US20050232839A1 - Compositions and processes for reducing NOx emissions during fluid catalytic cracking - Google Patents

Compositions and processes for reducing NOx emissions during fluid catalytic cracking Download PDF

Info

Publication number
US20050232839A1
US20050232839A1 US10/909,709 US90970904A US2005232839A1 US 20050232839 A1 US20050232839 A1 US 20050232839A1 US 90970904 A US90970904 A US 90970904A US 2005232839 A1 US2005232839 A1 US 2005232839A1
Authority
US
United States
Prior art keywords
metal
catalyst
reduction
composition
zeolite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US10/909,709
Inventor
George Yaluris
Michael Ziebarth
Xinjin Zhao
Original Assignee
George Yaluris
Ziebarth Michael S
Xinjin Zhao
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US10/824,913 priority Critical patent/US7304011B2/en
Application filed by George Yaluris, Ziebarth Michael S, Xinjin Zhao filed Critical George Yaluris
Priority to US10/909,709 priority patent/US20050232839A1/en
Priority claimed from CN 200580019864 external-priority patent/CN1968748B/en
Priority claimed from TW94126051A external-priority patent/TWI396589B/en
Publication of US20050232839A1 publication Critical patent/US20050232839A1/en
Application status is Abandoned legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80Mixtures of different zeolites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084Y-type faujasite
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04Oxides
    • C10G11/05Crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • C10G11/182Regeneration
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30After treatment, characterised by the means used
    • B01J2229/42Addition of matrix or binder particles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/18Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/60Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007Zeolite Beta
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/0006Catalysts containing parts with different compositions
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027Powdering
    • B01J37/0045Drying a slurry, e.g. spray drying
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/405Limiting CO, NOx or SOx emissions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/80Additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/20C2-C4 olefins

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 particles of a zeolite having a pore size ranging from about 3 to about 7.2 Angstoms and a SiO2 to Al2O3 molar ratio of less than about 500. Preferably, the NOx reduction composition contains NOx reduction zeolite particles bound with an inorganic binder. In the alternative, the NOx reduction zeolite particles are incorporated into the cracking catalyst as an integral component of the catalyst. 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

    CROSS REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation in part application of U.S. patent application Ser. No. 10/824,913, filed Apr. 15, 2004.
  • FIELD OF THE INVENTION
  • The present invention relates to NOx reduction compositions and the method of use thereof to reduce NOx emissions in refinery processes, and specifically in fluid catalytic cracking (FCC) processes. More particularly, the present invention relates to NOx reduction compositions and the method of use thereof to reduce the content of NOx off gases released from a fluid catalytic cracking unit (FCCU) regenerator during the FCC process without a substantial change in hydrocarbon conversion or the yield of valuable cracked products.
  • BACKGROUND OF THE INVENTION
  • In recent years there has been an increased concern in the United States and elsewhere about air pollution from industrial emissions of noxious oxides of nitrogen, sulfur and carbon. In response to such concerns, government agencies have placed limits on allowable emissions of one or more of these pollutants, and the trend is clearly in the direction of increasingly stringent regulations.
  • NOx, or oxides of nitrogen, in flue gas streams exiting from fluid catalytic cracking (FCC) regenerators is a pervasive problem. Fluid catalytic cracking units (FCCUs) process heavy hydrocarbon feeds containing nitrogen compounds, a portion of which is contained in the coke on the catalyst as it enters the regenerator. Some of this coke-nitrogen is eventually converted into NOx emissions, either in the FCC regenerator or in a downstream CO boiler. Thus, all FCCUs processing nitrogen-containing feeds can have a NOx emissions problem due to catalyst regeneration.
  • In the FCC process, catalyst particles (inventory) are continuously circulated between a catalytic cracking zone and a catalyst regeneration zone. During regeneration, coke deposited on the cracking catalyst particles in the cracking zone is removed at elevated temperatures by oxidation with oxygen containing gases such as air. The removal of coke deposits restores the activity of the catalyst particles to the point where they can be reused in the cracking reaction. In general, when coke is burned with a deficiency of oxygen, the regenerator flue gas has a high CO/CO2 ratio and a low level of NOx, but when burned with excess oxygen, the flue gas has a high level of NOx and a reduced CO content. Thus, CO and NOx, or mixtures of these pollutants are emitted with the flue gas in varying quantities, depending on such factors as unit feed rate, nitrogen content of the feed, regenerator design, mode of operation of the regenerator, and composition of the catalyst inventory.
  • Various attempts have been made to limit the amount of NOx gases emitted from the FCCU by treating the NOx gases after their formation, e.g., post-treatment of NOx containing gas streams as described in U.S. Pat. Nos. 4,434,147, 4,778,664, 4,735,927, 4,798,813, 4,855,115, 5,413, 699, and 5,547,648.
  • Another approach has been to modify the operation of the regenerator to partial burn and then treat the NOx precursors in the flue gas before they are converted to NOx, e.g., U.S. Pat. Nos. 5,173,278, 5,240,690, 5,372,706, 5,413,699, 5,705,053, 5,716,514, and 5,830,346.
  • Yet another approach has been to modify the operation of the regenerator as to reduce NOx emissions, e.g., U.S. Pat. No. 5,382,352, or modify the CO combustion promoter used, e.g., U.S. Pat. Nos. 4,199,435, 4,812,430, and 4,812,431. Enrichment of air with oxygen in a regenerator operating in partial burn mode has also been suggested, e.g., U.S. Pat. No. 5,908,804.
  • Additives have also been used in attempts to deal with NOx emissions. U.S. Pat. Nos. 6,379,536, 6,280,607, 6,129,834 and 6,143,167 disclose the use of NOx removal compositions for reducing NOx emissions from the FCCU regenerator. U.S. Pat. Nos. 6,165,933 and 6,358,881 also disclose a NOx reduction composition, which promotes CO combustion during the FCC catalyst regeneration process step while simultaneously reducing the level of NOx emitted during the regeneration step. NOx reduction compositions disclosed by these patents may be used as an additive which is circulated along with the FCC catalyst inventory or incorporated as an integral part of the FCC catalyst.
  • U.S. Pat. Nos. 4,973,399 and 4,980,052 disclose reducing emissions of NOx from the regenerator of the FCCU by incorporating into the circulating inventory of cracking catalyst separate additive particles containing a copper-loaded zeolite.
  • Many additive compositions heretofore used to control NOx emissions have typically caused a significant decrease in hydrocarbon conversion or the yield of valuable cracked products, e.g., gasoline, light olefins and liquefied petroleum gases (LPGs), while increasing the production of coke. It is a highly desirable characteristic for NOx additives added to the FCCU not to affect the cracked product yields or change the overall unit conversion. The operation of the FCCU is typically optimized based on the unit design, feed and catalyst to produce a slate of cracked products and maximize refinery profitability. This product slate is based on the value model of the specific refinery. For example, during the peak summer driving season many refiners want to maximize gasoline production, while during the winter season refiners may want to maximize heating oil production. In other cases a refinery may find it profitable to produce light olefins products that can be sold in the open market or used in an associated petrochemical plant as feedstocks.
  • When a NOx reduction additive increases coke production, the FCCU may have insufficient air capacity to burn the extra coke and may result in a lower feed throughput in the unit. If the additive increases the production of low value dry gas, the production of more valuable products may decrease. An increase in dry gas may exceed the ability of the unit to handle it, thus forcing a reduction of the amount of feed processed. While an additive that increases light olefins production may be desirable if the refinery values these products and the unit has the equipment necessary to process the extra light hydrocarbons, the additive may reduce profitability if the refinery's goal is to maximize gasoline production. Light olefins are typically made in the FCCU at the expense of gasoline production. Even an additive which increases unit conversion may be undesirable if it affects product yields, causes the unit to reach an equipment limitation, and/or decreases the amount of feed that can be processed.
  • Consequently, any change to the FCCU that affects the product slate or changes the ability to process feed at the desired rate can be detrimental to the refinery profitability. Therefore, there exists a need for NOx control compositions which do not significantly affect product yields and overall unit conversion.
  • SUMMARY OF THE INVENTION
  • It has now been discovered that the incorporation of a NOx reduction zeolite component with a catalytically cracking catalyst inventory, in particular a cracking catalyst inventory containing an active Y-type zeolite, being circulated throughout a fluid catalytic cracking unit (FCCU) during a fluid catalytic cracking (FCC) process provides superior NOx control performance without substantially changing or affecting the hydrocarbon conversion or the yield of cracked petroleum products produced during the FCC process.
  • In accordance with the present invention, novel NOx reduction compositions are provided. Typically, the compositions comprise a particulate composition containing particles of a NOx reduction zeolite component. In a preferred embodiment of the invention, the NOx reduction zeolite particles are bound with an inorganic binder. The binder preferably comprises silica, alumina or silica alumina. Preferably, the NOx reduction zeolite is exchanged with hydrogen, ammonium, alkali metal and combinations thereof. The preferred alkali metal is sodium, potassium and combinations thereof.
