MXPA06005000A

MXPA06005000A - FERRIERITE COMPOSITIONS FOR REDUCING NOx

Info

Publication number: MXPA06005000A
Application number: MXPA/A/2006/005000A
Authority: MX
Inventors: Scott Ziebarth Michael; Zhao Xinjin; Yaluris George
Original assignee: Yaluris George; Zhao Xinjin; Ziebarth Michael S
Priority date: 2003-11-06
Filing date: 2006-05-04
Publication date: 2006-10-17

Abstract

Compositions for reduction of NOx generated during a catalytic cracking process, preferably, a fluid catalytic cracking process, are disclosed. The compositions comprise a fluid catalytic cracking catalyst composition, preferably containing a Y-type zeolite, and a particulate NOx reduction composition containing ferricrite zeolite particles. Preferably, the NOx reduction composition contains ferrierite zeolite particles bound with an inorganic binder. In the alternative, the ferrierite zeolite particles are incorporated into the cracking catalyst as an integral component of the catalyst. NOx reduction compositions in accordance with the invention are very effective for the reduction of NOx emissions released from the regenerator of a fluid catalytic cracking unit operating under FCC process conditions without a substantial change in conversion or yield of cracked products. Processes for the use of the compositions are also disclosed.

Description

FERRIERITE COMPOSITIONS TO REDUCE NOx EMISSIONS DURING FLUIDIZED CATALYTIC DISINTEGRATION FIELD OF THE INVENTION The present invention relates to NOx reduction compositions and to the method for using them to reduce N0X emissions in refinery processes, and especially in the processes of disintegration or fluidized catalytic fractionation (FCC). More particularly, the present invention relates to N0X reduction compositions and their method of use for reducing the NOx content outside the gases released from a fluidized catalytic decay regenerative unit (FCCu) during the FCC process without a substantial change in the conversion of hydrocarbons or in the performance of the fractioned products. BACKGROUND OF THE INVENTION In recent years there has been increasing 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 imposed limits on the acceptable emissions of one or more of these pollutants, and the trend is clearly in the direction of increasingly stringent regulations.

The N0X, or nitrogen oxides, in the flue gas streams leaving the decomposition or fluidized catalytic fractionation (FCC) regenerators, without a global problem. The decomposition or catalytic fractionation units (FCCU) process heavy hydrocarbon feeds containing nitrogen compounds, a portion of which is contained in the coke on the catalyst when it enters the regenerator. Some of this coke-nitrogen eventually becomes NOx emissions, either in the FCC regenerator or in a downstream CO boiler. Therefore, all FCCUs that process nitrogen-containing feeds can have a problem of NOx emissions due to catalytic regeneration. In the FCC process, the catalyst particles (inventory) circulate continuously between the catalytic fractionation or decay zone and a catalyst regeneration zone. During regeneration, the coke deposited on the particles of the decomposition catalyst in the decomposition or fractionation zone is removed at elevated temperatures by oxidation with oxygen-containing gases such as air. The removal of the coke deposits restores the activity of the catalytic particles to the point where they can be reused in the decomposition or fractionation reaction. In general, when the coke is calcined with an oxygen deficiency, the regenerator's flue gas has a high CO / C02 ratio and a low level of N0X, but when it is calcined with excess oxygen, the flue gas has a high level of N0X, and a reduced content of CO. Therefore, the CO and N0X, or mixtures of these pollutants, are emitted with the flue gas in variable quantities, depending on factors such as the unit's feeding speed, the nitrogen content of the feed, the design of the regenerator, the mode of operation of the regenerator, and the composition of the catalyst inventory. Several attempts have been made to limit the amount of NOx gases emitted from the FCCU, treating the N0X gases after their formation, for example, post-treatment of gas streams containing N0X as described in US Patent Nos. 4,434,147, 4,778,664, 4,735,927, 4,798,813, 4,855,115, 5,413,699, and 5,547,648. Another technique has been to modify the operation of the regenerator to partially calcinate and then treat the NOx precursors in the flue gas before these are converted to NOx, for example, US Pat. Nos. 5,] 73,278, 5,240,690, 5,372,706, 5,413,699 , 5,705,053, 5,716,514, and 5,830,346.

Still another approach has been to modify the operation of the regenerator in terms of reducing N0x emissions, for example, US Patent 5,382,352, or modifying the used CO combustion promoter, for example, US Patent 4,199,435, 4,812,430, and 4,812,431. It has also been suggested to enrich the air with oxygen in a regenerator operating in the partial calcination mode, for example, US Pat. No. 5,908,804. Additives have also been used in attempts to deal with NOx emissions. U.S. Patent Nos. 6,379,536, 6,280,607, 6,129,834 and 6,143,167 describe the use of NOx removal compositions to reduce the measurements of the FCCU regenerator. US Patents Nos. 6,358,881 and 6,165,933 also describe a NOx reduction composition, which promotes the combustion of CO during the step of regenerating the FCC catalyst, while simultaneously reducing the NOx level emitted during the step of regeneration. The NOx reduction compositions described by these patents can be used as an additive which is circulated in conjunction with the FCC catalyst inventory, or incorporated as an integral component of the FCC catalyst. US Patents Nos. 4,973,399 and 4,980,052 describe the reduction of NOx emissions from the FCCU generator, incorporating in the circulating inventory of decomposition catalyst, the separated additive particles containing zeolite charged with copper. Many additive compositions used hitherto to control N0X emissions have typically caused a significant reduction in the conversion of hydrocarbons or the performance of valuable products of decomposition, for example, gasoline, light olefins and liquefied petroleum gases ( LPGs), while the production of coke is increased. A highly desirable feature of the NOx additives added to the FCCU is that it does not affect the yields of the fractionated products or change the overall conversion of the unit. The operation of the FCCU is typically optimized based on the design of the unit and the catalyst, to produce a slate of fractionated products, and maximize the profitability of the refinery. This product slate is based on the specific refinery's value model. For example, during the peak summer driving season many refineries want to maximize gasoline production, while during the winter season many refineries may wish to maximize the production of heating oil. In other cases a refinery may find it profitable to produce light olefins that can be sold on the open market or used in associated petrochemical plants as raw materials. When an N0X reduction additive increases the production of coke, the FCCU may have insufficient air capacity to burn the extra coke and may result in low feed performance in the unit. If the additive increases the production of dry gas of little value, it can decrease the production of the most valuable products. An increase in dry gas may exceed the capacity of the unit to handle it, thus forcing a reduction in the amount of processed feed. While an additive that increases the production of light olefins may be desirable if the refinery values these products and the unit has the necessary equipment to process the extra light hydrocarbons, the additive may, however, reduce profitability if the objective of the refinery is to maximize the production of gasoline. Light olefins are typically produced in the FCCU at the expense of gasoline production. Even an additive which increases the conversion of the unit may be undesirable if it affects the performance of the product, causes the unit to limit the equipment, and / or reduces the amount of power that can be processed.

Consequently, any change in the FCCU that affects the programming of the product, or changes the ability to process the feed at the desired speed can be detrimental to the profitability of the refinery. Therefore, there is a need for NOX control compositions which do not affect the performance of the products and the overall conversion of the unit. BRIEF DESCRIPTION OF THE INVENTION It has now been discovered that the incorporation of a ferrierite zeolite component with an inventory of catalytic cracking or decay catalyst, in particular an inventory of decay or fractionation catalyst containing an active type Y zeolite, which is circulated through a fluidized catalytic cracking or fractionation unit (FCCU) during a fluidized catalytic cracking or fractionation (FCC) process, provides superior N0X control efficiency without changing or substantially affecting hydrocarbon conversion or performance of fractionated petroleum products, produced during the FCC process. New NOx reduction compositions are provided according to the present invention. Typically the NOx reduction compositions comprise a particulate composition containing ferrierite zeolite particles.

The ferrierite zeolite can be added as separate additive particles to a circulating inventory of the catalyst or incorporated directly into the Y-type zeolite containing the decay catalyst as an integral component of the catalyst. In a preferred embodiment of the invention, the ferrierite zeolite constitutes separate particles bound with an inorganic binder. The binder preferably comprises alumina or silica alumina. Preferably, the ferrierite zeolite is exchanged with hydrogen, ammonium, alkali metals and combinations thereof. The preferred alkali metal is sodium, potassium and combinations thereof. In one aspect of the invention, new NOx reduction compositions containing ferrierite zeolite are provided, which are added to a circulating inventory of the decomposition catalyst or catalytic fractionation as a separate mixture of particles, to reduce the NOx emissions released of the FCCU regenerator during the FCC process. In another aspect of the invention, novel NOx reduction compositions are provided which comprise ferrierite zeolite incorporated as an integral component of the FCC catalyst, which preferably contains an active component of type Y zeolite.

