l -bottoms yield - LCO yield). When the NOX reduction composition is used as a separate additive, the baseline is the mean conversion or yield of a product in the FCCU, operating with the same or substantially the same feed and under the same or substaniially the same reacîion and unii conditions, but before the additive .of the present invention is added to the catalyst inventory.' When the NOx reduction composition is inîegrated or incorporated into the cracking catalyst particles to provide an integral NOx reduction catalyst system, a significant change in the hydrocarbon conversion or yield of cracked products is determined using a baseline defined as the mean conversion or yield of a product in the same or substantially the same FCCU operating with the same or substantially the same feed, under the same or substantially the same reaction and unit conditions, and with a cracking catalyst inventory comprising the same or subsiantially the same cracking catalysi composition as that containing the NOX reduction composition, except that the NOX reduction composition is replaced in the cracking catalyst with a matrix component
such as kaoJin or other filler. The^percent changes specified above are derived from statistica] analysis of DCR operating data.
[0026] Any f emerit e zeolite is useful îo prepare the NOX reduction compositions of the invention. However, it is preferred that the ferrierite zeolite has a surface areâ of at least 100 m2/g. m ore preferably at Jeast 200 m2/g and rnost preferably at least 300 m2/g and a S i Os to Al2Oa molar ratio of less than 500, preferably less than 250, most preferably, less than JOO. In one embodiment of the invention; the ferrierite zeolite-is exchanged wjth a maierial selecied from the group consisting of .hydrogen, ammonium, alkali metal and combinations thereof, prior to incorpdration into .the binder or FCC catajyst. The preferred -alkali metal is one selected from the group
t*
consisting of sodium, potassium and mixtures thereof.
[0027] Optionally, the'ferrierite zeolite may contain stabilizing amounts, e.g., up to about 25 weight percent, of a stabilizing metal (or metal ion), preferably incorporated into. the pores of the zeolite. Suitable stabilizing metals include, but are not limited to, metals selected from the group consisting of Groups ]]A, JJIB, IVB, VB, VIB, V1IB, V]D, 11B, ]]1A, IVA, VA, the Lanthanide Series of The Periodic Table, Ag and mixtures thereof. Preferably, the stabilizing metals are selected from the group consisting of Groups JJJB, ]]A, J1B, 111A and the Lanthanide Series of the Periodic Table, and mixtures thereof, Most preferably, the stabilizing metals are selected from the group consisting of lanthanum, aluminum, magnesium, zinc, and mixtures thereof. The metal may be incorporated into the pores of the ferrierite zeolite by any method known in the art, e.g,, ion exchange, impregnation or the like. For purposes of this invention, the Periodic Table referenced herein above is the Periodic Table as published by the American Chemical Society.
[0028] The amount of ferrierite zeolite used in the NOx reduction compositions of the invention will vary depending -upon severa] factors, including but pot limited to, the ' mode of combining the ferrierite zeolite with the catalytic cracking catalyst and the type of cracking catalyst used. In one embodiment of the invention, the NO* reduction compositions of the invention are separate catalyst/additive compositions and comprise a particulele composition formed by binding particles of a ferrierite zeolite with a suitable inoreanic binder. Generally, the amount of ferrierite zeolite present in the particuhite NOX reduction compositions is at least ]0, preferably at least
30, most preferably al least 40 and even more preferably at least 50, weight percent based on the total weight of the composition. Typically, the particulate catalyst/additive composition of the invention contains from about ] O to abouî 85, preferably from about 30 to about 80, most preferably, from about 40 to about 75, weight percent of ferrierite zeolite based on the total weight of the catalyst/additive composilion.
[0029] Binder materials useful to prepare the particulate compositions of the invention include any inorganic binder which is capable of binding ferrierite zeolite powder to form particles having properties suitable for use in the FCCU under FCC process conditions. Typical inorganic binder materials useful to prepare compositions in accordance wiih the present invention include, but are not limited to, alumina, silica, silica alumina, aluminum phosphate and the like, and mixtures thereof. Preferably, the binder is selected from the group consisting of alumina, silica, silica alumina. More preferably, the binder comprises alumina. Even more preferably, the binder comprises an acid or base peptized alumina, Most preferably, the binder comprises an alumina sol, e.g., alurninum chlorohydrol. Generally, the amount of ' binder material present in the particular NOX reduction compositions comprises from about 5 to about 50 weight percent, preferably from about 10 to about 30 weight percent, rnost preierably from about 15 to about 25 weight percent, of the NO* reduction composition of the invention.
[0030] Additional- materials optionally present in the compositions of the present invention include, but are not limited to, fillers-(e.g., kaolin clay) or matrix materials (e.g., alumina, silica, silica alumina, yttria, lanthana, ceria, neodymia, samaria, europia, gadolinia, litania, zirconia, praseodymia and mixtures thereof). When used, the additional materials are used in an amount which does not significantly adversely affect the performance of the compositions to reduce NOX emissions released from the FCCU regenerator under FCC conditions, the hydrocarbon feed conversion or the product yîeld of ihe cracking catalyst. In general the additional materials will comprise no more than about 70 weight percent of the compositions. It-is preferred, however, that the compositions of the invention consist essentially of ferrierite and an inoreanic binder.
[0031] Paniculate NOX reduciion compositions of the invention should have a partide
size sufficient io permit the composition to be circulated throughout Ihe FCCU
simulianeously with the inventory of cracking catalyst during the FCC process.
Typically the composition of the invention wj]] have a mean partide size of greater
than 45 |jm. Preferably, the mean panicle size is from about 50 to about 200 p.m,
most preferably from about 55 to about 150 um, even more preferred from about 60
to about 120 (.im. The compositions of the invention typically have a Davison
attrition index (DI) value of less than about 50, preferably less than about 20, most
preferably less than about 15. •• .
[0032] While the present invention is. not limited to any panicular process of
**
preparation, typically the particulaie NO* reduction compositions of the invention are prepared by forming an aqueous slurry containing the ferrierite zeolite, opţional zeolite components, the inorganic binder and opţional matrix materials, in an amount sufficient io provide at least 10.0 weight percent of ferrierite zeolite and at least 5.0 weight percent of binder material in the final NOX reduction composition and, thereafter, spray drying the aqueous slurry to form particles.' The spray-dried particles are optionally dried at a- sufficient temperature for a sufficient time to remove volatiles, e.g., at about 90 C to about 320 C for about 0.5 to about 24-hours. In a preferred ernbodiment of the invention, the ferrierite zeolite containing aqueous slurry is rnilled prior io spray-drying io reduce the mean partide size of materials contained in the slurry io 10 um or less, preferably 5 um or less, most preferably 3 (jm or less. The aqueous slurry containing ferrierite zeolite rnay be milled prior to or after incorporation of the binder and/or matrix materials as desired.