  • In one aspect of the invention, novel zeolite containing NOx reduction compositions are provided which are added to a circulating inventory of the catalytic cracking catalyst as a separate admixture of particles to reduce NOx emissions released from the FCCU regenerator during the FCC process.
  • In another aspect of the invention, novel NOx reduction compositions are provided which comprise a NOx reduction zeolite incorporated as an integral component of an FCC catalyst, preferably, containing a Y-type zeolite active cracking component.
  • In yet another aspect of the invention, novel NOx reduction compositions are provided which compositions reduce NOx emissions from the FCCU regenerator during the FCC process while substantially maintaining hydrocarbon conversion and the yield of cracked petroleum products and minimizing an increase in the production of coke.
  • It is another aspect of the present invention to provide a process for the reduction of the content of NOx in the off gas of the FCCU regenerator during the FCC process using NOx reduction compositions in accordance with the present invention.
  • Another aspect of the invention is to provide improved FCC processes for the reduction of the content of NOx in the off gases of the FCCU regenerator without substantially affecting hydrocarbon conversion or the yield of petroleum products produced during the FCC process.
  • These and other aspects of the present invention are described in further detail below.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The FIGURE is a graphic representation of the effectiveness of Additive A, Additive B, Additive C, Additive D and Additive E prepared in EXAMPLES 1, 2, 3, 4 and 5 respectively, to reduce NOx emissions from a DCR regenerator versus time on stream, when the additives are blended with an equilibrium cracking catalyst (having the properties as shown in Table 2) which contains 0.25 weight percent of a platinum promoter, CP-3® (obtained from Grace Davison, Columbia, Md. and deactivated using the Cyclic Propylene Steaming procedure as described in EXAMPLE 6).
  • DETAILED DESCRIPTION OF THE INVENTION
  • Although several nitrogen oxides are known which are relatively stable at ambient conditions, for purposes of the present invention, NOx will be used herein to represent nitric oxide, nitrogen dioxide (the principal noxious oxides of nitrogen) as well as N2O4, N2O5 and mixtures thereof.
  • The present invention encompasses the discovery that the use of certain zeolite containing NOx reduction compositions in combination with a fluid catalytic cracking (FCC) catalyst, preferably a catalyst comprising an active Y-type zeolite, is very effective for the reduction of NOx emissions released from the FCCU regenerator under FCC process conditions without a substantial change in hydrocarbon feed conversion or the yield of cracked products. Compositions of the invention typically comprise a particulate composition containing particles of a NOx reduction zeolite component. In a preferred embodiment of the invention, the NOx reduction zeolite particles are bound with an inorganic binder. The novel NOx reduction compositions may be added to the circulating inventory of the catalytic cracking catalyst as a separate particle additive or incorporated as an integral component into the cracking catalyst.
  • For purposes of the present invention, the phrase “a substantial change in hydrocarbon feed conversion or the yield of cracked products” is defined herein to mean in the alternative (i) less than a 30% relative change, preferably less than a 20% relative change and most preferably less than a 10% relative change in the yield of LCO (light cycle oils), bottoms and gasoline in combination with LPG as compared to the baseline yield of the same or substantially the same products; or (ii) less than a 10% relative change, preferably less than a 6.5% relative change and most preferably less than a 5% relative change in the hydrocarbon feed conversion as compared to the baseline conversion. The conversion is defined as 100% times (1—bottoms yield—LCO yield). When the NOx reduction composition is used as a separate additive, the baseline is the mean conversion or yield of a product in the FCCU, operating with the same or substantially the same feed and under the same or substantially the same reaction and unit conditions, 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 cracking catalyst particles to provide an integral NOx reduction catalyst system, a significant change in the hydrocarbon conversion or yield of cracked products is determined using a baseline defined as the mean conversion or yield of a product in the same or substantially the same FCCU operating with the same or substantially the same feed, under the same or substantially the same reaction and unit conditions, and with a cracking catalyst inventory comprising the same or substantially the same cracking catalyst composition as that containing the NOx reduction composition, except that the NOx reduction composition is replaced in the cracking catalyst with a matrix component such as kaolin or other filler. The percent changes specified above are derived from statistical analysis of DCR operating data.
  • Zeolites useful as the NOx reduction zeolite component in the present invention include zeolites having a pore size ranging from about 3 to about 7.2 Angstroms with SiO2 to Al2O3 molar ratio of less than about 500, preferably less than 250, most preferably less than 100. Preferably, the NOx reduction zeolite component is a zeolite selected from the group consisting of ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite, omega or mixtures thereof. In the most preferred embodiment of the invention, the NOx reduction zeolite component is a zeolite selected from the group consisting of beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, Offretite, A, ZSM-12, ZSM-23, omega and mixtures thereof.
  • In a preferred embodiment of the invention, the NOx reduction zeolite has a surface area of at least 100 m2/g, preferably at least 200 m2/g and most preferably at least 300 m2/g. In another embodiment of the invention, the NOx reduction zeolite is exchanged with a material selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof, prior to 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 NOx reduction zeolite may contain stabilizing amounts, e.g., up to about 25 weight percent, of a stabilizing metal (or metal ion), preferably incorporated into the pores of the zeolite. Suitable stabilizing metals include, but are not limited to, metals selected from the group consisting of Groups 2A, 3B, 4B, 5B, 6B, 7B, 8B, 2B, 3A, 4A, 5A, and the Lanthanide Series of The Periodic Table, Ag and mixtures thereof. Preferably, the stabilizing metals are selected from the group consisting of Groups 3B, 2A, 2B, 3A and the Lanthanide Series of the Periodic Table, and mixtures thereof. Most preferably, the stabilizing metals are selected from the group consisting of lanthanum, aluminum, magnesium, zinc, and mixtures thereof. The metal may be incorporated into the pores of the NOx reduction zeolite by any method known in the art, e.g., ion exchange, impregnation or the like. For purposes of this invention, the Periodic Table referenced herein above is the Periodic Table as published by the American Chemical Society.
  • The amount of NOx reduction zeolite used in the catalyst/additive compositions of the invention will vary depending upon several factors, including but not limited to, the mode of combining the NOx reduction zeolite with the catalytic cracking catalyst and the type of cracking catalyst used. In one embodiment of the invention, the compositions of the invention are separate catalyst/additive compositions and comprise a particulate composition formed by binding particles of a NOx reduction zeolite component with a suitable inorganic binder. Generally, the amount of the NOx reduction zeolite component present in the particulate compositions of the invention is at least 10, preferably at least 30, most preferably at least 40 and even more preferably at least 50, weight percent based on the total weight of the composition. Typically, the particulate catalyst/additive composition of the invention contains from about 10 to about 85, preferably from about 30 to about 80, most preferably, from about 40 to about 75, weight percent of the NOx reduction zeolite component based on the total weight of the catalyst/additive composition.
  • Binder materials useful to prepare the particulate compositions of the invention include any inorganic binder which is capable of binding a zeolite powder to form particles having properties suitable for use in the FCCU under FCC process conditions. Typical inorganic binder materials useful to prepare compositions in accordance with the present invention include, but are not limited to, alumina, silica, silica alumina, aluminum phosphate and the like, and mixtures thereof. Preferably, the binder is selected from the group consisting of alumina, silica, silica alumina. More preferably, the binder comprises alumina. Even more preferably, the binder comprises an acid or base peptized alumina. Most preferably, the binder comprises an alumina sol, e.g., aluminum chlorohydrol. Generally, the amount of binder material present in the particular catalyst/additive compositions comprises from about 5 to about 50 weight percent, preferably from about 10 to about 30 weight percent, most preferably from about 15 to about 25 weight percent, of the catalyst/additive 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, silica alumina, yttria, lanthana, ceria, neodymia, samaria, europia, gadolinia, titania, zirconia, praseodymia and mixtures thereof). When used, the additional materials are used in an amount which does not significantly adversely affect the performance of the compositions to reduce NOx emissions released from the FCCU regenerator under FCC conditions, the hydrocarbon feed conversion or the product yield of the cracking catalyst. In general the additional materials will comprise no more than about 70 weight percent of the compositions. It is preferred, however, that the compositions of the invention consist essentially of the NOx reduction zeolite and an inorganic binder.
  • Particulate catalyst/additive compositions of the invention should have a particle size sufficient to permit the composition to be circulated throughout the FCCU simultaneously with the inventory of cracking catalyst during the FCC process. Typically the composition of the invention will have a mean particle size of greater than 45 μm. Preferably, the mean particle size is from about 50 to about 200 μm, most 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 attrition index (DI) value of less than about 50, preferably less than about 20, most preferably less than about 15.
  • While the present invention is not limited to any particular process of preparation, typically the particulate NOx reduction compositions of the invention are prepared by forming an aqueous slurry containing the NOx reduction zeolite, optional zeolite components, the inorganic binder, and optional matrix materials, in an amount sufficient to provide at least 10.0 weight percent of NOx reduction zeolite and at least 5.0 weight percent of binder material in the final catalyst/additive composition and, thereafter, spray drying the aqueous slurry to form particles. The spray-dried particles are optionally dried at a sufficient temperature for a sufficient time to remove volatiles, e.g., at about 90° C. to about 320° C. for about 0.5 to about 24 hours. In a preferred embodiment of the invention, the NOx reduction zeolite containing aqueous slurry is milled prior to spray-drying to reduce the mean particle size of materials contained in the slurry to 10 μm or less, preferably 5 μm or less, most preferably 3 μm or less. The aqueous slurry may be milled prior to or after incorporation of the binder and/or matrix materials as desired.