In yet another aspect of the invention, new N0X reduction compositions are provided which compositions reduce the N0X emissions of the FCCU regenerator during the FCC process, while substantially maintaining the conversion of hydrocarbons and the performance of the products of fractionated oil and minimizing an increase in coke production. Another aspect of the present invention is to provide a process for reducing the N0X content in the outlet gas of the FCCU regenerator during the FCC process, using NOx reduction compositions according to the present invention. Another aspect of the invention is to provide improved FCC processes for reducing the NOx content in the exhaust gases of the FCCU regenerator without substantially affecting the conversion of hydrocarbons or the performance of petroleum products produced during the FCC process. These and other aspects of the present invention are described in more detail below. BRIEF DESCRIPTION OF THE DRAWINGS The figure is a graphic representation of the effectiveness of Additive A and Additive B, prepared in EXAMPLES 1 and 2, respectively, to reduce the NOx emissions of a DCR regenerator versus time in the stream, when the additives are mixed with a commercially available decomposition or fractionation catalyst (SUPERNOVA®-DMR +, obtained from Grace Davidson, Columbia, MD), which contains 9.25 weight percent of a platinum promoter, CP-3® (obtained from Grace Davidson, Columbia, MD) and which is activated using the Vaporization procedure of Cyclic propylene as described in EXAMPLE 3. DETAILED DESCRIPTION OF THE INVENTION Although several nitrogen oxides are known which are relatively stable at ambient conditions, for the purposes of the present invention, NOx will be used here to represent nitric oxide , nitrogen dioxide (the main noxious nitrogen oxides) as well as N20, N2O5 and mixtures thereof. The present invention encompasses the discovery that the use of NOx reduction compositions containing ferrierite zeolite in combination with a fluidized catalytic disintegration catalyst (FCC). Preferably a catalyst comprising an active Y-type zeolite, is very effective for the reduction of NOx emissions released from the FCCU regenerator under the FCC process conditions, without a substantial change in hydrocarbon feed conversion or yield. of the fractioned products. The N0X reduction compositions typically comprise a particulate composition containing particles of ferrierite zeolite. In a preferred embodiment of the invention the feriecite particles are agglutinated with an inorganic binder. The new N0X reduction compositions containing ferrierite zeolite can be added to the circulating inventory of the catalytic disintegration catalyst as separate additive particles or incorporated as an integral component in the decay catalyst. For the purposes of the present invention, the phrase "a substantial change in the conversion of the hydrocarbon feed or the yield of the fractioned products" is defined herein to denote, in the alternative, (i) a relative change less than 50%. %, preferably a relative change of less than 30% and more preferably a relative change of less than 15% in the performance of the LPG (liquefied petroleum gas) when compared to the baseline yield of the same or substantially the same product; or (ii) a relative change of less than 30%, preferably a relative change of less than 20% and more preferably a relative change of less than 10% in the performance of LCO (light cyclic oils), bottoms and gasoline in combination with the LPG when compared to the baseline performance of the same or substantially the same products; or (iii) a relative change of less than 10%, preferably a relative change less than 6.5% and more preferably a relative change less than, 5% in the conversion of the hydrocarbon feed when compared to the line conversion base. The conversion is defined as 100% times (1 fund yield - LCO performance). When the reduction composition is used as a separate additive, the baseline is the conversion or average yield of a product in the FCCU, operating with the same or substantially the same feed and under the same or substantially the same reaction conditions and of the unit, but before the additive of the present invention is added to the catalyst inventory. When the NOx reduction composition is integrated or incorporated into the decay or fractionation catalyst particles, to provide an integral NOx reduction catalyst system, a significant change in the conversion or yield of fractionated hydrocarbon products is determined. , using a baseline defined as the conversion or average yield of a product in the same or substantially the same FCCU operating with the same or substantially the same operation, under the same or substantially the same reaction and conditions of the unit, with a disintegration or fractionation catalyst comprising the same or substantially the same decay or fractionation catalyst as that containing the N0X reduction composition, except that the NOx reduction composition is replaced in the decay or fractionation catalyst with one component of matrix such as kaolin or other filling. The percentage changes specified above are derived from the statistical analysis of the DCR operation data. Any ferrierite zeolite is useful for preparing the NOx reduction compositions of the invention, however, it is preferred that the ferrierite zeolite has a surface area of at least 100 m2 / g, more preferably at least 200 m2 / g and more preferably at least 300 m2 / g and a molar ratio of Si02 to A1203 less than 500, preferably less than 250, more preferably less than 100. In one embodiment of the invention, the ferrierite zeolite is exchanged with a material selected from the group it consists of hydrogen, ammonium, alkali metals and combinations thereof, before incorporation into the binder or FCC catalyst. The preferred alkali metal is one selected from the group consisting of sodium, potassium and mixtures thereof. Optionally, the ferrierite zeolite may contain stabilizing amounts, for example, up to 25 weight percent, of a stabilizing metal (or metal ions), preferably incorporated in the pores of the zeolite. Suitable stabilizing metals include, but are not limited to metals selected from the group consisting of Groups HA, IIIB, IVB, VB, VIB, VIIB, VIII, IIB, IIIA, IVA, VA, the Lanthanide Series of the Table Periodic, Ag and mixtures thereof. Preferably, the stabilizing metals are selected from the group consisting of Groups IIIB, HA, IIB, IIIA and the Lanthanide Series of the Periodic Table, and mixtures thereof. More preferably, the stabilizing metals are selected from the group consisting of lanthanum, aluminum, magnesium, zinc, and mixtures thereof. The metal can be incorporated into the pores of the ferrierite zeolite by any method known in the art, for example, impregnation or the like. For the purposes of this invention, the Periodic Table referenced here is the Periodic Table that is published by the American Chemical Society. The amount of ferrierite zeolite used in the NOx reduction compositions of the invention will vary depending on several factors including but not limited to, how to combine the ferrierite zeolite with the catalytic cracking or decay catalyst and the catalyst type of the catalyst. disintegration used. In one embodiment of the invention, the N0X reduction compositions of the invention are separate catalyst / additive compositions and comprise a particulate composition formed by agglutinating particles of a ferrierite zeolite with a suitable inorganic binder, generally, the amount of zeolite The ferrierite present in the particulate N0X reduction compositions is at least 10, preferably at least 30, more preferably at least 40 and even more preferably at least 50, weight percent based on the total weight of the composition. Typically, the catalyst / particulate additive composition of the invention contains from about 10 to about 85, preferably from about 30 to about 80, more preferably, from about 40 to about 75, percent by weight of ferrierite zeolite, based on the total weight of the catalyst / additive composition. Binder materials useful in preparing the particulate compositions of the invention include any inorganic binder that is capable of binding the ferrierite zeolite powder to form particles having properties suitable for use in the FCCU under the conditions of the FCC process. Typical inorganic binder materials useful for preparing the compositions according to the present invention include, but are not limited to, alumina, silica, silica alumina, aluminum phosphate and the like, and mixtures thereof. Preferably, the binders are selected from the group consisting of alumina, silica, silica alumina. More preferably, the binder comprises alumina. Even more preferably, the binder comprises an alumina peptized by acid or base. More preferably, the binder comprises a sol or liquid colloid of alumina, for example, aluminum chlorohydrol. In general, 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, more preferably from about 15 to about 25 weight percent. percent by weight of the NOx reduction composition of the invention. 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, alumina silica, yttria, lanthana, ceria, neodymium, samaria, europia, gadolinium, titania, zirconium, praseodium, and mixtures thereof). When used, the materials are used in an amount which does not significantly adversely affect the performance of the compositions to reduce the NOx emissions released from the FCCU regenerator under the conditions of FCC, the conversion of the hydrocarbon feedstock or the product yield of the disintegration or fractionation catalyst. In general, the additional materials will comprise no more than about 70 percent by weight of the compositions. It is preferred, however, that the compositions of the invention consist essentially of ferrierite and an inorganic binder. The particulate NOx reduction compositions of the invention should have a sufficient particle size to allow the composition to circulate throughout the FCCU simultaneously with the disintegration catalyst inventory during the FCC process. Typically, the composition of the invention will have an average particle size greater than 45 μm. preferably, the average particle size is from about 50 to about 200 μm, more preferably from about 55 to about 150 μm, even more preferred from about 60 to about 120 μm. The compositions of the invention typically have a Davison wear index (DI) of less than about 50, preferably less than about 20, more preferably less than about 15.