[0033] The spray-dried composition may be calcined at a temperature and for a time sufficieni to remove volatiles and provide sufficient hardness to the binder for use in the FCCU under FCC process conditions, preferably from about 320°C to about 900°C from about 0.5 to about 6 hours.
[0034] Optionally, the dried or calcined composition is washed or exchanged with -an aqueous solution of ammonia or ammonium salt (e.g., ammonium sulfate, nitrate, chloride, carbonate, phosphate and the like), or an inorganic or organic acid (e.g., sulfuric, nitric, phosphoric, hydrochloric, acetic, formic and the like) to reduce the amount of alkaline rnetals, e.g. sodium or potassium, in the finished product.
[0035] Participate NOX reduction compositions of the invention are circulated in the form of separate partide addhives along with the rnain cracking catalyst throughout the FCCU. Generally, the catalyst/additive composition is used in an amount of at least 0.1 weight pcrcent of the FCC catalyst inventory. Preferably the amount of the catalyst/additive composition used ranges from about 0.1 to about 75 weight percent, most preferably from about ] to about 50 weight percent of the FCC caîalyst inventory. Separate partide caialyst/additive compositions of the invention may be added to the FCCU in the convenţional manner, e.g., with make-up catalyst to the regenerator or by any oiber convenient method.
[0036] In a second embodiment of the invention, the ferrierite zeolite is integrated or incorporated into the cracking catalyst panicles thernselves to provide an integra) NO* reduction catalyst system. In accordance with this embodiment of the invention, the ferrierite zeolite may be added to the catalyst at any stage during catalyst manufacturing prior io spray drying the cracking catalyst slurry to obtain the fluid cracking catalyst, regardless of any additional opţional or required processing steps needed to finish the cracking catalyst preparation. Without intending to limit the incorporation of the ferrierite, and any opţional zeolite components, within the
cracking catalyst to any specific method of cracking catalyst manufacturing, typically
> the ferrierite zeolite, any additional zeolites, the cracking catalyst zeolite, usually
USY or REUSY-type, and any matrix materials are slurried in water. The slurry is milled to reduce the mean partide size of solids in the slurry to less than ]0 pm, preferably to less than 5 um, most preferably less than 3 um. The milled 'slurry is combined with a suitable inorganic binder, i.e., a silica sol binder, and an opţional matrix material, e.g. clay. The resulting slurry is mixed and spray-dried io provide a catalyst material. The spray-dried catalyst is optionally washed using an aqueous solution of ammonium hydroxide, an arnmonium salt, an inorganic or organic acid, and water to remove the undesirable salts. The washed catalyst may be exchanged with a water soluble rare-earth salt, e.g., rare-earţb chlorides, nitrates and the like. [0037] Alternative]y, the ferrierite zeolite, opţional addilional z.eolites, the cracking catalysl zeoJite, any matrix materials, a rare-earth water soluble salt, clay and alumina s o] binder are slurried in water and blended. The slurry is milled'and spray-dried. The spray-dried catalyst is calcined at aboui 250°C to about 900 C. The spray-dried
catalyst may then optionally be washed using an aqueous solution of ammonium hydroxide, an ammonium sa]t, ari inorganic or organic acid, and water to remove the undesirable salts. Optionally, ihe catalyst may be exchanged with a water-soluble rare-earth salt after it has been washed, by any of the methods known in the art. [0038] When integrated into the FCC catalyst panicles, the ferrierite zeolite compound lypically represents at least about 0.] weight percent of the FCC catalyst-partide. Preferably, the amoum of the ferrierite zeolite use'd ranges frorn about 0.1. to about 60 weight percent, moşi preferably from about ] to about 40 wejght percent, of the FCC cataJyst particJes.
[0039] The integrated FCC catalyst will.typically comprise the ferrierite zeolîte along with the cracking catalyst zeolite, inorganic binder materials and optionally, matrix, fillers, and other additive components such as metals traps (for examp]e, traps for Ni and V) to make up the cracking catalyst. The cracking catalyst zeolite, usually a Y, USY or REUSY-type, provides the majority of the cracking activity and is typically present in a range from about 10 io about 75, preferably from about 15 to about 60 and most preferably from about 20 to about 50 weight percent based on the total weight of the composition. Inorganic binder materials useful to prepare integrated catalyst cornpositions in accordance with the present invention include, any inorganic materia] capable of bmding the components of the integrated catalyst to form particles having propenies suitable for use in the FCCU under FCC process conditions. Typically, the inorganic binder materials include, but are .not limited to, alumina, silica, silica alumina, aluminum phosphate and the like, and mixtures thereof. Preferably, the binder is selected from the group consisting of alumina, silica, silica alumina. Generally, the amount of binder material .present in the integrated catalyst composition is less than 50 weight percent, based on the total weight of the catalyst composition. Preferably, the amount of binder materia] present in the integrated catalyst composition ranges from about 5 to about 45 weight percent, most preferably from about J O to about 30 weight percent and even more preferably from about 15 to about 25 weight percent, based on the total weight of the composition. [0040] The matrix maierials optionally present in the integrated catalyst cornpositions of the presenl invention include, but are not limited to alumina, silica alumina, rare earth oxides such as lanthana, transition metal oxides such as titania, zirconia, and
manganese oxide, Group 11A oxides such as magnesium and barium oxides, clays such as kaolin, and mixtures thereof. The matrix.or fillers may be present in the integra] catajyst in' the amouni of less than 50 weight percent based on the total weight of the composition. Preferably, the matrix and fillers, if any, are present in an amount ranging from about ] io about 45 weight present based on the total weight of the catalyst composition.
[0041] The partide size and attrition propenies of the integral catalyst affect fluidization propenies in the unit and determine how well the catalyst is relained in the commercia] FCC unit. The iniegral catalyst composition of the invention typically has a mean partide size of about 45 to about 200um, more preferabJy from about 50unrto about J50fjm. The attrition propenies of the integral catalyst, as measured by the Davison A'tirition Index (DI), have.a Dl value of less'than 50, more preferably less than 20 and most preferably less than 15.
[0042] In a preferred embodiment of the invention, the FCC cracking catalyst contains a Y-type zeolite. The ferrierite zeolite may be added as a separate additive partide to a circulating inventory of the cracking catalyst or incorporated directly into the Y-type zeoliîe containing cracking catalyst as an integra] component of the catalyst. In either case, it is preferred that ferrierite zeolite is present in the final composition in an amount sufficient to provide in the total catalyst inventory a ratio of ferrierite zeolite to Y-type zeolite of less than 2, preferably less than J. [0043] ]t is also wjtbin the scope of the invention-to include additional zeolite components in the ferrierite zeolite containing NO* reduction compositions of the invention. The additional zeolite component may be any zeolite which does not adversely affect the NO* reduction performance or căuşe a substanţial change in hydrocarbon conversion or cracked product yields during the FCC process. Preferably, the addilional zeolite component is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms with a SiO? to AlsO.i molar ratio of less than about 500, preferably less than 250. Preferably, the additional zeolite component is a zeolite selected from the group consisting of ZSM-5, ZSM-]], beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-32, ZSM-23, ZSM-18, ZSM-22, ZSM-35, ZSM-57, ZSM-61, ZK-5, Nai Nu-87, Cit-], SSZ-35, SSZ-48, SSZ-44,