  • The spray-dried composition may be calcined at a temperature and for a time sufficient to remove volatiles and provide sufficient hardness to the binder for use in the FCCU under FCC process conditions, preferably from about 320° C. to about 900° C. from about 0.5 to about 6 hours.
  • Optionally, the dried or calcined composition is washed or exchanged with an aqueous solution of ammonia or ammonium salt (e.g., ammonium sulfate, nitrate, chloride, carbonate, phosphate and the like), or an inorganic or organic acid (e.g., sulfuric, nitric, phosphoric, hydrochloric, acetic, formic and the like) to reduce the amount of alkaline metals, e.g. sodium or potassium, in the finished product.
  • Particulate compositions of the invention are circulated in the form of separate particle additives along with the main cracking catalyst throughout the FCCU. Generally, 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, most preferably from about 1 to about 50 weight percent of the FCC catalyst inventory. Separate particle catalyst/additive compositions of the invention may be added to the FCCU in the conventional manner, e.g., with make-up catalyst to the regenerator or by any other convenient method.
  • In a second embodiment of the invention, the NOx reduction zeolite is integrated or incorporated into the cracking catalyst particles themselves to provide an integral NOx reduction catalyst system. In accordance with this embodiment of the invention, the NOx reduction zeolite may be added to the catalyst at any stage during catalyst manufacturing prior to spray drying the cracking catalyst slurry to obtain the fluid cracking catalyst, regardless of any additional optional or required processing steps needed to finish the cracking catalyst preparation. Without intending to limit the incorporation of the NOx reduction zeolite component, and any optional zeolites, within the cracking catalyst to any specific method of cracking catalyst manufacturing, typically the NOx reduction zeolite component, any additional zeolites, the cracking catalyst zeolite, usually USY or REUSY-type, and any matrix materials are slurried in water. The slurry is milled to reduce the mean particle size of solids in the slurry to less than 10 μm, preferably to less than 5 μm, most preferably less than 3 μm. The milled slurry is combined with a suitable binder, i.e., a silica sol binder, and optional matrix material, e.g. clay. The slurry is then mixed and spray-dried to form a catalyst. The spray-dried catalyst is optionally washed using an aqueous solution of ammonium hydroxide, an ammonium salt, an inorganic or organic acid, and water to remove the undesirable salts. The washed catalyst may be exchanged with a water soluble rare-earth salt, e.g., rare-earth chlorides, nitrates and the like.
  • Alternatively, the NOx reduction zeolite component, optional additional zeolites, the cracking catalyst zeolite, any matrix materials, a rare-earth water soluble salt, clay and alumina sol binder are slurried in water and blended. The slurry is milled and spray-dried. The spray-dried catalyst is calcined at about 250° C. to about 900° C. The spray-dried catalyst may then optionally be washed using an aqueous solution of ammonium hydroxide, an ammonium salt, an inorganic or organic acid, and water to remove the undesirable salts. Optionally, the catalyst may be exchanged with a water-soluble rare-earth salt after it has been washed, by any of the methods known in the art.
  • When integrated into the FCC catalyst particles, the NOx reduction zeolite component typically represents at least 0.1 weight percent of the FCC catalyst particle. Preferably, the amount of the NOx reduction zeolite component used ranges from about 0.1 to about 60 weight percent, most preferably from about 1 to about 40 weight percent, of the FCC catalyst particles.
  • The integrated FCC catalyst will typically comprise the NOx reduction zeolite component along with the cracking catalyst zeolite, inorganic binder materials and optionally, matrix, fillers, and other additive components such as metals traps (for example, traps for Ni and V) to make up the cracking catalyst. The cracking catalyst zeolite, usually a Y, USY or REUSY-type, provides the majority of the cracking activity and is typically present in a range from about 10 to about 75, preferably from about 15 to about 60 and most preferably from about 20 to about 50 weight percent based on the total weight of the composition. Inorganic binder materials useful to prepare integrated catalyst compositions in accordance with 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 FCC process conditions. Typically, the inorganic binder materials include, but are not limited to, alumina, silica, silica alumina, aluminum phosphate and the like, and mixtures thereof. Preferably, the binder is selected from the group consisting of alumina, silica, silica alumina. Generally, the amount of binder material present in the integrated catalyst composition is less than 50 weight percent based on the total weight of the catalyst composition. Preferably, the inorganic binder materials is present in the integrated catalyst in an amount ranging from about 5 to about 45 weight percent, more preferably from about 10 to about 30 weight percent and most 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 lanthana, transition metal oxides such as titania, zirconia, and manganese oxide, group 2A oxides such as magnesium and barium oxides, clays such as kaolin, and mixtures thereof. The matrix and/or fillers are typically present in the integral catalyst in an amount of less than 50 weight percent based on the total weight of the catalyst composition. Preferably, the matrix and/or fillers are present in an amount ranging from about 1 to about 45 weight percent based on the total weight of the catalyst composition.
  • The particle size and attrition properties of the integral catalyst affect fluidization properties in the unit and determine how well the catalyst is retained in the commercial FCC unit. The integral catalyst composition of the invention typically has a mean particle size of about 45 to about 200 μm, more preferably from about 50 μm to about 150 μm. The attrition properties of the integral catalyst, as measured by the Davison Attrition Index (DI), have a DI value of less than 50, more preferably less than 20 and most preferably less than 15.
  • In a preferred embodiment of the invention, the FCC cracking catalyst contains a Y-type zeolite. The NOx reduction zeolite may be added as a separate additive particle to a circulating inventory of the cracking catalyst or incorporated directly into the Y-type zeolite containing cracking catalyst as an integral component of the catalyst. In either case, it is preferred that the NOx reduction zeolite be present in that amount sufficient to provide in the total catalyst inventory a ratio of NOx reduction zeolite to Y-type zeolite of less than 2, preferably less than 1.
  • It is also within the scope of the invention to include additional zeolite components in the catalyst/additive compositions of the invention. The additional zeolite component may be any zeolite which does not adversely affect the NOx reduction performance or cause a substantial change in hydrocarbon conversion or cracked product yields during the FCC process. Preferably, the additional zeolite component is a zeolite selected from the group consisting of ferrierite, ZSM-5, ZSM-35 and mixtures thereof. The additional zeolite component is used in any amount that does not significantly adversely affect the performance of the NOx reduction zeolite compositions to reduce NOx emissions and substantially maintain the hydrocarbon conversion and product yields of the cracking catalyst relative to the use of the cracking catalyst without the NOx reduction 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, weight percent of the catalyst/additive composition. Where the NOx reduction zeolite 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, most preferably from about 1 to about 40, weight percent of the catalyst composition.
  • Somewhat briefly, the FCC process involves the cracking of heavy hydrocarbon feedstocks to lighter products by contact of the feedstock in a cyclic catalyst recirculation cracking process with a circulating fluidizable cracking catalyst inventory consisting of particles having a mean size ranging from about 50 to about 150 μm, preferably from about 60 to about 120 μm. The catalytic cracking of these relatively high molecular weight hydrocarbon feedstocks results in the production of a hydrocarbon product of lower molecular weight. The significant steps in the cyclic FCC process are:
      • (i) the feed is catalytically cracked in a catalytic cracking zone, normally a riser cracking zone, operating at catalytic cracking conditions by contacting feed with a source of hot, regenerated cracking catalyst to produce an effluent comprising cracked products and spent catalyst containing coke and strippable hydrocarbons;
      • (ii) the effluent is discharged and separated, normally in one or more cyclones, into a vapor phase rich in cracked product and a solids rich phase comprising the spent catalyst;
      • (iii) the vapor phase is removed as product and fractionated in the FCC main column and its associated side columns to form gas and liquid cracking products including gasoline;
      • (iv) the spent catalyst is stripped, usually with steam, to remove occluded hydrocarbons from the catalyst, after which the stripped catalyst is oxidatively regenerated in a catalyst regeneration zone to produce hot, regenerated catalyst which is then recycled to the cracking zone for cracking further quantities of feed.
  • Conventional FCC catalysts include, for example, zeolite based catalysts with a faujasite cracking component as described in the seminal review by Venuto and Habib, Fluid Catalytic Cracking with Zeolite Catalysts, Marcel Dekker, New York 1979, ISBN 0-8247-6870-1, as well as in numerous other sources such as Sadeghbeigi, Fluid Catalytic Cracking Handbook, Gulf Publ. Co. Houston, 1995, ISBN 0-88415-290-1. Preferably, the FCC catalyst is a catalyst comprising a Y-type zeolite active cracking component. In a particularly preferred embodiment of the invention, the FCC catalysts consist of a binder, usually silica, alumina, or silica alumina, a Y-type zeolite active component, one or more matrix aluminas and/or silica aluminas, and fillers such as kaolin clay. The Y-type zeolite may be present in one or more forms and may have been ultra stabilized and/or treated with stabilizing cations such as any of the rare-earths.