While the present invention is not limited to any particular process of preparation, typically the particulate N0X reduction compositions of the invention are prepared by forming an aqueous suspension containing the ferrierite zeolite, optional zeolite components, the inorganic binder and materials optionally available in an amount sufficient to provide at least 10.0 by weight of ferrierite zeolite and at least 5.0 weight percent binder material in the final NOx reduction composition and then spray dry the suspension to form particles . The spray dried particles are optionally dried at a sufficient temperature for a sufficient time to remove the volatiles, for example, at about 90 ° C to about 320 ° C, for about 0.5 to about 24 hours. In a preferred embodiment of the invention, the ferrierite zeolite containing the aqueous suspension is ground prior to spray drying to reduce the average particle size of the materials contained in the suspension to 10 μm or less, preferably 5 μm or less, more preferably 3 μm or less. The aqueous suspension containing the ferrierite zeolite can be milled before or after incorporation into the binder and / or matrix materials as desired. The spray dried composition can be calcined at a temperature and for a time sufficient to remove the volatiles and provide sufficient hardness to the binder for use in the FCCU under the conditions of the FCC process, preferably from about 320 ° C to about 900 ° C. C from about 0.5 to about 6 hours. Optionally, the dried or calcined composition is washed or exchanged with an aqueous solution of ammonia or ammonium salt (for example, sulfate, nitrate, chloride, carbonate, ammonium phosphate, and the like), or an organic or inorganic acid ( for example, sulfuric, nitric, phosphoric, hydrochloric, acetic, formic acid and the like) to reduce the amount of alkali metals, eg, sodium or potassium, in the finished product. The NOx reduction compositions of the invention are circulated throughout the FCCU in the form of separate particle additives together with the main fractionation or decay catalyst. In general, the catalyst / additive composition is used in an amount of at least 0.1 weight percent of the FCC catalyst inventory. Preferably, the amount of the catalyst / additive composition used ranges from about 0.1 to about 75 weight percent, more preferably from about 1 to about 50 weight percent of the FCC catalyst inventory. The separate particle catalyst / additive compositions of the invention can be added to the FCCU in the conventional manner, for example, with the replacement catalyst to the regenerator or by another convenient method. In a second embodiment of the invention, the ferrierite zeolite is integrated or incorporated into the decay catalyst particles themselves, to provide an integral NOx reduction catalyst system. According to this embodiment of the invention, the ferrierite zeolite can be added to the catalyst at any stage during the manufacture of the catalyst prior to spray drying the decay or fractionation catalyst slurry to obtain the fluidized disintegration catalyst, independently of any optional or additional required processing step necessary to complete the preparation of the disintegration catalyst. Without attempting to limit the incorporation of ferrierite, and any optional zeolite component, into the decay catalyst to any specific method of manufacturing the decay or fractionation catalyst, typically ferrierite zeolite, any additional zeolite, the zeolite of the disintegration catalyst, usually of the USY or REUSY type, and any matrix material are suspended in water. The suspension is milled to reduce the average particle size of the solids in the suspension to less than 10 μm, preferably to less than 5 μm, more preferably less than 3 μm. The milled suspension is combined with a suitable inorganic binder, i.e., a liquid silica colloid binder, and an optional matrix material, e.g., clay. The resulting suspension is mixed and spray dried to provide a catalyst material. The catalyst is spray dried by optionally using an aqueous solution of ammonium hydroxide, an ammonium salt, an inorganic or organic acid, and water to remove undesirable salts. The washed catalyst can be exchanged with a water-soluble rare earth salt, for example chloride, nitrates and the like of rare earths. Alternatively, the ferrierite zeolite, optional additional zeolites, the zeolite of the decay catalyst, any matrix material, a water soluble salt of rare earths, the liquid colloid binder of clay or alumina are suspended in water and mixed. The suspension is milled and spray dried. The spray-dried catalyst is calcined at about 250 ° C to about 900 ° C. The spray-dried catalyst optionally can be washed using an aqueous solution of ammonium hydroxide, an ammonium salt, an inorganic or organic acid, and water to remove undesirable salts. Optionally, the catalyst can be exchanged with a water-soluble rare earth salt after it has been washed, by any of the methods known in the art. When integrated into the FCC catalyst particles, the ferrierite zeolite compound typically represents at least about 0.1 weight percent of the FCC catalyst particles. Preferably, the amount of ferrierite zeolite used ranges from about 0.1 to about 60 weight percent, more preferably from about 1 to about 40 weight percent, of the FCC catalyst particles. The integrated FCC catalyst will typically comprise the ferrierite zeolite together with the catalyst zeolite, the inorganic binder materials and optionally the matrix, fillers, and other additive components such as metal traps (e.g., Ni and V traps) to complete the disintegration or fractionation catalyst. The zeolite of the decay catalyst, usually of a Y, USY or REUSY type, provides the majority of the decay activity and typically occurs in a range from about 10 to about 75, preferably from about 15 to about 60 and more preferably from about about 20 to about 50 weight percent based on the total weight of the composition. Inorganic binder materials useful in preparing the integrated catalyst compositions according to the present invention include any inorganic material capable of binding the components of the integrated catalyst to form particles having properties suitable for use in the FCCU under the FCC process conditions. . Typically, 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. In general, 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 material present in the integrated catalyst composition ranges from about 5 to about 45 weight percent, more preferably from about 10 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. The matrix materials optionally present in the integrated catalyst compositions of the present invention include, but are not limited to, alumina, silica alumina, rare earth oxides such as lanthanum, transition metal oxides such as titania, zirconium, and sodium oxide. manganese, oxides of the HA Group such as magnesium and barium oxides, clays such as kaolin, and mixtures thereof. The matrix or fillers may be present in the integral catalyst in the amount of less than 50 weight percent based on the total weight of the composition. Preferably, the matrix and the fillers, if any, are present in an amount ranging from about 1 to about 45 weight percent, present based on the total weight of the catalyst composition. The particle size and the wear properties of the integral catalyst affect the fluidization properties in the unit and determine how well the catalyst is retained in the commercial FCC units. The integral catalyst composition of the invention typically has an average particle size of from about 45 to about 200 μm, more preferably from about 50 μm to about 150 μm. The wear properties of the integral catalyst, when measured by the Davison Wear Index (DI), have a DI value of less than 50, more preferably less than 20 and more preferably less than 15. In a preferred embodiment of the invention , the FCC disintegration or fractionation catalyst contains a Y-type zeolite. The ferrierite zeolite can be added as separate additive particles to a circulating inventory of the decay or fractionation catalyst or is directly incorporated into the decay or fractionation catalyst containing Y type zeolite, as an integral component of the catalyst. In any case, it is preferred that the ferrierite zeolite be present in the final composition in an amount sufficient to provide in the total catalyst inventory a ratio of ferrierite zeolite to type Y zeolite less than 2, preferably less than 1. Also Within the scope of the invention is to include additional zeolite components in the N0X reduction compositions containing ferrierite zeolite of the invention. The additional zeolite component can be any zeolite that does not adversely affect the N0X reduction performance or that causes a substantial change in the conversion of hydrocarbons or the yields of the fractioned products during the FCC process. Preferably, the additional zeolite component is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms with a molar ratio of SiO2 to A1203 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-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, Rho zeolite, heroinite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Bid, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-35, ZSM-57, ZSM-61, ZK-5, NaJ, Un-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, Diaquiardite, Merlinoite, Lovdarite, Levite, Laumontite, Epistilbite, Gmelonite, Gismondin, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreecite, Natrolite or mixtures thereof. More preferably, the additional zeolite component is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, Rho zeolite, heroinite, chabazite, clinoptilolite, MCM- 22, MCM-35, Ofertite, A, ZSM-12 and mixtures thereof. The additional zeolite component is used in any amount that does not significantly adversely affect the performance of the N0X reduction compositions to reduce N0X emissions and substantially maintain the conversion of hydrocarbons or product yields of the disintegration catalyst with relation to the use of the disintegration catalyst without the catalyst / additive composition. Typically, the additional zeolite component, is used in an amount ranging from about 1 to about 80, preferably from about 10 to about 70, percent by weight of the catalyst / additive composition. When the NOx reduction composition is used as an integral component of the catalyst, the additional zeolite component is preferably used in an amount ranging from about 0.1 to about 60, more preferably from about 1 to about 40 weight percent of the catalyst composition. Rather succinctly, the FCC process involves the disintegration or molecular fractionation of a heavy hydrocarbon feed to lighter products by feed contact in a disintegration process by cyclic recirculation of catalyst with an inventory of fluidizable molecular disintegrating catalysts circulating , which consists of particles having an average size ranging from about 50 to about 150 μm, preferably from about 60 to about 120 μm. The disintegration or catalytic fractionation of this relatively high molecular weight hydrocarbon feed results in the production of a lower molecular weight hydrocarbon product. Significant steps in the cyclic FCC process are: (i). the feed is catalytically disintegrated or fractionated in a catalytic disintegration zone, usually a rising column decay zone, operating at catalytic disintegration conditions by contacting the feed with a hot, regenerated disintegration catalyst source to produce an effluent that it comprises the fractionated products and the spent catalyst containing coke and hydrocarbons that can be separated; (ii) the effluent is discharged and separated, usually into one or more cyclones, into a vapor phase rich in fractionated products and a phase rich in solids comprising the spent catalyst; (iii) the vapor phase is removed as a product and fractionated in the main FCC column and the associated side columns to form the gaseous and liquid disintegration products, including gasoline; (iv) the spent catalyst is resorbed, usually with steam, to remove the occluded hydrocarbons from the catalyst, after which the desorbed catalyst is oxidatively regenerated in a regeneration zone of the catalyst to produce the hot regenerated catalyst, which is recycled then to the disintegration zone to disintegrate or fractionate additional amounts of food. Conventional FCC catalysts include, for example, zeolite-based catalysts with a faujasite disintegration component as described in the transcendental reports of Venuto and Habib, Fluid Catalytic Cracking with Zeolite Catalysts, Marcel Dekker, New York, 1979, ISBN 0-8247-6870, as well as in several other sources such as Sadeghbeigi, Fluid Catalytic Cracking Handbook, Gula Publ. Co. Houston, 1995, ISBN 0-88415-1. Preferably, the FCC catalyst is a catalyst comprising a disintegration component of active zeolite of the Y type. In a particularly preferred embodiment of the invention, the FCC catalysts consist of a binder, usually silica, alumina or silica alumina, a component active type Y zeolite, one or more aluminas and / or silica matrix aluminas, and fillers such as kaolin clay. The Y type zeolite is 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. Typical FCC processes are conducted at reaction temperatures of 480 ° C to 600 ° C with catalyst regeneration temperatures of 600 ° C to 800 ° C. As is well known in the art, the regeneration zone of the catalyst may consist of one or more reactor vessels. The compositions of the invention can be used in the processing by FCC of any typical hydrocarbon feedstock. Suitable raw materials include petroleum distillates or crude petroleum residues, which when fractionated or catalytically disintegrate provide either gasoline or a gaseous petroleum product. Synthetic feeds having boiling points from about 204 ° C