SSZ-23, Dachiardiie, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite or mixtures thereof. Most preferably the addilional zeolite component is selecied from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenhe, MC3V1-56, Zeo]ite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, Offretite, A, ZSM-12 and mixtures thereof. The additional zeolite component is used in any arriounî ihat does not significantly adversely affect the performance of the NOX reduction compositions to reduce NOX emissions and substantialjy maintain the hydrocarbon conversion or the product yields of the cracking catalyst relative to the use of the cracking catalyst without the catalyst/additive composition. Typic'ally, the
t*
additiona] zeolhe component is used in an amount ranging from about l to about 80, preferably from about '10 to about 70, weight percent of the catalyst/additive composition. Where the NO* reduction composition is used as an integra] component of the catalyst, the additional zeolite component is preferably used in an amount ranging from about 01 io about 60, moşi preferably from about 1-to about 40, weight percent of the catalyst composition.
[0044] Somewhat briefly, the FCC process involves the cracking of heavy hydrocarbon feedstocks to lighter products by contact of the feedstock in a cyclic cataJyst recircuJalion crack'ing process with a circulating fluidizable cracking catalyst inventory consisting of panicles having a mean size ranging from.about 50 to about 150 pm, preferably from about 60 to about 120 um. The catalytic cracking of these relatively high molecular weight hydrocarbon feedstocks results in the production of a hydrocarbon product of lower molecular weight. The significant sieps in the cyclic FCC process are:
(i). tbe feed is catalytically cracked in a catalytic cracking zone, hormally a riser cracking zone, operating at catalytic cracking conditions by contactîng feed with a source of hoţ, regenerated cracking catalyst to produce an effluent comprising cracked products and spent catalyst • containing coke and strippable hydrocarbons;
(ii) the effjuent is discharged and separated, normally. in one or more cyclones, into a vapor phase rich in cracked product and a solids n eh phase comprising the spent catalyst;
(iii) Lhe vapor phase is removed as product and fractionated in the FCC main column and its associated .side columns to form gas and liquid cracking products including gasoline; (iv) the spent catalyst is stripped, usually with steam, to remove occluded hydrocarbons from the catalyst, after which the stripped catalyst is oxidatively regenerated in a catalyst • regeneration zone to produce hoţ, regenerated catalyst which is then recycled to the cracking zone for cracking further . quantities of feed.
[0045] Convenţional FCC catatysts include, for example, zeolite based catalysts with a faujasite cracking component as described in the seminal review by Venuto and Habib, Fluid Caialyiic Cracking with Zeoliie Caialysis, Marcel Dekker, New York 1979, ISBN 0-8247-6870-1, as well as in numerous other sources such as Sadeghbeigi, Fluid Caialytic Cracking Handbook, Gulf Publ. Co. Houston, 1995, ISBN 0-88415-290-1. Preferably, the FCC catalyst is a catalyst comprising a Y-t.ype zeolite active cracking component. In a particulari)' preferred embodiment of the invention, the FCC catalysts consist of a binder, usually silica, alumina, or silica alumina, a Y-type zeolite active component, one or more matrix aluminas and/or silica aluminas, and fillers such as kaolin clay. The Y-type zeolite may be present in one or more forms and may have been ultra stabilized and/or treated with stabilizing cations such as any of the rare-earths.
[0046] Typical FCC processes are conducied at reaction temperatures of 480°C to 600°C with catalyst regeneration temperatures of 600 C to 800 C. As it is well known in the an, the catalysî regeneration zone may consist of a single or multiple reactor vessels. The compositions of ihe invention may be used in FCC processing of any ţypical hydrocarbon feedstock. Suitable feedstocks include petroleum distillates or residuals of crude oils, which when catalytically cracked, provide either a gasoline or a gas oii product. Synthetic feeds having boiling points of about 204°C to about 816°C, such as oii from coal, tar sands or shale oii, can also be included. [0047] In order to remove coke from the catalyst, oxygen or ajr is added to the reeeneration zone. This is performed by a suitable sparging device in the bonom of
he regeneration] zone, or if desired, additional oxygen is added to the dilute or dense phase of the regeneration zone.
[0048] NO„ reduction compositions in accordance with the invention dramatically reduce, i.e., by at least 10%, preferably at least 20%, the emissions of NOx in the FCCU regenerator effluent during the catalyst regeneration, while substantially maintaining the hydrocarbon feed conversion or the yield of cracked products, e.-g., • gasoline and lignt olefins, obtained from the cracking catalyst. In some casfes, NOX reduction of 90% or greater is readily achievable using the compositions and.method of the inventJon without significantly affecting the cracked products yields or feed conversion. However, as will be understood by one skilled in the catalyst' art, the
â*
extent of NOX reduction will depend on such factors as, for example, the composition and amount of the additive utilized; the design and the manner in which the catalytic cracking unit is operated, including but not limited to oxygen level and distribution of air in the regenerator, catalyst bed depth in the regenerator, stripper operation and regenerator lemperalure, the properties of the hydrocarbon feedstock cracked, and the presence of other catalytic additives that may affect the chemistry and operation of the regenerator. Thus, since each FCCU is different in some or al l of these respects, the effectiveness of the process of the invenlion may be expected to vary from unit to unit. NO* reduclioii compositions of the invention also prevent a significant increase in Ihe production of coke during the FCC process.
[0049] lt is also within the scope of the invenlion that NOX reduction compositions of the invention may be used alone or in combination with one or more additional NOX reduction component to achieve NOx reduction more efficiently than the use of either of the compositions alone. Preferably, the additiorial NOX reduction component is â non-zeolitic materia], that is, a material that comains no or substantially no (i.e., less than 5 weight percent, preferably less than l weight percent) zeolite. [0050] One such class of non-zeolitic maierials suitable for use in combination with the NOX reduction compositions of the invention include noble metal containing NO* reduction compositions such as disclosed and described in U.S. Patent No. 6,660,683 the entire disclosure of which is herein incorporated by reference. Compositions in this class will typically comprise a particulate mixture of (•]) an acidic metal oxide containing substantially no zeolite (preferably containing silica and alumina, most