  • 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 it is well known in the art, the catalyst regeneration zone may consist of a single or multiple reactor vessels. The compositions of the invention may be used in FCC processing of any typical hydrocarbon feedstock. Suitable feedstocks include petroleum distillates or residuals of crude oils having a boiling point range of about 150° C. to about 900° C., preferably, about 200° C. to about 800° C., which when catalytically cracked provide a gasoline or other petroleum product. Synthetic feeds having boiling points of about 200° C. to about 800° C., such as oil from coal, tar sands or shale oil, can also be included.
  • In order to remove coke from the catalyst, oxygen or air is added to the regeneration zone. This is performed by a suitable sparging device in the bottom of the regeneration zone, or if desired, additional oxygen is added to the dilute or dense phase of the regeneration zone.
  • Catalyst/additive compositions in accordance with the invention dramatically reduce, i.e., by at least 10%, preferably at least 20%, the emissions of NOx in the FCCU regenerator effluent during the catalyst regeneration, while substantially maintaining the hydrocarbon feed conversion or the yield of cracked products, e.g., gasoline and light olefins, obtained from the cracking catalyst. In some cases, NOx reduction of 90% or greater is readily achievable using the compositions and method of the invention without significantly affecting the cracked products yields or feed conversion. However, as will be understood by one skilled in the catalyst art, the extent of NOx reduction will depend on such factors as, for example, the composition and amount of the additive utilized; the design and the manner in which the catalytic cracking unit is operated, including but not limited to oxygen level and distribution of air in the regenerator, catalyst bed depth in the regenerator, stripper operation and regenerator temperature, the properties of the hydrocarbon feedstock cracked, and the presence of other catalytic additives that may affect the chemistry and operation of the regenerator. Thus, since each FCCU is different in some or all of these respects, the effectiveness of the process of the invention may be expected to vary from unit to unit. NOx reduction compositions of the invention also prevent a significant increase in the production of coke during the FCC process.
  • It is also within the scope of the invention that NOx reduction compositions of the invention may be used alone or in combination with one or more additional NOx reduction component to achieve NOx reduction more efficiently than the use of either of the compositions alone. Preferably, the additional NOx reduction component is a non-zeolitic material, that is, a material that contains no or substantially no (i.e., less than 5 weight percent, preferably less than 1 weight percent) zeolite.
  • One such class of non-zeolitic materials suitable for use in combination with the NOx reduction compositions of the invention include noble metal containing NOx reduction compositions such as disclosed and described in U.S. Pat. No. 6,660,683 B1, the entire disclosure of which is herein incorporated by reference. Compositions in this class will typically comprise a particulate mixture of (1) an acidic metal oxide containing substantially no zeolite (preferably containing silica and alumina, most 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) and mixtures thereof; (3) at least 0.1 weight percent of an oxygen storage metal oxide component (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 an oxygen storage capable transition metal oxide or a rare-earth (preferably, ceria); and (4) at least 0.1 ppm of a noble metal selected from the group consisting of Pt, Rh, Ir, and a combination thereof, all percentages being based on the total weight of the oxidative catalyst/additive composition.
  • Another class of non-zeolitic materials suitable for use in combination with the NOx reduction compositions of the invention include a low NOx, CO combustion promoter as disclosed and described in U.S. Pat. Nos. 6,165,933 and 6,358,881, the entire disclosure of these patents being herein incorporated by reference. Typically, the low NOx CO combustion promoter compositions comprise (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) palladium. The acidic 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 CeO2; and (4) about 0.01-5.0 parts by weight of Pd, all of said parts by weight of components (2)-(4) being per 100 parts by weight of said acidic metal oxide support material.
  • Yet another class of non-zeolitic materials suitable for use in combination with the NOx reduction compositions of the invention include NOx reduction compositions as disclosed and described in U.S. Pat. Nos. 6,379,536, 6,280,607 B1, 6,143,167 and 6,129,834, the entire disclosure of these patents being herein incorporated by reference. In general, the NOx reduction compositions comprise (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) a transition metal selected from Groups IB and IIB of the Periodic Table. Preferably, the acidic oxide support contains at least 50 weight percent alumina and preferably contains silica alumina. Ceria is the preferred oxygen storage oxide. In a preferred embodiment of the invention, the NOx reduction compositions comprise (1) an acidic 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 CeO2; and (4) 0.01-5.0 parts weight percent of a transition metal, measured as metal oxide, of Cu or Ag, all parts by weight of components (2)-(4) being per 100 parts by weight of said acidic oxide support.
  • 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 heretofore being useful for the removal, of sulfur oxides from a FCC regenerator. Exemplary patents which disclose and describe this type of materials include U.S. Pat. Nos. 4,963,520, 4,957,892, 4,957,718, 4,790,982, 4,471,070, 4,472,532, 4,476,245, 4,728,635, 4,830,840, 4,904,627, 4,428,827, 5,371,055, 4,495,304, 4,642,178, 4,469,589, 4,758,418, 4,522,937, 4,472,267 and 4,495,305 the entire disclosure of said patents being herein incorporated by reference. Preferably, compositions in this class comprise at least one metal-containing spinel which includes a first metal and a second metal having a valence higher than the valence of said first metal, at least one component of a third metal other than said first and second metals and at least one component of a fourth metal other than said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group VIA metals, the rare-earth metals, the Platinum Group metals and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof. Preferably, the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal, and the atomic ratio of magnesium to aluminum in said spinel is at least about 0.17. The third metal in the spinel preferably comprises a metal selected from the group consisting of the Platinum Group metals, the 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 elemental third metal, and said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent, calculated as elemental fourth metal.
  • 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 disclosed and described in U.S. Pat. No. 5,002,654; antimony based NOx reduction additives such as described and disclosed in U.S. Pat. No. 4,988,432; perovskite-spinel NOx reduction additives such as described and disclosed in U.S. Pat. Nos. 5,364,517 and 5,565,181; hydrotalcite catalyst and additive compositions such as described and disclosed, for example, in U.S. Pat. Nos. 4,889,615, 4,946,581, 4,952,382, 5,114,691, 5,114,898, 6,479,421 B1 and PCT International Publication No. WO 95/03876; and low NOx promoter additive compositions such as described, for example in U.S. Pat. No. 4,290,878; the entire disclosure of each patent being herein incorporated by reference.
  • It is also within the scope of the invention to use the NOx reduction compositions of the invention in combination with NOx removal compositions as disclosed and described in PCT International Publication Number WO 03/046112 A1 and PCT International Publication No. WO 2004/033091 A1, the entire disclosures of which are herein incorporated by reference. Such NOx removal composition generally comprises (i) an acidic oxide support, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.
  • When used, the additional non-zeolitic NOx reduction compositions are used in an amount sufficient to provide increased NOx reduction when compared to the use of the catalyst/additive compositions alone. Typically, the additional non-zeolitic compositions are used in an amount up to about 50 weight percent of the FCC catalyst inventory. Preferably, the non-zeolitic composition is used in an amount up to about 30 weight percent, most preferably up to about 10 weight percent of the FCC catalyst inventory. The additional NOx reduction composition may be blended with the FCC catalyst inventory as a separate particle additive. Alternatively, the additional NOx reduction composition may 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 catalyst/additive compositions in accordance with the present invention may be used in combination with other additives conventionally used in the FCC process, e.g., SOx reduction additives, gasoline-sulfur reduction additives, CO combustion promoters, additives for the production of light olefins, and the like.
  • The scope of the invention is not in any way intended to be limited by the examples set forth below. The examples include the preparation of catalyst/additives useful in the process of the invention and the evaluation of the invention process to reduce NOx in a catalytic cracking 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 solid compositions or concentrations, are by weight unless otherwise specified. Concentrations of gaseous mixtures are by volume unless otherwise specified.
  • Further, any range of numbers recited in the specification or claims, such as that representing a particular set of properties, units of measure, conditions, physical states or percentages, is intended to literally incorporate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited.
  • EXAMPLES Example 1
  • A composition containing 40% MCM-49 and 40% clay bound with 20% silica sol (Additive A) was prepared as follows. An aqueous slurry containing 25% MCM-49 (SiO2/Al2O3=18) was milled in a Drais mill. The milled MCM-49 slurry (4880 g) was combined with 1200 g Natka clay (dry basis) and 6000 g silica sol binder (10% solids). The silica sol binder was prepared from sodium silicate and acid alum. The catalyst slurry was then spray dried in a Bowen spray drier. The resulting spray dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a Na2O level of less than 0.1 wt %. The properties of the catalyst are shown in Table 1.