to about 816 ° C, such as mineral coal oil, tar sands or shale oil, may also be included. To remove the coke from the catalyst, oxygen or air is added to the regeneration zone. This is carried out by means of a suitable induction device at the bottom of the regeneration zone, or if desired, the additional oxygen is added to the diluted or dense phase of the regeneration zone. The N0X reduction compositions according to the invention reduce dramatically, i.e. at least 10%, preferably at least 20%, the NOx emissions in the effluent of the FCCU regenerator during the regeneration of the catalyst, while substantially maintaining the conversion of hydrocarbons or the yield of the fractionated products, for example, gasoline and light olefins, obtained from the disintegration catalyst . In some cases, NOx reduction of 90% or greater can be easily achieved using the compositions and method of the invention without significantly affecting the yields of the fractionated products or the conversion of the feed. However, as will be understood by a person skilled in the catalytic art, the extent of the NOx reduction will depend on factors such as, for example, the composition and amount of the additive used.; the design and the manner in which the catalytic fractionation or disintegration unit is operated, including, but not limited to, the oxygen level and air distribution in the regenerator, the depth of the catalyst bed in the regenerator, the desorption operation and the temperature of the regenerator, the properties of the fractionated hydrocarbon feed, and the presence of other catalytic additives that may affect the chemistry and operation of the regenerator. Therefore, since each FCCU is different in some or all of these aspects, it can be expected that the effectiveness of the process of the invention varies from unit to unit. The N0X reduction compositions of the invention also prevent a significant increase in coke production during the FCC process. Also within the scope of the invention are that the NOx reduction compositions of the invention can be used alone or in combination with one or more NOx reduction components to achieve NOx reduction more efficiently than the use of any composition alone. Preferably, the further N0X reduction component is a non-zeolitic material, ie, a material that does not contain or substantially without (ie, less than 5 weight percent, preferably less than 1 weight percent) zeolite. One of such kind of non-zeolitic materials suitable for use in combination with the N0X reduction compositions of the invention include the NOx reducing compositions containing noble metals such as are shown and described in US Pat. No. 6,660, 683 the full description of which is incorporated herein by reference. The compositions in this class will typically comprise a particulate mixture of (1) an acidic metal oxide that substantially does not contain zeolite (preferably containing silica and alumina, more preferably containing at least 1 weight percent alumina); (2) an alkali metal (at least 0.5 weight percent, preferably about 1 to about 15 weight percent), an alkaline earth metal (at least 0.5 weight percent, preferably about 0.5 to about 50 weight percent) weight) and mixtures thereof); (3) at least 0.1 weight percent of a metal oxide component of oxygen storage (preferably ceria); and (4) at least 0.1 ppm of a noble metal component (preferably Pt, Pd, Rh, Ir, Os, Ru, Re, and mixtures 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 mixtures thereof; (3) about 1 to about 25 weight percent of a transition metal oxide capable of storing oxygen 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 based on the total weight of the catalyst / oxidative additive composition. Another class of non-zeolitic materials suitable for use in combination with the N0X reduction compositions of the invention include a low N0X CO combustion promoter, as shown and described in US Pat. Nos. 6,165,933 and 6,358,881, full description of these patents which is incorporated herein by reference. Typically, the low NO x CO combustion promoting compositions comprise (1) an acid oxide support; (2) an alkali metal and / or alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capacity; and (4) palladium. The acid oxide support preferably contains silica alumina. Ceria is the preferred oxygen storage oxide. Preferably, the NOx reduction composition comprises (1) an acidic metal oxide support 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 mixtures thereof; (3) at least 1 part by weight of Ce20; and (4) about 0.01-5.0 parts by weight of Pd, all said parts by weight of the components (2) - (4) are "per 100 parts by weight of said acidic metal oxide support material. of suitable materials to be used in combination with the N0X reduction compositions of the invention include the N0X reduction compositions as shown and described in US Pat. Nos. 6,280,607 Bl, 6,143,167, 6,379,536 and 6,129,834, the full description of these patents which is incorporated herein by reference In general, the NOx reduction compositions comprise (1) an acid oxide support, (2) an alkali metal and / or alkaline earth metal or mixtures thereof; transition that has oxygen storage capacity, and (4) a transition metal selected from Groups IB and HB of the Periodic Table.Preferably, the acid oxide support contains at least 50 weight percent of alumina and preferably contains silica alumina. Ceria is the preferred oxygen storage oxide. In a preferred embodiment of the invention, the N0X reduction compositions comprise (1) an acid oxide support containing at least 50 weight percent alumina; (2) 1.10 weight percent, measured as the metal oxide, of an alkali metal, an alkaline earth metal or mixtures thereof; (3) at least 1 weight percent Ce20; and (4) 0.01-5.0 parts by weight of a transition metal, measured as the metal oxide, of Cu or Ag, all parts by weight of the components (2) - (4) are per 100 parts by weight of the support of acid oxide. Another class of non-zeolitic NOx reduction materials suitable for use in combination with the NOx reduction compositions of the invention include magnesium-aluminum spinel-based additives which are useful so far for the removal of sulfur oxides from a regenerator. of FCC. Exemplary patents that show and describe this type of material include U.S. Patent Nos. 4,963,520, 4,957,892, 4,957,718, 4,790,982, 4, 47], 070, 4,472,532, 4,476,245, 4,728,635, 4,830,840, 4,904,627, 4,428,827, 5, 37], 055 , 4,495,304, 4,642178, 4,469,589, 4,758,418, 4,522,937, 4,472,267 and 4,495,305 the full description of said patents which is incorporated herein by reference. Preferably, the compositions in this class comprise at least one spinel containing metals which include a first metal and a second metal having a valence greater than the valence of said first metal, at least one component of a third metal different from the first said one. and second metals and at least one component of a fourth metal different from said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, metals from the VIA Group, rare earth metals , the metals of the Platinum group and mixtures thereof and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, olibdenum, antimony, vanadium and mixtures thereof. Preferably, the spinel containing metals comprises magnesium as said first metal and aluminum as said second metal, 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 Platinum Group metals, rare earth metals and mixtures thereof. The third metal component is preferably present in an amount in the range of about 0.001 to about 20 weight percent, calculated as the third elemental metal, and said fourth metal component is present in an amount in the range of about 0.001 to about 10. percent by weight, calculated as the fourth elemental metal. Other non-zeolitic materials useful in combination with the NOx reduction additives of the invention include, but are not limited to, zinc-based catalysts such as are shown and described in U.S. Patent No. 5,002,654; antimony-based NOx reduction additives such as are shown and described in U.S. Patent No. 4,988,432; perovskite-spinel N0X reduction additives such as are shown and described in U.S. Patent Nos. 5,364,517 and 5,565,181; hydrotalcite catalysts and additive compositions such as are described and shown, 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 the low NOx promoting additive compositions such as described, for example, in U.S. Patent No. 4,290,878; the full description of each patent that is incorporated herein by reference. Also within the scope of the invention is the use of NOx reduction compositions of the invention in combination with NOx removal compositions as shown and described in PCT International Publication Number WO 03/046112 Al and International Publication PCT WO Number 2004 / 033091A1, the full descriptions of which are incorporated herein by reference. Such a NOx removal composition generally comprises (i) an acidic oxide carrier, (ii) cerium oxide, (iii) a lanthanide oxide other than cerium and (iv) optionally, at least one transition metal oxide. selected from Groups IB and IIB of the Periodic Table, noble metals, and mixtures thereof. When the non-zeolitic N0X reduction compositions are used they are used in an amount sufficient to provide increased reduction of N0X when compared to the use of the N0X reduction compositions of ferrierite individually. Typically, the additional non-zeolitic compositions are used in an amount of up to about 50 weight percent of the FCC catalyst inventory. Preferably, the non-zeolitic composition is used in an amount of up to about 30 weight percent, more preferably up to about 10 weight percent of the FCC catalyst inventory. The additional NOx reduction composition can be mixed with the FCC catalyst inventory as a separate particulate additive. Alternatively, the additional NOx reduction composition can be incorporated into the FCC catalyst as an integral component of the catalyst. It is also contemplated within the scope of the present invention that the NOx reduction compositions according to the present invention can be used in combination with other additives conventionally used in the FCC process, for example, SOx, reduction additives, additives of sulfur reduction of gasoline, promoters of combustion of CO, additives for the production of light olefins, and the like. The scope of the invention is not intended in any way to be limited by the examples set forth below. Examples include the preparation of the catalyst / additives useful in the process of the invention and the evaluation of the process of the invention to reduce N0X in a catalytic disintegration environment. The examples are given as specific illustrations of the claimed invention. It should be understood, however, that the invention is not limited to the specific details set forth in the examples. All parts and percentages in the examples, as well as the remainder of the specification which refers to compositions or solids concentrations, are by weight unless otherwise specified. The concentrations of gas mixtures are by volume unless otherwise specified. In addition, any range of numbers mentioned in the specification or claims such as those representing a particular set of properties, units of measurement, conditions, physical states or percentages, are intended to be incorporated literally, expressly there as reference or otherwise, any number that falls within such a range, including any subset of numbers within any such range. EXAMPLES EXAMPLE 1 A composition comprising 40% ferrierite, 40% clay and 20% silica liquid colloid (Additive A) was prepared as follows. An aqueous suspension containing 29% ferrierite (Si02 / Al203 = 20) was ground in a Drais mill at an average particle size of less than 2.5 μm. The suspension of ground ferrierite (4160 g) was combined with 1200 g of Naika clay (dry base) and 6000 g of liquid silica colloid binder (10% solids). The liquid silica colloid binder was prepared from sodium silicate and acid alum. The catalyst suspension was spray dried in a Bowen spray dryer. The resulting spray-dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a Na20 level of less than 0.1 weight percent. The properties of the additive are shown in Table 1 below. Example 2 A composition comprising 75% ferrierite and 25% liquid alumina colloid (Additive B) was prepared as follows. An aqueous suspension was prepared which contained 2174 g of aluminum chlorohydrol solution (23% solids), 1500 g (dry base) of ferrierite (Si02 / Al203 = 20, Na20 + K20 <; 0.2) and enough additional water to make a suspension which contained approximately 40% solids. The suspension was ground in a Drais mill at an average particle size of less than 2.5 μm and then spray dried in a Bowen spray dryer. The spray-dried product was calcined for 90 minutes at 1100 ° F. The properties of the catalyst are shown in Table 1 below. Example 3 Additives A and B were evaluated for their ability to reduce NOx emissions from a FCCU using the Davison Circulating Ascending Column (DCR). The description of the DCR has been published in the following documents; G. W. Young, G. D. Weatherbee, and S. W. Davey, "Simulating Commercial FCCU Yields' With The Davison Circulatrng Riser (DCR) Pilot P] ant Unit," Nationa "Petroleum Refiners_Association (NPRA) Paper AM88-52; G. W. Young, "Realistic Assessment of FCC Catalyst Performance in the Laboratory," in Fluid Catalytjc Cracking: Science and Technology, J. S. Magee and M. M. Mitchell, Jr. Eds. Studies in Surface Science and Calalysis Volume 76, p. 257, Elsevir Science Publishers B.V., Amsterdam 1993, ISBN 0-444-89037-8.The DCR was started by loading the unit with approximately 1800 g of a commercially available fractionation catalyst, SUPERNOVA®-DMR +, obtained from Grace Davidson, hydrothermally deactivated in a fluidized bed reactor with 100% steam for 4 hours at 816 ° C.