preferably containing al least l weight percent alumina); (2) an alkali metal (at least 0.5 weighî percent, preferably about l to about 15 weight percent), an alkaline earth metal (at least 0.5 weight percent, preferably about 0.5 to about 50 weight percent) and rnixtures thereof; (3) al least 0.] weight percent of an oxygen storage metal oxide component (preferably ceria); and (4) at least 0.1 ppm of a nobîe metal component (preferably Pt, Pd, Rh, Ir,- Os, Ru, Re and rnixtures thereof). Preferred compositions in this class of materials comprise (1) an acidic oxide containing at least 50 weight percent alumina and substantially no zeolite; (2) at least 0.5 weight percent of.an alkali metal and/or an alkaline earth metal or rnixtures thereof; (3) about l to about 25 weight percent of an oxygen siorage capable transition metal oxide or a rare-earth (preferably, ceria); and (4) at least 0.1 ppm of a noble metal selected from the group consisting of Pt, Rh, Ir, and a combination thereof, all percentages being based on the total weight of the oxidative cătaiyst/additive cbmposhion.
[0051] Another class of non-zeolitic materials suitable for use in combination with the NOX reduction compositions of the invention include a low NOx, CO combustion promoier as disclosed and described in U.S. Patent Nos.' 6,165,933 and 6,358,881, the entire disdosure of these patents being herein incorporated by reference. Typically, the low NO CO combustion promoier compositions comprise (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or rnixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) palladium... The acidic oxide suppon preferably contains silica alumina. Ceria is the preferred oxygen storage oxide. Preferably, the NOX reduction composition comprises (1) an acidic metal oxide suppon containing at least 50 weight percent alumina; (2) about 1-10 • parts by weight, measured as metal oxide, of at least one alkali metal, alkaline earth metal or rnixtures thereof; (3) at least l part by weight of CeOs; and (4) about 0.01-5.0 parts by weight of Pd, all of said parts by weight of components (2) - (4) being per J 00 parts by weight ofsaid acidic metal oxide support material. [0052] Yet another class of non-zeolitic materials suitable for use in combination with the NOX reduction compositions of the invention include NOX reduction composilions as disclosed and described in U.S. Patent Nos. 6,280,607 Bl, 6,143,167, 6,379,536 and 6,129,834, the entire disclosure of these patents being herein incorporated by reference. In general, the NO* reduction compositions comprise (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 1B and 31B of the Periodic Table. Preferably, the acidic oxide support contains at least 50 weight percent alumina.and preferably contains silica alumina. Ceria is the preferred oxygen storage oxide. In a -preferred embodiment of the invention, the NO* reduction compositions comprise (1) an acidic oxide support containing at least 50 weight percent alumina; (2)']-]0 weight percent, measured as the metal oxide, of an alkali meta], an alkaline earth metal or mixtures thereof; (3) at least l weight percent CeC>2; and (4) 0.01-5.0 parts weight percent of a transition metal, measured as metal oxide, of Cu or Ag, al] parts by weight of
'*
components (2) - (4) being per 100 parts by weight of said acidic oxide support. [0053] Another class of non-zeolitic. NO„ reduction material suitable for .use in combination with the NOX reduction compositions of the invention include magnesium-aluminum spinel based additives heretofore being-usefuî for the removal of sulfur oxides from a FCC regenerator. Exemplary patents which disclose and describe this type of materials include U.S. Patent Nos. 4,963,520, 4,957,892, 4,957,718, 4,790,982, 4,471,070, 4,472,532, 4,476,245, 4,728,635, 4,830,840, 4,904,627, 4,428,827, 5,371,055, 4,495,304, 4,642^178, 4,469,589,- 4,758,418, 4,522,937, 4,472,267 and 4,495,305 the entire disclosure of said patents beingherein incorporated by reference. Preferably, compositions in this class comprise 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 selecîed from the group consisting of Group 1B metals, Group 1IB 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. ţin, bismuth, molybdenum, antimon-y, vanadium and mixiures thereof. Preferably, the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal, and the atomic' ratio of magnesium to aluminum in said spinel is at least about 0.17. The third metal in the spinel preferably comprises a metal selected from the group consisting of the