  • Example 2
  • A composition containing 40% beta and 40% clay bound with 20% silica sol (Additive B) was prepared as follows. An aqueous slurry containing 21% beta (SiO2/Al2O3=28) was milled in a Drais mill. The milled beta slurry (5670 g) was combined with 1200 g Natka clay (dry basis) and 6000 g silica sol binder (10% solids). The silica sol binder was prepared from sodium silicate and acid alum. The catalyst slurry was then spray dried in a Bowen spray drier. The resulting spray dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a Na2O level of less than 0.1 wt %. The properties of the catalyst are shown in Table 1.
  • Example 3
  • A composition containing 40% mordenite and 40% clay bound with 20% silica sol (Additive C) was prepared as follows. An aqueous slurry containing 21% Mordenite (SiO2/Al2O3=19) was milled in a Drais mill. The milled mordenite slurry (3850 g) was combined with 800 g Natka clay (dry basis) and 4000 g silica sol binder (10% solids). The silica sol binder was prepared from sodium silicate and acid alum. The catalyst slurry was then spray dried in a Bowen spray drier. The resulting spray dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a Na2O level of less than 0.1 wt %. The properties of the catalyst are shown in Table 1.
  • Example 4
  • A composition containing 40% Zeolite L and 40% clay bound with 20% silica sol (Additive D) was prepared as follows. An aqueous slurry containing 25% Zeolite L (SiO2/Al2O3=6) was milled in a Drais mill. The milled Zeolite L slurry (5050 g) was combined with 1200 g Natka clay (dry basis) and 6000 g silica sol binder (10% solids). The silica sol binder was prepared from sodium silicate and acid alum. The catalyst slurry was then spray dried in a Bowen spray drier. The resulting spray dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a Na2O level of less than 0.1 wt %. The properties of the catalyst are shown in Table 1.
  • Example 5
  • A composition containing 40% MCM-56 and 40% clay bound with 20% silica sol (Additive E) was prepared as follows. An aqueous slurry containing 21.8% MCM-56 (SiO2/Al2O3=19) was milled in a Drais mill. The milled MCM-56 slurry (5765 g) was combined with 1200 g Natka clay (dry basis) and 6000 g silica sol binder (10% solids). The silica sol binder was prepared from sodium silicate and acid alum. The catalyst slurry was then spray dried in a Bowen spray drier. The resulting spray dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a Na2O level of less than 0.1 wt %. The properties of the catalyst are shown in Table 1.
    TABLE 1
    Properties of Additives A through E.
    Additive A Additive B Additive C Additive D Additive E
    TV @ 1750° F. Wt. % 5.68 3.72 4.76 5.11 5.09
    SiO2 Wt. % 75.9 75.1 76.3 70.5 75.4
    Al2O3 Wt. % 23.0 22.8 22.4 17.0 22.2
    RE2O3 Wt. % 0.02 0.02 0.19 0.01 0.01
    Na2O Wt. % <0.023 <0.027 <0.020 <0.023 <0.022
    Fe Wt. % 0.44 0.44 0.43 0.23 0.42
    TiO2 Wt. % 0.96 0.95 1.10 0.52 0.02
    K2O Wt. % 1.681
    SA m2/g 244 238 269 258 218
    Zeolite m2/g 182 174 224 196 124
    Matrix m2/g 62 64 45 62 94
  • Example 6
  • The ability of Additives A-E to reduce NO emissions from the FCC unit was evaluated using the Davison Circulating Riser (DCR). The description of the DCR has been published in the following papers: G. W. Young, G. D. Weatherbee, and S. W. Davey, “Simulating Commercial FCCU yields with the Davison Circulating Riser (DCR) pilot plant unit,” National Petroleum Refiners Association (NPRA) Paper AM88-52; G. W. Young, “Realistic Assessment of FCC Catalyst Performance in the Laboratory,” in Fluid Catalytic Cracking: Science and Technology, J. S. Magee and M. M. Mitchell, Jr. Eds., Studies in Surface Science and Catalysis Volume 76, p. 257, Elsevier Science Publishers B. V., Amsterdam 1993, ISBN 0-444-89037-8. The DCR was started up by charging the unit with approximately 1800 g of equilibrium catalyst having properties as shown in Table 2 below. The properties of the additives tested are summarized in Table 1 above. For the purposes of this test, a commercial FCC feed was used having the properties as shown in Table 3 below.
    TABLE 2
    Properties of equilibrium catalyst used in DCR tests.
    SiO2 wt. % 50.9
    Al2O3 wt. % 45.5
    RE2O3 wt. % 0.37
    Na2O wt. % 0.37
    Fe wt. % 0.6
    TiO2 wt. % 1.2
    MgO wt. % 0.319
    Ni ppm 681
    V ppm 1160
    SA m2/g 188
    Zeolite m2/g 128
    Matrix m2/g 60
  • TABLE 3
    Properties of feed used in DCR tests
    API Gravity @ 60° F. 23.2
    Sulfur, wt. % 0.023
    Total Nitrogen, wt. % 0.13
    Basic Nitrogen, wt. % 0.0378
    Conradson Carbon, wt. % 0.03
    Fe, ppm 0.7
    Na, ppm 0.7
    K Factor 11.4
    Simulated Distillation,
    vol. %, ° F.
     5 453
    20 576
    40 660
    60 743
    80 838
    FBP 1153
  • The DCR was operated with 1% excess O2 in the regenerator, and with the regenerator operating at 1300° F. (705° C.). After the unit stabilized the baseline NO emissions data were collected using an on-line Lear-Siegler SO2/NO Analyzer (SM8100A). Subsequently, 100 g of catalyst were injected into the DCR consisting of 4.725 g of a commercial sample of a Pt-based combustion promoter (CP®-3) which had been deactivated for 20 h at 1450° F. (788° C.) without any added Ni or V using the Cyclic Propylene Steaming method (CPS) and equilibrium catalyst. 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 Steaming 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 NO emissions data was collected. Thereafter, 210 g of the additive to be tested along with 0.525 g of Pt based CO promoter was added to the DCR. The results are recorded in Table 4 below.
  • As shown in that table and the FIGURE, Additives A through E are effective in reducing NO emissions from the DCR regenerator. The additives are especially effective in decreasing NO emissions without significantly affecting the cracked products yields as shown below in Table 5.
    TABLE 4
    Reduction of NO emissions from the regenerator of the
    Davison Circulating Riser (DCR) when using Zeolite
    based additives. TOS is time on stream from the time
    of adding Pt CO combustion promoter to the unit.
    Level TOS Gas Flow NO NO Reduction
    Additive (%) (h) (l/h) (nppm) (%)
    ECAT 888 32
    CP-3, CPS 0.25 1 889 156
    Additive A 10 4 906 63 60
    ECAT 886 49
    CP-3, CPS 0.25 1.3 884 148
    Additive B 10 4 917 56 62
    ECAT 864 27
    CP-3, CPS 0.25 1.3 877 124
    Additive C 10 4 912 81 35
    ECAT 887 19
    CP-3, CPS 0.25 1.2 877 125
    Additive D 10 4 913 97 22
    ECAT 878 39
    CP-3, CPS 0.25 1.4 872 152
    Additive E 10 4 864 109 28
  • TABLE 5
    Activity of the cracking catalyst inventory and product yields during testing of zeolite based additives in the DCR.
    ECAT ECAT W/ ECAT W/ ECAT W/ ECAT W/ ECAT W/
    Average 0.25% Pt Prom. 0.25% Pt Prom. 0.25% Pt Prom. 0.25% Pt Prom. 0.25% Pt Prom.
    Catalyst Name of 6 runs 10% Additive A 10% Additive B 10% Additive C 10% Additive D 10% Additive E
    Conversion wt % 71.07 69.53 70.92 71.09 71.20 70.38
    C/O RATIO 8.19 7.87 8.08 8.19 7.85 8.11
    H2 Yield wt % 0.05 0.05 0.05 0.05 0.05 0.05
    C1 + C2′s wt % 1.61 1.70 1.79 1.79 1.73 1.63
    Total C3 wt % 5.50 6.11 6.48 6.23 5.99 5.84
    C3 = wt % 4.74 5.08 5.36 5.09 4.98 5.01
    Total C4 wt % 10.03 9.92 10.56 10.47 10.35 10.14
    iC4 wt % 3.55 3.65 4.02 3.78 3.80 3.61
    Total C4 = wt % 5.88 5.59 5.80 5.98 5.80 5.92
    iC4 = wt % 1.63 1.74 1.80 1.79 1.67 1.77
    GASOLINE wt % 50.95 48.80 48.69 49.49 49.93 49.74
    LCO wt % 23.84 25.12 23.94 23.64 23.70 24.37
    BOTTOMS wt % 5.09 5.35 5.14 5.27 5.10 5.25
    Coke wt % 2.93 2.95 3.34 3.07 3.16 2.98

Claims (190)

1. A process of reducing NOx emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said process comprising
a) contacting a hydrocarbon feedstock during a fluid catalytic cracking (FCC) process wherein NOx emissions are released from a regeneration zone of a fluid catalytic cracking unit (FCCU) operating under FCC conditions with a circulating inventory of an FCC cracking catalyst and a particulate NOx reduction catalyst/additive composition having a mean particle size of greater than 45 μm and comprising (i) at least 10 weight percent of a NOx reduction zeolite component selected from the group consisting of ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite, omega or mixtures thereof, and (ii) from about 5 to about 50 weight percent of an inorganic binder selected from the group consisting of alumina, silica, silica alumina, alumina phosphate and mixtures thereof; and
b) reducing the amount of NOx emissions released from the regeneration zone of the FCCU by at least 10% as compared to the amount of NOx emissions released in the absence of the particulate NOx reduction composition.