• •• - -. . Table 1 Properties of the Additives Prepared in Example 1 and Example 2 Additive A Additive B TV @ 1750 F 30.78 • 4.68 SiO2% weight - - '. AI2O3% weight 23,741 29.4 RE2O3% weight o.op < Ó, 025 Na2Q% weight 0.035 • 0.30 Fe% weight 0.441 • o.r TiO2% weight 0.913 0.0% weight SA% weight 245 320"Matrix% weight 58 85. Zeolite% weight 187 235.

Average particle size um. 76 83 For evaluation purposes, a commercial FCC feed described in Table 2 below was used.

Table 2 Properties of the Feed Used in the DCR Tests Described in Example 3 API Gravity at 60 ° F 21.2 Sulfur,% weight 0.206 Total Nitrogen,% weight 0.31 Basic Nitrogen,% weight 0.0868 Conradson Carbon,% Weight 0.3 Ni, ppm 1.5 V, ppm 2.5 Factor K 11.61 Simulated Distillation,% vol, of 5 498 20 682 40 789 60 865 80 943 FBP 1265 The DCR was operated with 1% excess of 02 in the regenerator and with the regenerator operating at 705 ° C. After the unit stabilized, baseline NOx emission data were collected using an online Lear-Siegler SO2 / NO2 analyzer (SM8100A). Subsequently, 100 g of catalyst was injected into the DCR consisting of 4. 75 g of a commercial sample of combustion promoter based on Pt, CP-3® (obtained from Grace Davison) which had been deactivated by hours at 788 ° C without any Ni or V aggregates using the Cyclic Propylene Vaporization (CPS) and 95 method. 25 grams of SUPERNOVA-DMR + hydrothermally deactivated. The description of the CPS method has been published in L. T. Boock, T.F. Petti and J. A. Rudesill, "Contaminant-Metal Deactivation and Metal- Dehydrogenation Effects During Cyclic Propylene Stea ing of Fluid Catalytic Cracking Catalysts". Deactivation and Testing of Hydrocarbon Processing Catalysts, ACS Symposium Series 634, p. 171 (1996), ISBN 0-8412-3411-6. After the unit stabilized again, the NOx emission data were collected. Then, 0.25 g of the CO promoter was added to the DCR with 210 g of Additive A, or 105 g of the same deactivated disintegration catalyst by vaporization originally loaded in the DCR with 105 g of Additive B. The results are recorded in Table 3 down. TOS is the time in flow from the time of addition of the CO combustion promoter from Pt to unity. As shown in that table and FIGURE, additives A and B are effective in reducing NOx emissions from the DCR regenerator. Table 4 shows the conversion and yields of products with and without the composition of this invention. In Table 4, the conversion media and the yields of fractionated products were calculated using a sample of 7 baseline DCR tests. As shown in Table 4, when the expected variation from experiment to experiment is taken into account, both Additives A and B are especially effective in reducing N0X emissions without significantly affecting the yields of fractionated products. In particular, both the overall conversion and the gasoline yield do not change substantially, even though the FCC raw material used in these experiments is a high nitrogen content feed.

Table 3 Reduction of NOv Emissions from the regenerator of the Ascending column of Davison Circulation (DCR) When Additives A and B are used based on Ferrierite Zeolite Additive Amount TOS Speed NOx Reduction (%) (h) Gas (nppm) of NOx Chimney (%) (1 / hNPT) Catalyst 918 17 CP-3® CPS 0.25 1.9 928 534 Additive A 10 3 906 42 92 4 902 69 87 24 874 141 74 Catalyst 943 32 CP-3® CPS 0.25 1.6 937 474 Additive B 5 3 889 55 88 4 874 82 83 24 874 165 65 TABLE 4 Conversion and Performance of the Fractional Products Name of the Catalyst Catalyst of Additive A Additive B Additive Disintegration 10% weight 5% by weight E 5% in 0.25% weight CP-TOS = lh TOS = 3 h weight 3 (CPS) TOS = 23 'of all the tests Temp. of Exit of the Rx, C 521 521 521 521 Conversion,% weight 58.52 57.16 58.14 57.97 RELATION C / O 8.72 8.59 8.69 8.60 Yield H2,% weight 0.05 0.05 0.05 0.05 Dry Gas,% weight 2.00 2.08 2.10 2.03 C3 Total,% weight 4.00 4.36 4.48 4.07 C3 =% weight 3.44 3.78 3.90 3.51 C4 Total,% weight 7.03 7.04 7.22 7.26 iC4 =% weight 1.66 1.53 1.62 1.59 C4 Total =,%? That 5.00 5.15 5.24 5.31 iC4 =% weight 1.52 1.59 1.62 1.65 Total LPG 11.03 11.39 11.71 11.33 Gasoline,% weight 42.08 40.46 41.12 41.48 G-With RON EST 93.21 93.12 93.20 93.12 LCO,% weight 25.93 25.77 25.40 25.51 Funds,% weight 15.55 17.07 16.45 16.52 Coke,% weight 3.37 3.17 3.16 3.13 EXAMPLE 4 A composition comprising 65% ferrierite, 20% liquid alumina colloid and 15% kaolin clay (ADITIVE C) was prepared as follows: An aqueous suspension was prepared which contained 40. 1 Ibs of aluminum chlorohydrol solution (23% solids). 29.3 pounds (dry basis) of ferrierite (Si02 / Al203 = 16, Na20 + K20 <0.2). 7.9 lbs of kaolin clay (as is), and 32.5 lbs of additional water, enough to make a suspension which contained approximately 40% solids. The slurry was ground in a Drais mill at an average particle size of less than 2.5 μm and then spray-dried in a spray drier.

Bowen Engineering. The spray-dried product was calcined for 60 minutes at 1100 ° C. The properties of the catalyst are shown in Table 5 below Table 5 Properties of the Additive Prepared in Example 4 Additive C T.V.,%: 4.76 SiO2,%: 64.73 Al2O3,% 33.004 RE2O3,% 0.049 Na2O,%: 0.135 Fe2O3,%: 0.295 TiO2,% 0.448 DI: 1.3 APS, microns: 93 Surface Area, m2 / g: 257 ZSA, prVg: 205 MSA, m2 / g: 52 EXAMPLE 5 A particulate N0X reduction composition (Additive D) was prepared as follows. A suspension of an aqueous suspension having 20% solids of a peptizable alumina (Versal 700 alumina powder obtained from La Roche Industries Inc., 99% A1203, 30% humidity) was prepared. The alumina suspension was prepared using 31.6 Ibs of the alumina. To the suspension alumina was added 3.87 lbs of an aqueous solution of sodium hydroxide (50% NaOH). Then 10.4 lbs of cerium carbonate crystals (obtained from Rhone Poulenc, Inc., 96% Ce02, 4% La3, 50% moisture) were added to the suspension. The suspension was diluted with a sufficient amount of water to bring the solids concentration of the suspension to 12%. Finally, 3.38 lbs of sol or ion-exchanged silica liquid colloid of Nalco 1140 (obtained from Nalco Chemicals Co.) was added to the suspension. The mixture was stirred to ensure good mixing and then ground in a mill with stirring medium to reduce the agglomerates to substantially less than 10 μm. The ground mixture was spray dried to form microspheres of about 70 μm and then calcined at about 650 ° C to remove the volatiles. The resulting material was impregnated with an aqueous solution of a Cu-containing salt (for example, CuSO4) to achieve approximately 2% Cu in the final product, and dried by flash evaporation. The final product had the following analysis (dry basis) 7.8% Si02, 7.1% Na20, 18.5% Ce02, 60.2% A1203, 1.9% Cu and BET Surface area of 111 m2 / g. EXAMPLE 6 Additive C and a mixture of Additives C and D consisting of 755 of Additive C and 25% of Additive D were evaluated in the DCR with a raw material having the properties shown in Table 6. The unit was loaded with 1995g of an equilibrium disintegration catalyst (ECAT) having the properties shown in Table 7 below and 5 g of the CP-3® CO combustion promoter, which had been deactivated for 20 hours at 788 ° C without nothing of Ni or V aggregates, using the CPS method. After the unit stabilized, baseline NOx emission data were collected. Subsequently, 42 g of Additive C or the mixture of Additives C and D were injected into the unit together with 0.25 g of the combustion promoter., and 157.75 g of equilibrium catalyst. The results are shown in Table 8 below. TOS is the time in the current from the time of addition of the CO combustion promoter from Pt to unity. As this Table shows, both the additive c and the mixture of additives C and D are effective in reducing the NOx emissions in the regenerative unit of the DCR. However, additives C and D when used in the catalyst inventory in some quantity such as Additive C are only more effective in reducing N0X than Additive C.

Table 6 Feed Properties Used in the DCR Tests Described in Example 6 Gravity API at 60 ° F 25.5 Sulfur,% weight 0.369 Total Nitrogen,% weight 0.12 Basic Nitrogen,% weight 0.05 Conradson carbon,% weight 0.68 Fe, ppm 4 Na, ppm 1.2 Factor k 11.94 Simulated distillation,% vol, ° F 5 513 20 691 40 782 60 859 80 959 FBP 1257 Table 7 Balance Catalyst Properties Table 8 Reduction of NO emissions; From the Regenerator of the Ascending Column of Davison (DCR) when the Additive C or the Mix of Additives C v D Additive Amount TOS Speed of the NOx Reduction of the Additive is used (h) Gas of (nppm) of NOx (%) Chimney (%) (1 / hNPT) Catalyst + CP-3® 0.25 2 895 152 Additive C 1.9 7 895 91 40 12 895 90 41 Catalyst + CP-3® 0.25 2.8 907 169 54 Additives C + D 1.9 7.8 918 78 54 12.3 922 78