P]atinum Group metals, the rare-eanh melals and mixtures thereof. The third. metal component is preferably present in an amount in the.range of about 0.001 to about 20 weigbt percent, calculated as elemental third metal, and 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.
[0054] Other non-zeolitic materials useful in combination with the NOX reduction
additives of tne invention mcJude, but are not limited to, zinc based catalysts such as
disclosed and described in U.S. Patent No. 5,002,654; antimony based NOX reduction
additives such as described and disclosed in U.S. Patent No. 4,988,432; perovskite-
spinel NO* reduction additives such as described and disclosed in U.S. Patent Nos.
5,364,517 and 5,565,181; hydrotalcite catalyst and additive compositions such as
described and di'sclosed, for example, in U.S. Patent Nos. 4,889,615, 4,946,581,
4,952,382, 5,114,691, 5,114,898, 6,479,421 Bl and PCT International Publication
No. WO 95/03876; and low NO* promoter additive compositions such as described,
for example in U.S. Patent No. 4,290,878; the entire disclosure of each.patent being
herein incorporaied by reference.
[0055] It is aJso vvithin the scope of the invention to use the NOX reduction compositions of the invention in combinalion with NOX removal compositions as disclosed and described in PCT International Publication Number WO 03/046112 Al and PCT International Publication No. WO 2004/033091 Al, the entire disclosures of which are herein incorporated by reference. Such NO, removal composition generally comprises (i) an acidic oxide support, (ii) cerium oxide, (iii) a lanthanide oxide other than ceri a and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and 11B of the Periodic Table, noble metals, and mixtures thereof.
[0056] When used, the additional non-zeolitic NOX reduction compositions are used in an amount sufficient toprovide increased NOX reduction when compare'd to the use of the ferrierite NOX reduction compositions alone. Typically, the additional non-zeolitic compositions are used in an amounl up to about 50 weight percent of the FCC catalyst inventory. Preferably, the non-zeolitic composition is used in an amount up to about 30 weight percent, moşi preferably up io about l O weight percent of the FCC catalyst inveniory. The additional NO* reduction composition may be blended with
the FCC catalysl inventory as. a separate partide additive. A]temativ.e]y, the
additional NOx reduction composition may be incorporated into the FCC catalyst as
an integral component of the catalyst.
[0057] h is aJso contemplated within the scope of the present invention that MOX
reduction compositions in accordance wiih the present invention may be used in
combination wjth other additives conventionally used in the FCC process, e.g., SOX
reduction additives, gasoline-sulfur reduction additives, CO combustion prdmoters,
additives for the production of light olefins, and the like.
[0058] The scope of the invention is not-in any way imended to be' limited by the
examples set forth below. The examples include the preparation of catalyst/âdditives
*'
useful in the process of the invention and the evaluation of the invention process to reduce NOX in a catolytic cracking environment. The examples-are given as specific illustrations of the daimed invention. Jt should be understood, however, that the invention is not limiied to the specific details set forth in the examples. [0059] AII parts and percentages in the examples, as well as the remainder of the specification which refers to solid compositions or concentrations, are by weight unless otherwise specified. Concentrations of gaseous 'mixtures are by volume unless otherwise specified.
[0060] Further, any range of numbers recited in the specification or claims, such as that representing a panicular set of propenies, units of measure, conditioris, physical states or percentages, is imended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited.
EXAMPLES
EXAMPLE l
[0061] A composition comprising 40% ferrierite, 40% clay and 20% silica sol (Additive A) was prepared as follows. An aqueous slurry containing 29% ferrierite (SiO2/Al2O3 = 20) was milled in a Drais mill to an average partide size of less th'an 2.5 um. The milled ferrierite slurry (4160g) was combined with 1200g Natka clay (dry basis) and 6000g silica sol binder (10% solids). The silica sol binder was
prepared from sodium silicate and acid alum. The catalyst slurry was then spray-dried in a Bowen spray drier. The resuhing spray-dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a Na„O level of less than 0.1 weight percent. The properties of the additive are shown in Table ] below.
EXAMPLE 2
[0062] A composition comprising 75% ferrierite and 25% alumina sol' (Additive B) was prepared as follows. An aqueous slurry was prepared which contained 2174g of aluminum chJorohydrol solution (23%- solids), 1500g (dry basis) of. ferrierite (SiO2/Al2O3 = 20, NaoO -f K^O EXAMELE3 .
[0063] Additives A and B were evaluated for their ability to reduce NO* emissions from a FCCU using the Davison Circulating Riser (DCR). The description of the DCR has been published in the following papers: G. W. Young, G. D. Weatherbee, and S. W. Davey, "Simulating Commercia] FCCU Yields' With The Davison Circulating Riser (DCR) Pitoî Plant "Unit," National Petroleum Refiners_Association (NPRA) Paper AM88-52; G. W. Young, "Realistic Assessment of FCC Catalyst Performance in the Laboratory," in Fluid Catalytic Cracking: Science and Technology, J. S. Magee and M. M. Muche]], Jr. Eds. Studies in Surface Science and Catalysis Volume 76, p. 257, Elsevier Science Publishers B.V., Amsterdam 1993, ISBN 0-444-89037-R.
[0064] The DCR was started up by charging the unit with approximately 1800g of a
® commercially available cracking catalyst, SUPERNOVA -DMR+, obtained from
Grace Davison. hydrothermally deactivated in a fluidiz,ed bed reactor with 100% steam for 4 hours at 816'C.
(Table Removed)
[0066] The DCR was operated with l % excess 02 in the regenerator, and with the regenerator operaiing at 705 C. After the unit stabilized the baseline NO* emissions data were collected using an on-line Lear-Siegler SO,/NOX Analyzer (SM8100A). Subsequently, lOOg of catalyst were injected into the DCR consisting of 4.75g of a commercial sample of a Pt-based combustion promoter, CP-3® (obtained'from Grace Davison), which hâd been deactivated for 20 hours at 788°C without any added Ni or V using the Cyclic Propylene Steaming method (CPS) and 95.25 grams of hydrothermally deactivated SUPERNOVA®-DMR+. The description of the CPS method has been published in L.T. BoocL T.F. Peni. and J.A Rudesill, "Contaminant-Metal Deactivation and Metal-Dehydrogenation Effects During Cyclic Propylene
Sieaming of Fluid Catalytic Cracking CaîaJysts," Deactivation and Testing of Hydrocarbon Processing Catalysts, ACS Symposium Series 634, p. 171 (1996), ISBN 0-8412-3411-6.
[0067] After the unii was again stabilized, the NO* emissions data were collected. Thereafter, 0.525g of the CO promoter wjth 2]0g of Additive A, or ]05g of the same sieamed deactivated cracking cata]yst originally loaded into the DCR with I05g-of Additive B was added to the DCR; The resuhs are recorded in Table 3 beJow." TOS is lime on stream from the lime of adding Pt CO combuslion promoter ,to the unit. As shown in that table and the FJGURE, Additives A and B are effective in-reducing NOX emissions from the DCR regenerator.
[0068] Table 4 shows the conversion and product yields with and without the compositjon of this invention. In Table 4 the means of conversion and cracked product yields were calculated using a sample of 7 baseh'ne DCR tests. Aş shbwn in Table 4, when acconnting for the expected variation from-experiment to experiment, both Additives A and B are especially effective in decreasing NOX emissions without signifi'cantly affecting the cracked products yields. In' particular, both overall conversion and gasoline yield do not change.substantialîy, even though the FCC feedstock used in these experiments is a high nitrogen feed.
EXAMPLE 4
[0069] A composition comprising 65% ferrierite, 20% Alumina Sol and 15% kaolin clay (ADDITJVE C) was prepared as follows: An aqueous slurry was prepared which comained 40.3 Ibs of alurninurrr chlorohydrol solution (23% solids), 29.3 Ibs (dry basis) of ferrierite (SiO2/AI203 = 36, Na20 -f K20 and 32.5 Ibs additional water, enough to make a slurry which contained about 40% solids. The slurry was milled in a Drais mill to an average partide size of less' than 2.5 um and then spray-dried in a Bowen Engineering spray drier. The spray-dried product was calcined for 60 minutes at ]]009F. The properties of the catalyst are shown in Table 5 below.
(Table Removed)