2. The process of claim 1 wherein the FCC cracking catalyst comprises a Y-type zeolite.
3. The process of claim 1 wherein step (b) is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone.
4. The process of claim 1 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition is at least 30 weight percent of the composition.
5. The process of claim 4 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition is at least 40 weight percent of the composition.
6. The process of claim 5 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition is at least 50 weight percent of the composition.
7. The process of claim 1 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition ranges from about 10 to about 85 weight percent of the composition.
8. The process of claim 7 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition ranges from about 30 to about 80 weight percent of the composition.
9. The process of claim 8 wherein the amount of the NOx reduction zeolite component present in the catalyst/additive composition ranges from about 40 to about 75 weight percent of the composition.
10. The process of claim 1 or 3 wherein the NOx reduction zeolite component is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof.
11. The process of claim 1 wherein the NOx reduction zeolite component further comprises at least one stabilizing metal.
12. The process of claim 11 wherein the stabilizing metal is a metal selected from the group consisting of Groups 2A, 3B, 4B, 5B, 6B, 7B, 8B, 2B, 3A, 4A, 5A, the Lanthanide Series of The Periodic Table, Ag and mixtures thereof.
13. The process of claim 12 wherein the stabilizing metal is selected from the group consisting of Groups 3B, 2A, 2B, 3A and the Lanthanide Series of the Periodic Table, and mixtures thereof.
14. The process of claim 13 wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof.
15. The process of claim 11 wherein the stabilizing metal is incorporated into the pores of the NOx reduction zeolite component.
16. The process of claim 1 wherein the inorganic binder is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof.
17. The process of claim 16 wherein the inorganic binder is alumina.
18. The process of claim 17 wherein the alumina is an acid or base peptized alumina.
19. The process of claim 17 wherein the alumina is aluminum chlorohydrol.
20. The process of claim 1 wherein the amount of inorganic binder present in the particulate catalyst/additive composition ranges from about 10 to about 30 weight percent of the composition.
21. The process of claim 20 wherein the amount of inorganic binder present in the particulate catalyst/additive composition ranges from about 15 to about 25 weight percent of the composition.
22. The process of claim 1 wherein the NOx reduction zeolite component has a SiO2 to Al2O3 molar ratio of less than 500.
23. The process of claim 1 wherein the NOx reduction zeolite component is a zeolite selected from the group consisting of beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, Offretite, A, ZSM-12, ZSM-23, omega and mixtures thereof.
24. The process of claim 1 wherein the particulate catalyst/additive composition further comprises an additional zeolite other than the NOx reduction zeolite.
25. The process of claim 24 wherein the additional zeolite is selected from the group consisting of ferrierite, ZSM-5, ZSM-35 and mixtures thereof.
26. The process of claim 24 or 25 wherein the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.
27. The process of claim 26 wherein the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition.
28. The process of claim 1 or 3 wherein the catalyst/additive composition further comprises a matrix material selected from the group consisting of alumina, silica, silica alumina, titania, zirconia, yttria, lanthana, ceria, neodymia, samaria, europia, gadolinia, praseodymia, and mixtures thereof.
29. The process of claim 28 wherein the matrix material is present in an amount less than 70 weight percent.
30. The process of claim 1 or 3 further comprising recovering the cracking catalyst from said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst.
31. The process of claim 30 wherein the cracking catalyst and the particulate catalyst/additive composition are fluidized during contacting said hydrocarbon feedstock.
32. The process of claim 1 or 3 further comprising contacting the hydrocarbon feed with at least one additional NOx reduction composition.
33. The process of claim 32 wherein the additional NOx reduction composition is a non-zeolitic composition.
34. The process of claim 33 wherein the additional NOx reduction composition comprises (1) an acidic metal oxide containing substantially no zeolite; (2) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (3) an oxygen storage metal oxide component; and (4) at least one noble metal component.
35. The process of claim 32 wherein the additional NOx reduction composition is a low NOx CO combustion promoter composition which comprises (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) palladium.
36. The process of claim 32 wherein the additional NOx reduction composition comprises (1) an acidic oxide support; (2) an alkali metal and/or alkaline earth metal or mixtures thereof; (3) a transition metal oxide having oxygen storage capability; and (4) a transition metal selected from Groups IB and IIB of the Periodic Table, and mixtures thereof.
37. The process of claim 32 wherein the additional NOx reduction composition comprises at least one metal-containing spinel which includes a first metal and a second metal having a valence higher than the valence of said first metal, at least one component of a third metal other than said first and second metals and at least one component of a fourth metal other than said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group VIA metals, the rare-earth metals, the Platinum Group metals and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
38. The process of claim 37 wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal.
39. The process of claim 37 wherein the third metal component in the metal containing spinel is selected from the group consisting of a Platinum Group metal, the rare-earth metals and mixtures thereof.
40. The process of claim 37 wherein the third metal component is present in an amount in the range of about 0.001 to about 20 weight percent, calculated as elemental third metal.
41. The process of claim 37 wherein said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent, calculated as elemental fourth metal.
42. The process of claim 32 wherein the additional NOx reduction additive is a zinc based catalyst.
43. The process of claim 32 wherein the additional NOx reduction additive is an antimony based NOx reduction additive.
44. The process of claim 32 wherein the additional NOx reduction additive is a perovskite-spinel NOx reduction additive.
45. The process of claim 32 wherein the additional NOx reduction additive is a hydrotalcite containing composition.
46. The process of claim 32 wherein the additional NOx reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.
47. The process of claim 1 wherein the particulate NOx reduction composition has a mean particle size from about 50 to about 200 μm.
48. The process of claim 47 wherein the particulate NOx reduction composition has a mean particle size from about 55 to about 150 μm.
49. The process of claim 1 or 3 wherein the particulate NOx reduction composition has a Davison attrition index (DI) value of less than 50.
50. The process of claim 49 wherein the particulate NOx reduction composition has a DI value of less than 20.
51. The process of claim 50 wherein the particulate NOx reduction composition has a DI value of less than 15.
52. The process of claim 2 wherein the amount of the catalyst/additive composition in the catalyst inventory is that amount sufficient to provide a ratio of NOx reduction zeolite component to Y-type zeolite in the total catalyst inventory of less than 2.
53. The process of claim 52 wherein the ratio of NOx reduction zeolite component to Y-type zeolite in the total catalyst inventory is less than 1.
54. The process of claim 2 wherein step (b) is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone.
55. A fluid cracking catalyst (FCC) composition, which composition comprises (a) a FCC cracking component suitable for catalyzing the cracking of hydrocarbons under FCC conditions, and (b) a particulate NOx reduction catalyst/additive composition having a mean particle size of greater than 45 μm and comprising (i) at least 10 weight percent of NOx reduction zeolite component selected from the group consisting of ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite, omega or mixtures thereof, 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.
56. The catalyst of claim 55 wherein the FCC cracking component contains a Y-type zeolite.
57. The catalyst of claim 56 wherein the catalyst/additive composition is present in the total catalyst inventory in an amount sufficient to provide a ratio of NOx reduction zeolite component to Y-type zeolite of less than 2.
58. The catalyst of claim 55 wherein the amount of NOx reduction zeolite component present in the catalyst/additive composition is at least 30 weight percent of the composition.
59. The catalyst of claim 58 wherein the amount of NOx reduction zeolite component present in the catalyst/additive composition is at least 40 weight percent of the composition.
60. The catalyst of claim 59 wherein the amount of NOx reduction zeolite component present in the catalyst/additive composition is at least 50 weight percent of the composition.
61. The catalyst of claim 55 wherein the amount of NOx reduction zeolite component present in the catalyst/additive composition ranges from about 10 to about 85 weight percent of the composition.
62. The catalyst of claim 61 wherein the amount of NOx reduction zeolite component present in the catalyst/additive composition ranges from about 30 to about 80 weight percent of the composition.
63. The catalyst of claim 62 wherein the amount of NOx reduction zeolite component present in the catalyst/additive composition ranges from about 40 to about 75 weight percent of the composition.
64. The catalyst of claim 55 wherein the NOx reduction zeolite component is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof.
65. The catalyst of claim 55 wherein the NOx reduction zeolite component further comprises at least one stabilizing metal.
66. The catalyst of claim 65 wherein the stabilizing metal is a metal selected from the group consisting of Groups 2A, 3B, 4B, 5B, 6B, 7B, 8B, 2B, 3A, 4A, 5A, the Lanthanide Series of The Periodic Table, Ag and mixtures thereof.
67. The catalyst of claim 66 wherein the stabilizing metal is selected from the group consisting of Groups 3B, 2A, 2B, 3A and the Lanthanide Series of the Periodic Table, and mixtures thereof.