Claims

CLAIMS 1. A process for reducing the N0X emissions of the regeneration zone during the fluidized catalytic disintegration of a hydrocarbon feed in components of lower molecular weight, said process, characterized in that it comprises a. contacting the raw material during a fluidized catalytic disintegration (FCC) process where the N0X emissions are released from a regeneration zone of a fluidized catalytic disintegration unit (FCCU) operating under FCC conditions with a circulating inventory of a disintegration catalyst and a particulate NOx reduction composition having an average particle size greater than 45 μm and comprising (i) at least 10 weight percent of ferrierite zeolite, and (ii) from about 5 about 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, alumina phosphate and mixtures thereof; and b. reduce the amount of NOx emissions released from the FCCU regeneration zone by at least 10% compared to the amount of NOx emissions released in the absence of the particulate NOx reduction composition.
2. The process of claim 1, characterized in that, the FCC disintegration catalyst comprises a Y-type zeolite.
The process of claim 1, characterized in that step (b) is achieved without a substantial change in the conversion of the hydrocarbon feedstock or the yield of the fractionated hydrocarbons compared to the conversion of the hydrocarbon feedstock or the yield of the fractionated hydrocarbons obtained only with the catalyst 4.
The process of claim 1, characterized in that the The ferrierite zeolite present in the NOx reduction composition is at least 30 weight percent of the composition 5.
The process of claim 4 characterized in that, the amount of ferrierite zeolite present in the reduction composition is at least 40 percent by weight of the composition 6.
The process of claim 5, characterized in that, the amount of Ferrie zeolite. rite present in the NOx reduction composition is at least 50 weight percent of the composition.
The process of claim 1, characterized in that, the amount of ferrierite zeolite present in the reduction composition varies from about 10 to about 85 weight percent of the composition.
The process of claim 7, characterized in that, the amount of ferrierite zeolite present in the N0X reduction composition varies from about 30 to about 80 weight percent of the composition.
The process of claim 8, characterized in that, the amount of ferrierite zeolite present in the NOx reduction composition varies from about 40 to about 75 weight percent of the composition.
10. The process of claim 1 or 3, characterized in that the ferrierite zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metals or combinations thereof.
11. The process of claim 1, characterized in that the ferrierite zeolite further comprises at least one stabilizing metal.
The process of claim 11, characterized in that, the stabilizing metal is a metal selected from the group consisting of HA, HIB, IVB, VB, VIB, VIV., HIV, HB, HIA, IVA, VA, Series of Lantánidos of the Periodic Table, Ag and mixtures of the same.
The process of claim 12, characterized in that, the stabilizing metal is selected from the group consisting of the HIB, HA, HB, HIA, and Lanthanide Series of the Periodic Table, and mixtures thereof.
The process of claim 13, characterized in that, the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc and mixtures thereof.
15. The process of claim 11, characterized in that, the stabilizing metal is incorporated into the pores of the ferrierite zeolite.
16. The process of claim 1, characterized in that the inorganic binder is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof.
17. The process of claim 16, characterized in that the inorganic binder is alumina.
18. The process of claim 17, characterized in that the alumina is an alumina peptized by acid or base.
19. The process of claim 17, characterized in that the alumina is aluminum chlorohydrol.
The process of claim 1, characterized in that, the amount of the inorganic binder present in the particulate NOx reduction composition varies from about 10 to about 30 weight percent of the composition.
21. The process of claim 20, characterized in that the amount of inorganic binder present in the particulate NOx reduction composition varies from about 15 to about 25 weight percent of the composition.
22. The process of claim 1, characterized in that, the NOx reduction composition comprises an additional zeolite different from the ferrierite zeolite.
23. The process of claim 22, characterized in that, the additional zeolite is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms and a molar ratio of Si02 to Al20 less than 500.
24. The process of claim 23, characterized in that, the molar ratio of Si02 to A1203 is less than 250.
The process of claim 22, characterized in that, the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta , MCM-49, mordenite, MCM-56, Zeolite-L, Rho zeolite, heroinite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Ofertite, A, ZSM-12, ZSM-23, ZSM- 18, ZSM-22, ZSM-35, ZSM-57, ZSM-61, ZK-5, NaJ, Un-87, Cit-1, SSz-35, SSZ-48, SSZ-44, SSZ-23, Diaquardite, Merlinoite, Lovdarite, Levite, Laumontite, Epistilbite, Gmelonite, Gismondin, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreecite, Natrolite or mixtures thereof.
26. The process of claim 25, characterized in that, the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, 'Zeolite-L, Rho zeolite, errionite, chabazite, clinoptilite, MCM-22, MCM-35, Ofertite, A, ZSM-12 and mixtures thereof.
The process of claim 22, 23, or 25 characterized in that, the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.
The process of claim 27, characterized in that the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition.
29. The process of claim 1 or 3, characterized in that, the NOx reduction composition further comprises a matrix material selected from the group consisting of alumina, silica, alumina silica, titania, zirconia, yttria, lantana, ceria, neodymium , Samaria, Europia, Gadolinia, Praseodymia, and mixtures thereof.
30. The process of claim 29, characterized in that the matrix material is present in an amount of less than 70 percent by weight.
31. The process of claim 1 or 3, characterized in that it further comprises recovering the disintegration catalyst from said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst.
32. The process of claim 31, characterized in that the disintegration catalyst and the particulate N0X reduction composition are fluidized and contacted with said hydrocarbon feedstock.
The process of claim 1 or 3, characterized in that it further comprises contacting the hydrocarbon feed with at least one additional NOx reduction composition.
34. The process of claim 33, characterized in that, the additional NOx reduction composition is a non-zeolitic composition.
35. The process of claim 34, characterized in that, the additional NOx reduction composition comprises (1) an acidic metal oxide that substantially does not contain zeolite; (2) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (3) an oxygen storage metal oxide component; Y (4) at least one noble metal component.
36. The process of claim 33, characterized in that, the additional NOx reduction composition is a low NOx CO combustion promoting composition which comprises (1) an acid oxide support; (2) an alkali metal and / or an alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capacity; and (4) palladium.
37. The process of claim 33, characterized in that, the additional NOx reduction composition comprises (1) an acid oxide support; (2) an alkali metal and / or an alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capacity; and (4) a transition metal selected from Groups IB and IIB of the Periodic Table, and mixtures thereof.
38. The process of claim 33, characterized in that, the additional NOx reduction composition comprises at least one spinel containing metals which includes a first metal and a second metal having a valence greater than the valence of said first metal, at least one component of a third metal different from said first and second metals and at least one component from a fourth metal different from said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals , Group HB metals, Group VIA metals, rare earth metals, metals of the Platinum group and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
39. The process of claim 38, characterized in that the spinel containing metals comprises magnesium as said first metal and aluminum as said second metal.
40. The process of claim 39, characterized in that, the third metallic component in the metal-containing spinel is selected from the group consisting of a Platinum Group metal, the rare earth metals and mixtures thereof.
41. The process of claim 38, characterized in that, the third metal component is present in an amount in the range of about 0.001 to 20 weight percent, calculated as the third elemental metal.
42. The process of claim 38, characterized in that said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent calculated as the fourth elemental metal.
43. The process of claim 33, characterized in that, the additional N0X reduction additive is present in a zinc-based catalyst.
44. The process of claim 33, characterized in that, the additional N0X reduction additive is an antimony-based N0X reduction additive.
45. The process of claim 33, characterized in that, the additional reduction additive of N0X is a N0X reduction additive of perovskite-spinel.
46. The process of claim 33, characterized in that, the additional NOx reduction additive is a hydrotalcite-containing composition.
47. The process of claim 1, characterized in that, the particulate NOx reduction composition has an average particle size from about 50 to about 200 μm.
48. The process of claim 1, characterized in that the particulate NOx reduction composition has an average particle size from about 55 to about 150 μm.
49. The process of claim 1 or 3, characterized in that the particulate NOx reduction composition has a Davison wear index value (DI) of less than 50.
50. The process of claim 49, characterized in that, the particulate NOx reduction composition has a DI value of less than 20.
51. The process of claim 49, characterized in that, the particulate NOx reduction composition has a DI value. less than 15.
52. The process of claim 2, characterized in that, the amount of the NOx reduction composition is that amount sufficient to provide a ratio of ferrierite zeolite to type Y zeolite in the inventory of total catalyst less than 2.
53. The process of claim 33, characterized in that, the additional N0X reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than cerium, and (iv) optionally, at least one transition metal oxide selected from Groups IB and HB of the Periodic Table, noble metals and mixtures thereof.
54. A fluidized disintegration catalyst (FCC) composition which composition is characterized in that it comprises (a) a FCC disintegration component suitable for catalyzing the disintegration or fractionation of hydrocarbons under the conditions of FCC, and (b) a composition of particulate NOx reduction having an average particle size greater than 45 μm and comprising (i) at least 10 weight percent ferrierite zeolite, and (ii) about 5 to about 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, alumina phosphate, and mixtures thereof.
55. The catalyst of claim 54, characterized in that, the FCC disintegration component contains Y type zeolite.
The catalyst of claim 55, characterized in that, the NOx reduction composition is present in an amount sufficient to provide a ratio of ferrierite zeolite to type Y zeolite less than 2 in the total catalyst composition.
57. The catalyst of claim 54, characterized in that the amount of ferrierite zeolite present in the NOx reduction composition is at least 30 weight percent of the composition.
58. The catalyst of claim 57, characterized in that the amount of ferrierite zeolite present in the NOx reduction composition is at least 40 weight percent of the composition.
59. The catalyst of claim 58, characterized in that the amount of ferrierite zeolite present in the N0X reduction composition is at least 50 percent by weight of the composition.
60. The catalyst of claim 54, characterized in that, the amount of ferrierite zeolite present in the N0X reduction composition varies from about 10 to about 85 weight percent of the composition.
61. The catalyst of claim 60, characterized in that, the amount of ferrierite zeolite present in the NOx reduction composition varies from about 30 to about 80 weight percent of the composition.
62. The catalyst of claim 61, characterized in that, the amount of ferrierite zeolite present in the NOx reduction composition varies from about 40 to 75 weight percent of the composition.
63. The catalyst of claim 54, characterized in that, the ferrierite zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium; alkali metals or mixtures thereof.
64. The catalyst of claim 54, characterized in that the ferrierite zeolite further comprises at least one stabilizing metal.
65. The catalyst of claim 64, characterized in that, the stabilizing metal is a metal selected from the group consisting of HA, HIB, IVB, VB, VIB, HBV, HIV, HB, HIA, IVA, VA, Lanthanide Series. of the Periodic Table, Ag and mixtures thereof.
66. The catalyst of claim 65, characterized in that, the stabilizing metal is selected from the group consisting of Groups HIB, HA, HB, HIA, and the Lanthanide Series of the Periodic Table, and mixtures thereof.