EXAMPLE 5
[0070] A paniculaie NO* reduction composition (Additive D) was prepared as follows: A slurry was prepared from an aqueous slurry having 20% solids of a peptizable alumina (Versal 700 alumina powder obtained from La Roche Industries Inc., 99% A^Oa, 30% moisture). The alumina slurry was prepared using 31.6 Ibs of the alumina. To the alumina slurry 3.87 Ibs of an aqueous sodium hydroxide'solution (50% NaOH) was added. Next, 10.4 Ibs of cerium carbonate crystals .(obtained from Rhone Poulenc, Inc., 96% CeOj, 4% La203, 50% moisture) was added to the'slurry.
The slurry was diluted with a sufficient amount of water to bring .the solids
»» conceniration of the slurry to 12%. Finally, 3.38 Ibs of ion exchanged silica sol of
Nalco 1140 (obtained from Nalco Chemicals Co.) was added to the slurry. The mixture was agilated to assure good mixing and then milled in a stirred media mi]] to reduce agglomerates to substantially less than 10 pm. The milled mixture was then spray-dried to form approximately 70 um microspheres and thereafter calcined at approximately 650°C to remove volatiles. The resuhing material was impregnated with an aqueous solution of a Cu containing salt (e.g., CuSO^) to achieve about 2% Cu on the final product, and was flash dried. The final product hâd the following analysis (dry basis): 7.8% SiO2, 7.1% Na2O, 18.5% Ce02, 60.2% A12O3,1.9% Cu and BET surface area of 111 m2/g.
EXAMPLE 6
[0073] Additive C and a blend of Additives C and D consisting of 75% Additiye C and 25% Additive D where tested in the DCR with a feedstock having the properties shown in Table 6. The unit was loaded with I995g of an equilibrium cracking caialyst (ECAT) having the properties as shown in Table 7 below, and 5g' of the. commercially available CO combustion promoter CP-3®,-which hâd been deactivated for 20 hours at 788°C without any added Ni or V using the CPS method. After the unit was stabilized, the baseline NO* emissions data were collected. Subsequently, 42g of Additive C or the blend of Additive C and D were injected into the unit alo'ng with 0.25g of the combustion promoter, and ]57.75g of the equilibrium catalyst. The results are shown in Table 8 below. TOS is time on stream from the time of adding