68. The catalyst of claim 67 wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof.
69. The catalyst of claim 65 wherein the stabilizing metal is incorporated into the pores of the NOx reduction zeolite component.
70. The catalyst of claim 55 wherein the inorganic binder in the particulate catalyst/additive composition is selected from the group consisting of silica, alumina, silica alumina and mixtures thereof.
71. The catalyst of claim 70 wherein the inorganic binder is alumina.
72. The catalyst of claim 71 wherein the inorganic binder is an aluminum chlorohydrol.
73. The catalyst of claim 71 wherein the alumina is an acid or base peptized alumina.
74. The catalyst of claim 55 wherein the amount of inorganic binder present in the particulate catalyst/additive composition ranges from about 10 to about 30 weight percent of the composition.
75. The catalyst of claim 74 wherein the amount of inorganic binder present in the particulate catalyst/additive composition ranges from about 15 to about 25 weight percent of the composition.
76. The catalyst of claim 55 wherein the NOx reduction zeolite component is selected from the group consisting of beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, Offretite, A, ZSM-12, ZSM-23, omega and mixtures thereof.
77. The catalyst of claim 55 wherein the NOx reduction zeolite component has a SiO2 to Al2O3 molar ratio of less than 500.
78. The catalyst of claim 55 wherein the particulate catalyst/additive composition further comprises a zeolite other than the NOx reduction zeolite component.
79. The catalyst of claim 78 wherein the other zeolite is a zeolite selected from the group consisting of ferrierite, ZSM-5, ZSM-35 and mixtures thereof.
80. The catalyst of claim 78 wherein the other zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.
81. The catalyst of claim 80 wherein the other zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition.
82. The catalyst of claim 55 wherein the composition further comprises a matrix material selected from the group consisting of alumina, silica, silica alumina, titania, zirconia, yttria, lanthana, ceria, neodymia, samaria, europia, gadolinia, praseodymia and mixtures thereof.
83. The catalyst of claim 82 wherein the matrix material is present in an amount less than 70 weight percent.
84. The catalyst of claim 55 further comprising at least one additional NOx reduction composition.
85. The catalyst of claim 84 wherein the additional NOx reduction composition is a non-zeolitic composition.
86. The catalyst of claim 85 wherein the additional NOx reduction composition comprises (a) an acidic metal oxide containing substantially no zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and, (d) at least one noble metal component.
87. The catalyst of claim 84 wherein the additional NOx reduction composition comprises (a) an acidic metal oxide support; (b) an alkali metal, alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and, (d) a transition metal selected from Groups IB and IIB of the Periodic Table, and mixtures thereof.
88. The catalyst of claim 84 wherein the additional NOx reduction composition is a low NOx CO combustion promoter composition which comprises (a) an acidic oxide support; (b) an alkali metal, an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) palladium.
89. The catalyst of claim 84 wherein the additional NOx reduction composition comprises at least one metal-containing spinel which includes a first metal and a second metal having a valence higher than the valence of said first metal, at least one component of a third metal other than said first and second metals and at least one component of a fourth metal other than said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group VIA metals, the rare-earth metals, the Platinum Group metals and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
90. The catalyst of claim 89 wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal.
91. The catalyst of claim 89 wherein the third metal component in the metal containing spinel is selected from the group consisting of a Platinum Group metal, the rare-earth metals and mixtures thereof.
92. The catalyst of claim 89 wherein the third metal component is present in an amount in the range of about 0.001 to about 20 weight percent, calculated as elemental third metal.
93. The catalyst of claim 89 wherein said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent, calculated as elemental fourth metal.
94. The catalyst of claim 84 wherein the additional NOx reduction additive is a zinc based catalyst.
95. The catalyst of claim 84 wherein the additional NOx reduction additive is an antimony based NOx reduction additive.
96. The catalyst of claim 84 wherein the additional NOx reduction additive is a perovskite-spinel NOx reduction additive.
97. The catalyst of claim 84 wherein the additional NOx reduction additive is a hydrotalcite containing composition.
98. The catalyst of claim 55 wherein the particulate catalyst/additive composition has a mean particle size from about 50 to about 200 μm.
99. The catalyst of claim 98 wherein the particulate catalyst/additive composition has a mean particle size from about 55 to about 150 μm.
100. The catalyst of claim 55 wherein the particulate catalyst/additive composition has a Davison attrition index (DI) value of less than 50.
101. The catalyst of claim 100 wherein the particulate catalyst/additive composition has a DI value of less than 20.
102. The catalyst of claim 101 wherein the particulate catalyst/additive composition has a DI value of less than 15.
103. The catalyst of claim 84 wherein the additional NOx reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.
104. The catalyst of claim 57 wherein the ratio of NOx reduction zeolite component to Y-type zeolite in the total catalyst inventory is less than 1.
105. A method of reducing NOx emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said method comprising contacting a hydrocarbon feedstock with a cracking catalyst at elevated temperature whereby lower molecular weight hydrocarbon components are formed, said cracking catalyst comprising the composition of claim 55, 56 or 57.
106. The method of claim 105 further comprising recovering the cracking catalyst from said contacting step and treating the used catalyst in a regeneration zone to regenerate said catalyst.
107. The method of claim 106 wherein the cracking catalyst is fluidized during contacting said hydrocarbon feedstock.
108. The method of claim 105 wherein the reduction of NOx emissions is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone.
109. A fluid cracking catalyst comprising (a) a cracking component suitable for catalyzing the cracking of hydrocarbons and (b) at least 0.1 weight percent of a NOx reduction zeolite selected from the group consisting ZSM-11, beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, MCM-35, MCM-61, Offretite, A, ZSM-12, ZSM-23, ZSM-18, ZSM-22, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ-44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, Goosecreekite, Natrolite, omega or mixtures thereof.
110. The cracking catalyst of claim 109 wherein said catalyst comprises integral particles which contain both components (a) and (b).
111. The cracking catalyst of claim 109 wherein component (b) comprises from about 0.1 to about 60 wt % of the cracking catalyst.
112. The cracking catalyst of claim 111 wherein component (b) comprises from about 1 to about 40 wt % of the cracking catalyst.
113. The catalyst of claim 109 further comprising at least one additional NOx reduction composition.
114. The catalyst of claim 113 wherein the additional NOx reduction composition is a non-zeolitic composition.
115. The catalyst of claim 114 wherein the additional NOx reduction composition comprises (a) an acidic metal oxide containing substantially no zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and (d) at least one noble metal component.
116. The catalyst of claim 113 wherein the additional NOx reduction composition comprises (a) an acidic metal oxide support; (b) an alkali metal, alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and, (d) a transition metal selected from Groups IB and IIB of the Periodic Table, and mixtures thereof.
117. The catalyst of claim 113 wherein the additional NOx reduction composition is a low NOx CO combustion promoter composition which comprises (a) an acidic oxide support; (b) an alkali metal, an alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) palladium.
118. The catalyst of claim 113 wherein the additional NOx reduction composition comprises at least one metal-containing spinel which includes a first metal and a second metal having a valence higher than the valence of said first metal, at least one component of a third metal other than said first and second metals and at least one component of a fourth metal other than said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group VIA metals, the rare-earth metals, the Platinum Group metals and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
119. The catalyst of claim 118 wherein the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal.
120. The catalyst of claim 118 wherein the third metal component in the metal containing spinel is selected from the group consisting of a Platinum Group metal, the rare-earth metals and mixtures thereof.
121. The catalyst of claim 118 wherein the third metal component is present in an amount in the range of about 0.001 to about 20 weight percent, calculated as elemental third metal.
122. The catalyst of claim 118 wherein said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent, calculated as elemental fourth metal.
123. The catalyst of claim 113 wherein the additional NOx reduction additive is a zinc based catalyst.
124. The catalyst of claim 113 wherein the additional NOx reduction additive is an antimony based NOx reduction additive.
125. The catalyst of claim 113 wherein the additional NOx reduction additive is a perovskite-spinel NOx reduction additive.
126. The catalyst of claim 113 wherein the additional NOx reduction additive is a hydrotalcite containing composition.
127. The cracking catalyst of claim 109 wherein component (a) comprises a Y-type zeolite and component (b) is present in an amount sufficient to provide a ratio of NOx reduction zeolite to Y-type zeolite of less than 2 in the total catalyst.
128. The cracking catalyst of claim 127 wherein component (b) is present in an amount sufficient to provide a ratio of NOx reduction zeolite to Y-type zeolite of less than 1 in the total catalyst.
129. The cracking catalyst of claim 109 wherein component (b) further comprises at least one stabilizing metal.
130. The cracking catalyst of claim 129 wherein the stabilizing metal is a metal selected from the group consisting of Groups 2A, 3B, 4B, 5B, 6B, 7B, 8B, 2B, 3A, 4A, 5A, the Lanthanide Series of The Periodic Table, Ag and mixtures thereof.
131. The cracking catalyst of claim 130 wherein the stabilizing metal is selected from the group consisting of Groups 3B, 2A, 2B, 3A and the Lanthanide Series of the Periodic Table, and mixtures thereof.