67. The catalyst of claim 66, characterized in that, the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc and mixtures thereof.
68. The catalyst of claim 64, characterized in that, the stabilizing metal is incorporated into the pores of the ferrierite zeolite.
69. The catalyst of claim 54, characterized in that the inorganic binder in the N0X reduction composition is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof.
70. The catalyst of claim 69, characterized in that the inorganic binder is alumina.
71. The catalyst of claim 70, characterized in that the alumina is aluminum chlorohydrol.
72. The catalyst of claim 70, characterized in that the alumina is an alumina peptized by acid or base.
73. The catalyst of claim 54, characterized in that the amount of the inorganic binder present in the particulate NOx reduction composition varies from about 10 to about 30 weight percent of the composition.
74. The catalyst of claim 73, characterized in that, the amount of inorganic binder present in the particulate NOx reduction composition varies from about 15 to about 25 weight percent of the composition.
75. The catalyst of claim 54, characterized in that, the N0X reduction composition comprises an additional zeolite different from the ferrierite zeolite.
76. The catalyst of claim 75, characterized in that, the additional zeolite is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms and a molar ratio of SiO2 to A1203 of less than 500.
77. The catalyst of claim 76, characterized in that, the molar ratio of Si02 to I2O3 is less than 250.
78. The catalyst of claim 75, characterized in that, the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta , MCM-49, mordenite, MCM-56, Zeolite-L, Rho zeolite, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Ofretite, 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, Diaquardite, Merlinoite, Lovdarite, Levina, Laumontite, Epistilbita, Gmelonite, Gismondina, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreecite, Natrolite or mixtures thereof.
79. The catalyst of claim 78, characterized in that, the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, Rho zeolite, Errionite. , chabazite, clinoptilolite, MCM-22, MCM-35, Ofretite, A, ZSM-12 and mixtures thereof.
80. The catalyst of claim 75, 76, or 78 characterized in that, the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.
81. The catalyst of claim 80, characterized in that the additional zeolite is present in an amount ranging from about -10 to about 70 percent by weight of the composition.
82. The catalyst of claim 54, characterized in that the composition further comprises a matrix material selected from the group consisting of alumina, silica, silica alumina, titania, zirconia, yttria, lantana, ceria., neodymium, samaria, europia, gadolinia, praseodymia, and mixtures thereof.
83. The catalyst of claim 54, characterized in that the matrix material is present in an amount of less than 70 percent by weight.
84. The catalyst of claim 54, characterized in that it further comprises at least one additional NOx reduction composition.
85. The catalyst of claim 84, characterized in that, the additional NOx reduction composition is a non-zeolitic composition.
86. The catalyst of claim 85, characterized in that, the additional NOx reduction composition comprises (a) an acidic metal oxide that substantially does not contain zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and (d) at least one noble metal component.
87. The catalyst of claim 84, characterized in that, the additional NOx reduction composition comprises (a) an acid oxide support; (b) an alkali metal and / or an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capacity; and (d) a transition metal selected from Groups IB and HB of the Periodic Table, and mixtures thereof.
88. The catalyst of claim 84, characterized in that, the additional NOx reduction composition is a low NOx CO combustion promoting composition which comprises (a) an acid oxide support; (b) an alkali metal and / or an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capacity; and (d) palladium.
89. The catalyst of claim 84, characterized in that the additional NOx reduction composition comprises at least one spinel containing metals which includes a first metal and a second metal having a valence greater than the valence of said first metal, at least one component of a third metal different from said first and second metals and at least one component from a fourth metal different from said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals , Group IIB metals, VIA Group metals, rare earth metals, metals of the Platinum group and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
90. The catalyst of claim 89, characterized in that the spinel containing metals comprises magnesium as said first metal and aluminum as said second metal.
91. The catalyst of claim 89, characterized in that the third metallic component in the metal containing spinel is selected from the group consisting of a Platinum Group metal, the rare earth metals and mixtures thereof.
92. The catalyst of claim 89, characterized in that, the third metal component is present in an amount in the range of about 0.001 to 20 weight percent, calculated as the third elemental metal.
93. The catalyst of claim 89, characterized in that said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent calculated as the fourth elemental metal.
94. The catalyst of claim 84, characterized in that, the additional NOx reduction additive is a zinc-based catalyst.
95. The catalyst of claim 84, characterized in that, the additional NOx reduction additive is an antimony-based NOx reduction additive.
96. The catalyst of claim 84, characterized in that, the additional NOx reduction additive is a NOx reduction additive of perovskite-spinel.
97. The catalyst of claim 84, characterized in that, the additional NOx reduction additive is a hydrotalcite-containing composition.
98. The catalyst of claim 54, characterized in that the particulate NOx reduction composition has an average particle size from about 50 to about 200 μm.
99. The catalyst of claim 98, characterized in that, the particulate N0X reduction composition has an average particle size from about 55 to about 150 μm.
100. The catalyst of claim 54, characterized in that the particulate NOx reduction composition has a Davison wear index value (DI) less than 50.
101. The catalyst of claim 100, characterized in that the composition of particulate NOx reduction has a DI value of less than 20.
102. The catalyst of claim 101, characterized in that, the particulate NOx reduction composition has a DI value of less than 15.
103. The catalyst of claim 84, characterized in that, the additional NOx reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than cerium, and (iv) optionally, at least one oxide of a metal of transition selected from Groups IB and HB of the Periodic Table, noble metals and mixtures thereof.
104. A method for reducing NOx emissions from the regeneration zone during the fluidized catalytic disintegration of a hydrocarbon feedstock in lower molecular weight components, said method comprising contacting a hydrocarbon feedstock with a decay catalyst at elevated temperature, whereby hydrocarbon components of lower molecular weight are formed, said disintegration catalyst comprising the composition of claims 54, 56, 64 or 75.
The method of claim 104, characterized in that it comprises recovering the catalyst for disintegrating said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst.
106. The method of claim 105, characterized in that the disintegration catalyst is fluidized during the contact with said hydrocarbon feedstock.
107. The method of claim 104, characterized in that the decay catalyst further comprises an additive additive NOx reduction composition.
108. A fluidized disintegration catalyst, characterized in that it comprises (a) a disintegration component suitable for catalyzing the disintegration or fractionation of the hydrocarbons, (b) at least 0.1 weight percent ferrierite zeolite and (c) less than 50 weight percent of an inorganic binder material, components (b) and (c) which are based on the total weight of the disintegration catalyst.
109. The disintegration catalyst of claim 108, characterized in that the catalyst comprises integral particles which contain the components (a), (b) and (c).
110. The disintegration catalyst of claim 108, characterized in that the component (b) comprises from about 0.1 to about 60% by weight the disintegration catalyst.
111. The disintegration catalyst of claim 110, characterized in that the component (b) comprises from about 1 about 40% by weight of the disintegration catalyst
112. The catalyst of claim 108, characterized in that it further comprises at least one composition of additional NOx reduction.
113. The catalyst of claim 112, characterized in that, the additional NOx reduction composition is a non-zeolitic composition.
114. The catalyst of claim 113, characterized in that, the additional NOx reduction composition comprises (a) an acidic metal oxide that substantially does not contain zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and (d) at least one noble metal component.
115. The catalyst of claim 112, characterized in that, the additional N0X reduction composition comprises (a) an acid oxide support; (b) an alkali metal and / or an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capacity; and (d) a transition metal selected from Groups IB and HB of the Periodic Table, and mixtures thereof.
116. The catalyst of claim 112, characterized in that, the additional NOx reduction composition is a low NOx CO combustion promoting composition which comprises (a) an acid oxide support; (b) an alkali metal and / or an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capacity; and (d) palladium.
117. The catalyst of claim 112, characterized in that, the additional NOx reduction composition comprises at least one spinel containing metals which includes a first metal and a second metal having a valence greater than the valence of said first metal, at least one component of a third metal different from said first and second metals and at least one component from a fourth metal different from said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals , Group HB metals, Group VIA metals, rare earth metals, metals of the Platinum group and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
118. The catalyst of claim 117, characterized in that the spinel containing metals comprises magnesium as said first metal and aluminum as said second metal.
119. The catalyst of claim 117, characterized in that the third metallic component in the metal containing spinel is selected from the group consisting of a Platinum Group metal, the rare earth metals and mixtures thereof.
120. The catalyst of claim 117, characterized in that, the third metal component is present in an amount in the range of about 0.001 to 20 weight percent, calculated as the third elemental metal.
121. The catalyst of claim 117, characterized in that said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent calculated as the fourth elemental metal.
122. The catalyst of claim 112, characterized in that, the additional NOx reduction additive is a zinc-based catalyst.
123. The catalyst of claim 112, characterized in that, the additional NOx reduction additive is an antimony-based NOx reduction additive.
124. The catalyst of claim 112, characterized in that, the additional NOx reduction additive is a NOx reduction additive of perovskite-spinel.
125. The catalyst of claim 112, characterized in that, the additional NOx reduction additive is a hydrotalcite-containing composition.
126. A method for reducing NOx emissions from the regeneration zone during the fluidized catalytic disintegration of a hydrocarbon feedstock in components of lower molecular weight said process, characterized in that it comprises (a) contacting a hydrocarbon feedstock during a fluidized catalytic disintegration process wherein the N0X emissions are released from a regeneration zone of the FCCU operating under the conditions of the FCC with the disintegration catalyst composition of claim 108; and (b) reducing the amount of NOx emissions released from the FCCU regeneration zone by at least 10 percent, compared to the amount of NOx emissions released in the absence of the NOx reduction composition.
127. The method of claim 126, characterized in that step (b) is achieved without a substantial change in the conversion of the hydrocarbon feedstock or feedstock or the yield of the fractionated hydrocarbons obtained during the FCC process compared to the conversion of the hydrocarbon feedstock or the yield of the fractionated hydrocarbons obtained only with the catalyst.
128. The method of claim 126 or 127, characterized in that, the amount of ferrierite zeolite present in the disintegration catalyst compositions comprises at least 0.1% weight of the disintegration catalyst composition.
129. The method of claim 126 or 127, characterized in that, the amount of ferrierite zeolite present in the disintegration catalyst composition varies from about 0.1 to 60% by weight of the disintegration catalyst composition.
130. The method of claim 129, characterized in that, the amount of ferrierite zeolite present in the disintegration catalyst composition varies from about 1 to about 40% by weight of the disintegration catalyst composition.