the Pt CO combustion promoter to the unit. As this Table shows, both Additive C and the blend of Additives C and D are effective in decreasing NO, emissions in the DCR unit regenerator. However, the blend of Additives C and D when used in the catalyst inventory in the same amount as Additive C alone is more effective in reducing NOX than Additive C
. (Table Removed)

We claim:
1. A process of reducing NOX emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said process consisting of:
(i) contacting a hydrocarbon feedstock in a catalytic cracking zone operating at a temperature ranging from 480 °C to 600 °C under fluid catalytic cracking (FCC) conditions with a circulating catalyst inventory of FCC catalytic cracking catalyst comprising a Y-type zeolite and a particulate NOx reduction composition having a mean particle size of greater than 45 µm and comprising (i) at least 30 weight percent of ferrierite zeolite, and (ii) from 5 to 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, aluminum phosphate and mixtures thereof, to produce an effluent comprising cracked products and spent catalyst containing coke and strippable hydrocarbons;
(ii) discharging and separating a vapor phase rich in cracked products and a solids rich phase comprising the spent equilibrium cracking catalyst and NOx reduction composition;
(iii) removing the vapor phase as product;
(iv) stripping the spent FCC cracking catalyst and NOx reduction composition to remove the strippable hydrocarbons; and
(v) oxidatively regenerating the spent FCC cracking catalyst and the NOx reduction composition in a regeneration zone operating at a temperature of 600 °C to 800°C to remove the coke from the FCC cracking catalyst and NOx reduction composition and reduce the amount of NOx emissions released from the regeneration zone by at least 10% relative to the amount of NOx emissions released In the absenee of the NOx redustion composition; and