131. The method of claim 126 or 127, characterized in that, the ferrierite zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metals and combinations thereof.
132. The method of claim 126 or 127, characterized in that the ferrierite zeolite further comprises at least one stabilizing metal.
133. The method of claim 132, characterized in that, the stabilizing metal is a metal selected from the group consisting of HA, HIB, IVB, VB, VIB, VIV., HIV, HB, HIA, IVA, VA, Series of Lantánidos of the Periodic Table, Ag and mixtures of the same.
134. The method of claim 133, characterized in that, the stabilizing metal is selected from the group consisting of the HIB, HA, HB, HIA, and Lanthanide Series of the Periodic Table, and mixtures thereof.
135. The method of claim 134, characterized in that, the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc and mixtures thereof.
136. The method of claim 132, characterized in that, the stabilizing metal is incorporated into the pores of the ferrierite zeolite.
137. The method of claim 126 or 127, characterized in that it further comprises recovering the decay catalyst and treating the used catalyst in a regeneration zone to regenerate said catalyst.
138. The method of claim 126 or 127, characterized in that the disintegration catalyst is fluidized during the contacting of said hydrocarbon feedstock.
139. The method of claim 126, characterized in that the decay catalyst further comprises an additive additive NOx reduction composition.
140. The method of claim 139, characterized in that, the additional NOx reduction composition is a non-zeolitic composition.
141. The method of claim 140, characterized in that, the additional N0X reduction composition comprises (a) an acidic metal oxide that substantially does not contain zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and (d) at least one noble metal component.
142. The method of claim 139, characterized in that, the additional NOx reduction composition comprises (a) an acid oxide support; (b) an alkali metal and / or an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capacity; and (d) palladium.
143. The method of claim 139, characterized in that the additional NOx reduction composition comprises at least one spinel containing metals which includes a first metal and a second metal having a valence greater than the valence of said first metal. , at least one component of a third metal different from said first and second metals and at least one component from a fourth metal different from said first, second and third metals, wherein said third metal is selected from the group consisting of Group metals IB, metals of the HB Group, metals of the VIA Group, rare earth metals, metals of the Platinum group and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt , germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
144. The method of claim 143, characterized in that the spinel containing metals comprises magnesium as said first metal and aluminum as said second metal.
145. The method of claim 143, characterized in that the third metal component in the metal-containing spinel is selected from the group consisting of a Platinum Group metal, the rare earth metals and mixtures thereof.
146. The method of claim 143, characterized in that, the third metal component is present in an amount in the range of about 0.001 to 20 weight percent, calculated as the third elemental metal.
147. The method of claim 143, characterized in that said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent calculated as the fourth elemental metal.
148. The method of claim 139, characterized in that, the additional NOx reduction composition comprises (a) an acid oxide support; (b) an alkali metal and / or an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capacity; and (d) a transition metal selected from Groups IB and IIB of the Periodic Table.
149. The method of claim 139, characterized in that, the additional N0X reduction additive is a zinc-based catalyst.
150. The method of claim 139, characterized in that, the additional NOx reduction additive is an antimony-based NOx reduction additive.
151. The method of claim 139, characterized in that, the additional NOx reduction additive is a peroxide-spinel N0X reduction additive.
152. The method of claim 139, characterized in that, the additional NOx reduction additive is a hydrotalcite-containing composition.
153. The decay catalyst of claim 108, characterized in that the component (a) comprises a zeolite of the type Y and the component (b) is present in an amount sufficient to provide a ratio of ferrierite to zeolite of the smaller Y type and 2 in the total catalyst.
154. The disintegration catalyst of claim 108, characterized in that the component (b) further comprises at least one stabilizing metal.
155. The disintegration catalyst of claim 154, characterized in that, the stabilizing metal is a metal selected from the group consisting of the groups HA, HIB, IVB, VB, VIB, HBV, HIV, HB, HIA, IVA, VA, the Lanthanide Series of the Periodic Table, Ag and mixtures thereof.
156. The decay catalyst of claim 155, characterized in that, the stabilizer metal is selected from the group consisting of the HIB, HA, HB, HIA, and Lanthanide Series of the Periodic Table, and mixtures thereof.
157. The disintegration catalyst of claim 156, characterized in that, the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc and mixtures thereof.
158. The disintegration catalyst of claim 154, characterized in that, the stabilizing metal is incorporated into the pores of the component (b).
159. The decay catalyst of claim 112, (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide or other than cerium, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and HB of the Periodic Table, noble metals and mixtures thereof.
160. The disintegration catalyst of claim 108, characterized in that it further comprises an additional zeolite different from the ferrierite zeolite.
161. The decay catalyst of claim 160, characterized in that the additional zeolite is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms and a molar ratio of SiO2 to A1203 less than about 500.
162. The disintegration catalyst of claim 161, characterized in that, the molar ratio of Si02 to I2O3 is less than 250.
163. The disintegration catalyst of claim 160, characterized in that, the additional zeolite is selected from the group consisting of ZSM- 5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, Rho zeolite, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Ofretite, 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, Diaquiardita, Merlinoita, Lovdarita, Levina, Laumontita, Epistilbita, Gmelonita, Gismondina, Cancrinita, Brewsterita, Stilbita, Paulingita, Goosecreecita, Natro lita or mixtures thereof.
164. The disintegration catalyst of claim 163, characterized in that the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, Rho zeolite. , errionite, chabazite, clinoptilolite, MCM-22, MCM-35, Ofretite, A, ZSM-12 and mixtures thereof.
165. The disintegration catalyst of claim 160, 161, or 163, characterized in that the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.
166. The disintegration catalyst of claim 165, characterized in that, the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition.
167. The disintegration catalyst of claim 112, (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than cerium, and (iv) optionally, at least one oxide of a metal of transition selected from Groups IB and HB of the Periodic Table, noble metals and mixtures thereof.
168. The process of claim 2, characterized in that step (b) is achieved without a substantial change in the conversion of the hydrocarbon feedstock or the yield of the fractionated hydrocarbons compared to the conversion of the hydrocarbon feedstock or the yield of the fractionated hydrocarbons obtained only with the catalyst.
169. The disintegration catalyst of claim 108, characterized in that the component (c) comprises from about 1 to about 45 weight percent of the disintegration catalyst.
170. The method of claim 126, characterized in that the decay catalyst further comprises an additional zeolite different from the ferrierite zeolite.
171. The process of claim 170, characterized in that, the additional zeolite is a zeolite having a pore size ranging from about 3 to about 7.2 Angstroms and a molar ratio of SiO2 to A1203 less than about 500.
172. The process of claim 171, characterized in that, the molar ratio of Si02 to A1203 is less than 250.
173. The process of claim 170, characterized in that, the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, Rho zeolite, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Ofretite, 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, Diaquiardite , Merlinoite, Lovdarite, Levina, Laumontite, Epistilbite, Gmelonite, Gismondin, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreecite, Natrolite or mixtures thereof.
174. The process of claim 173, characterized in that the additional zeolite is selected from the group consisting of ZSM-5, ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, Rho zeolite, Errionite. , chabazite, clinoptilolite, MCM-22, MCM-35, Ofretite, A, ZSM-12 and mixtures thereof.
175. The process of claim 170, 171, or 173, characterized in that, the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.
176. The process of claim 175, characterized in that the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition.
177. The catalyst of claim 108, characterized in that the ferrierite zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metals and combinations thereof.
178. The method of claim 126, characterized in that, the disintegration catalyst composition comprises a Y-type zeolite as the component (a) and the component (b) is present in an amount sufficient to provide a ratio of ferrierite to zeolite of type Y less than 2 in the total catalyst composition.
179. The method of claim 104, characterized in that the reduction of NOx emissions is made without a substantial change in the conversion of the hydrocarbon feed or the yield of the fractionated hydrocarbons when compared to the conversion of the hydrocarbon feed. or the yield of the fractionated hydrocarbons obtained from the fractionation catalyst only.
180. The method of claim 107 characterized in that, the additive additive NOx reduction composition is a non-zeolitic composition.
181. The method of claim 107, characterized in that, the additive NOx reduction composition is a low NOx CO combustion promoting composition which comprises (a) an acid oxide support; (b) an alkali metal and / or an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capacity; and (d) palladium.
182. The method of claim 107, characterized in that, the additional NOx reduction composition comprises at least one spinel containing metals which includes a first metal and a second metal having a valence greater than the valence of said first metal, at least one component of a third metal different from said first and second metals and at least one component from a fourth metal different from said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, Group HB metals, metals from VIA group, rare earth metals, metals of the Platinum group and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
183. The method of claim 182, characterized in that the spinel containing metals comprises magnesium as said first metal and aluminum as said second metal.
184. The method of claim 182, characterized in that the third metallic component in the metal-containing spinel is selected from the group consisting of a Platinum Group metal, the rare earth metals and mixtures thereof.
185. The method of claim 182, characterized in that, the third metal component is present in an amount in the range of about 0.001 to 20 weight percent, calculated as the third elemental metal.
186. The method of claim 182, characterized in that said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent calculated as the fourth elemental metal.
187. The method of claim 107, characterized in that, the additional NOx reduction composition comprises (a) an acid oxide support; (b) an alkali metal and / or an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capacity; and (d) a transition metal selected from the Groups IB and HB of the Periodic Table.
188. The method of claim 107, characterized in that the additional additive NOx reduction composition is a zinc based catalyst.
189. The method of claim 107, characterized in that, the additional additive NOx reduction composition is a composition a is an antimony-based N0X reduction additive.
190. The method of claim 107, characterized in that, the additive additive N0X reduction composition is an NXX reduction additive of perovskite-spinel.
191. The method of claim 107, characterized in that the additional additive NOx reduction composition is a hydrotalcite-containing composition.
192. The method of claim 107, characterized in that, the additional NOx reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than cerium, and (iv) optionally, at least one transition metal oxide selected from Groups IB and HB of the Periodic Table, noble metals and mixtures thereof.
193. The method of claim 180, characterized in that, the additional NOx reduction composition comprises (a) an acidic metallic oxide that substantially does not contain zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; Y (d) at least one noble metal component.