(vi) recycling the regenerated FCC catalyst and regenerated NOX reduction composition to the cracking zone for further cracking and NOx reduction.
2. The process as claimed in claim 1 wherein step (v) 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.
3. The process as claimed in claim 1 wherein the amount of ferrierite zeolite present in the NOx reduction composition is at least 40 weight percent of the composition.
4. The process as claimed in claim 3 wherein the amount of ferrierite zeolite present in the NOx reduction composition is at least 50 weight percent of the composition.
5. The process as claimed in claim 1 wherein the amount of ferrierite zeolite present in the NOx reduction composition ranges from 30 to 80 weight-percent of the composition.
6. The process as claimed in claim 5 wherein the amount of ferrierite zeolite present in the NOx reduction composition ranges from 40 to 75 weight percent of the composition.
7. The process as claimed in claim 1 or 2 wherein the ferierite zeolite is exchanged with a cation selected from the - group consisting of hydrogen, ammonium, alkali metal and combinations thereof.
8. The process as claimed in claim 1 wherein the ferrierite zeolite further comprises at least one stabilizing metal.
9. The proceses as claimed in claim 8 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.

10. The process as claimed in claim 9 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.
11. The process as claimed in claim 10 wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof.
12. The process as claimed in claim 8 wherein the stabilizing metal is incorporated into the pores of the ferrierite zeolite.
13. The process as claimed in claim 1 wherein the inorganic binder is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof.
14. The process as claimed in claim 13 wherein the inorganic binder is alumina.
15. The process as claimed in claim 14 wherein the alumina is an acid or base peptized alumina.
16. The process as claimed in claim 14 wherein the alumina is aluminum chlorohydrol.
17. The process as claimed in claim 1 wherein the amount of inorganic binder present in the particulate NOx reduction composition ranges from 10 to 30 weight percent of the composition.
18. The process as claimed in claim 17 wherein the amount of inorganic binder present in the particulate NOx reduction composition ranges from 15 to 25 weight percent of the composition.
19. The process as claimed in claim 1 wherein the particulate NO* reduction composition further comprises an additional zeolite other than ferrierite zeolite,

20. The process as claimed in claim 19 wherein the additional zeolite is a zeolite having a pore size ranging from 3 to 7.2 Angstroms and a SiO2 to Al2O3 molar ratio less than 500.
21. The process as claimed in claim 20 wherein the SiO2 to Al2O3 molar ratio is less than 250.
22. The process as claimed in claim 19 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, Loydarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite and mixtures thereof.
23. The process as claimed in 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, Offretite, A, ZSM-12 and mixtures thereof.
24. The process as claimed in claim 19, 20 or 22 wherein the additional zeolite is present in an amount ranging from 1 to 80 weight percent of the composition.
25. The process as claimed in claim 24 wherein the additional zeolite is present in an amount ranging from 10 to 70 weight percent of the composition.
26. The process as claimed in claim 1 or 2 wherein the NOx 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.

27. The process as claimed in claim 26 wherein the matrix material is present in an amount less than 70 weight percent.
28. The process as claimed in claim 1 or 2 further comprising recovering the cracking catalyst from said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst
29. The process as claimed in claim 28 wherein the cracking catalyst and the particulate NOx reduction composition are fluidized during contacting said hydrocarbon feedstock.
30. The process as claimed in claim 1 or 2 further comprising contacting the hydrocarbon feed with at least one additional NOx reduction composition.
31. The process as claimed in claim 30 wherein the additional NOx reduction composition is a non-zeolitic composition.
32. The process as claimed in claim 31 wherein the additional NOx reduction, composition comprises (1) an acidic metal oxide; (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. .;
33. The process as claimed in claim 30 wherein the additional NOx reduction composition is a low NOx, 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.
34. The process as claimed in claim 30 wherein the additional NOx 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.
35. The process as claimed in claim 30 wherein the additional NOx 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.
36. The process as claimed in claim 35 wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal.
37. The process as claimed in claim 36 wherein the third metal component in the metal containing spinel is selected from the grpup consisting of a Platinum Group metal, the rare-earth metals and mixtures thereof.
38. The process as claimed in claim 35 wherein the third metal component is present in an amount in the range of 0.001 to 20 weight percent, calculated as elemental third metal.
39. The process as claimed in claim 35 wherein said fourth metal component is present in an amount in the range of 0.001 to 10 weight percent, calculated as elemental fourth metal.
40. The process as claimed in claim 30 wherein the additional NOx reduction additive is a zinc based catalyst.

41. The process as claimed in claim 30 wherein the additional NOx reduction additive is an antimony based NOx reduction additive.
42. The process as claimed in claim 30 wherein the additional NOx reduction additive is a perovskite-spinel NOx reduction additive.
43. The process as claimed in claim 30 wherein the additional NOx reduction additive is a hydrotalcite containing composition.
44. The process as claimed in claim 1 wherein the particulate NOx reduction composition has a mean particle size from 50 to 200 urn.
45. The process as claimed in claim 44 wherein the particulate NOx reduction composition has a mean particle size from 55 to 150um.
46. The process as claimed in claim 1 wherein the amount of the NOx 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.
47. The process as claimed in claim 30 wherein the additional NOx 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.

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Patent Number

250336

Indian Patent Application Number

2090/DELNP/2006

PG Journal Number

52/2011

Publication Date

30-Dec-2011

Grant Date

27-Dec-2011

Date of Filing

18-Apr-2006

Name of Patentee

W. R. GRACE & CO.- CONN.

Applicant Address

7500 GRACE DRIVE, COLUMBIA, MARYLAND 21044-4098, USA.

Inventors:

#	Inventor's Name	Inventor's Address
1	MICHAEL SCOTT ZIEBARTH	12071 LITTLE PATUXENT PARKWAY, CLOUMBIA, MD 21044, USA.
2	XINJIN ZHAO	1731 CATTAIL MEADOWS DRIVE, WOODBINE, MD 21797, USA.
3	GEORGE YALURIS	6702 SURREY LANE, COLUMBIA, MD 21029, USA.

PCT International Classification Number

C10G 11/18

PCT International Application Number

PCT/US2004/036642

PCT International Filing date

2004-11-04

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	10/702,240	2003-11-06	U.S.A.
2	10/909,706	2004-08-02	U.S.A.