132. The cracking catalyst of claim 131 wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof.
133. The cracking catalyst of claim 129 wherein the stabilizing metal is incorporated into the pores of component (b).
134. The cracking catalyst of claim 113 wherein the additional NOx reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.
135. The cracking catalyst of claim 109 wherein the NOx reduction zeolite is selected from the group consisting of beta, MCM-49, mordenite, MCM-56, Zeolite-L, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, Offretite, A, ZSM-12, ZSM-23, omega and mixtures thereof.
136. The cracking catalyst of claim 109 wherein the NOx reduction zeolite has a SiO2 to Al2O3 molar ratio of less than 500.
137. The cracking catalyst of claim 109 further comprising a zeolite other than the NOx reduction zeolite.
138. The cracking catalyst of claim 137 wherein the other zeolite is selected from the group consisting of ferrierite, ZSM-5, ZSM-35 and mixtures thereof.
139. The cracking catalyst of claim 137 or 138 wherein the other zeolite is present in an amount ranging from about 1 to about 80 weight percent of the composition.
140. The cracking catalyst of claim 139 wherein the other zeolite is present in an amount ranging from about 10 to about 70 weight percent of the composition.
141. The cracking catalyst of claim 109 wherein the NOx reduction zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof.
142. A method of reducing NOx emissions from the regeneration zone during fluid catalytic cracking of a hydrocarbon feedstock into lower molecular weight components, said method comprising (a) contacting a hydrocarbon feedstock during a fluid catalytic cracking (FCC) process wherein NOx emissions are released from a regeneration zone of the FCCU operating under FCC conditions with the FCC cracking catalyst composition of claim 109; and (b) reducing the amount of NOx emissions released from the regeneration zone of the FCCU by at least 10 percent as compared to the amount of NOx emissions released in the absence of the NOx reduction composition.
143. The method of claim 142 wherein step (b) is accomplished without a substantial change in the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained during the FCC process as compared to the hydrocarbon feedstock conversion or yield of cracked hydrocarbons obtained from the cracking catalyst alone.
144. The method of claim 142 or 143 wherein the amount of NOx reduction zeolite present in the cracking catalyst composition comprises at least about 0.1 wt % of the cracking catalyst composition.
145. The method of claim 142 or 143 wherein the amount of NOx reduction zeolite present in the cracking catalyst composition ranges from about 0.1 to about 60 wt % of the cracking catalyst composition.
146. The method of claim 145 wherein the amount of NOx reduction zeolite present in the cracking catalyst composition ranges from about 1 to about 40 wt % of the cracking catalyst composition.
147. The method of claim 142 or 143 wherein the NOx reduction zeolite is exchanged with a cation selected from the group consisting of hydrogen, ammonium, alkali metal and combinations thereof.
148. The method of claim 142 or 143 wherein the NOx reduction zeolite further comprises at least one stabilizing metal.
149. The method of claim 148 wherein the stabilizing metal is a metal selected from the group consisting of Groups 2A, 3B, 4B, 5B, 6B, 7B, 8B, 2B, 3A, 4A, 5A, the Lanthanide Series of The Periodic Table, Ag and mixtures thereof.
150. The method of claim 149 wherein the stabilizing metal is selected from the group consisting of Groups 3B, 2A, 2B, 3A and the Lanthanide Series of the Periodic Table, and mixtures thereof.
151. The method of claim 150 wherein the stabilizing metal is selected from the group consisting of lanthanum, aluminum, magnesium and zinc, and mixtures thereof.
152. The method of claim 148 wherein the stabilizing metal is incorporated into the pores of the NOx reduction zeolite.
153. The method of claim 142 or 143 further comprising recovering the cracking catalyst and treating the used catalyst in a regeneration zone to regenerate said catalyst.
154. The method of claim 142 or 143 wherein the cracking catalyst is fluidized during contacting said hydrocarbon feedstock.
155. The method of claim 142 further comprising contacting the hydrocarbon feed with at least one additional NOx reduction additive composition.
156. The method of claim 155 wherein the additional NOx reduction additive composition is a non-zeolitic composition.
157. The method of claim 156 wherein the additional NOx reduction additive composition comprises (a) an acidic metal oxide containing substantially no zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and (d) at least one noble metal component.
158. The method of claim 155 wherein the NOx reduction additive composition is a low NOx CO combustion promoter composition which comprises (a) an acidic oxide support; (b) an alkali metal and/or alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) palladium.
159. The method of claim 155 wherein the additional NOx reduction additive composition comprises at least one metal-containing spinel which includes a first metal and a second metal having a valence higher than the valence of said first metal, at least one component of a third metal other than said first and second metals and at least one component of a fourth metal other than said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group VIA metals, the rare-earth metals, the Platinum Group metals, and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
160. The method of claim 159 wherein the metal-containing spinel comprises magnesium as said first metal and aluminum as said second metal.
161. The method of claim 159 wherein the third metal component in the metal-containing spinel is selected from the group consisting of a Platinum Group metal, the rare-earth metals and mixtures thereof.
162. The method of claim 159 wherein the third metal component is present in an amount in the range of about 0.001 to about 20 weight percent, calculated as elemental third metal.
163. The method of claim 159 wherein said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent, calculated as elemental fourth metal.
164. The method of claim 155 wherein the additional NOx reduction additive composition comprises (a) an acidic oxide support; (b) an alkali metal, alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) a transition metal selected from the Groups IB and IIB of the Periodic Table.
165. The method of claim 155 wherein the additional NOx reduction additive composition is a zinc based catalyst.
166. The method of claim 155 wherein the additional NOx reduction additive composition is an antimony based NOx reduction additive.
167. The method of claim 155 wherein the additional NOx reduction additive composition is a perovskite-spinel NOx reduction additive.
168. The method of claim 155 wherein the additional NOx reduction additive composition is a hydrotalcite containing composition.
169. The method of claim 155 wherein the additional NOx reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.
170. The method of claim 142 wherein the cracking catalyst composition comprises an additional zeolite selected from the group consisting of ferrierite, ZSM-5, ZSM-35 and mixtures thereof.
171. The method of claim 170 wherein the additional zeolite is present in an amount ranging from about 1 to about 80 weight percent of the cracking catalyst composition.
172. The method of claim 171 wherein the additional zeolite is present in an amount ranging from about 10 to about 70 weight percent of the cracking catalyst composition.
173. The method of claim 142 wherein the cracking catalyst composition comprises a Y-type zeolite as component (a) and component (b) is present in an amount sufficient to provide a ratio of NOx reduction zeolite to Y-type zeolite of less than 2 in the total catalyst composition.
174. The method of claim 173 wherein component (b) is present in an amount sufficient to provide a ratio of NOx reduction zeolite to Y-type zeolite of less than 1 in the total catalyst composition.
175. The method of claim 142 wherein the NOx reduction zeolite in the cracking catalyst composition has a silica to alumina molar ratio of less than 500.
176. The method of claim 105 further comprising contacting the hydrocarbon feed with at least one additional NOx reduction additive composition.
177. The method of claim 176 wherein the additional NOx reduction additive composition is a non-zeolitic composition.
178. The method of claim 177 wherein the additional NOx reduction additive composition comprises (a) an acidic metal oxide containing substantially no zeolite; (b) a metal component, measured as the oxide, selected from the group consisting of an alkali metal, an alkaline earth metal and mixtures thereof; (c) an oxygen storage metal oxide component; and (d) at least one noble metal component.
179. The method of claim 176 wherein the NOx reduction additive composition is a low NOx CO combustion promoter composition which comprises (a) an acidic oxide support; (b) an alkali metal and/or alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) palladium.
180. The method of claim 176 wherein the additional NOx reduction additive composition comprises at least one metal-containing spinel which includes a first metal and a second metal having a valence higher than the valence of said first metal, at least one component of a third metal other than said first and second metals and at least one component of a fourth metal other than said first, second and third metals, wherein said third metal is selected from the group consisting of Group IB metals, Group IIB metals, Group VIA metals, the rare-earth metals, the Platinum Group metals, and mixtures thereof, and said fourth metal is selected from the group consisting of iron, nickel, titanium, chromium, manganese, cobalt, germanium, tin, bismuth, molybdenum, antimony, vanadium and mixtures thereof.
181. The method of claim 180 wherein the metal-containing spinel comprises magnesium as said first metal and aluminum as said second metal.
182. The method of claim 180 wherein the third metal component in the metal-containing spinel is selected from the group consisting of a Platinum Group metal, the rare-earth metals and mixtures thereof.
183. The method of claim 180 wherein the third metal component is present in an amount in the range of about 0.001 to about 20 weight percent, calculated as elemental third metal.
184. The method of claim 180 wherein said fourth metal component is present in an amount in the range of about 0.001 to about 10 weight percent, calculated as elemental fourth metal.
185. The method of claim 176 wherein the additional NOx reduction additive composition comprises (a) an acidic oxide support; (b) an alkali metal, alkaline earth metal or mixtures thereof; (c) a transition metal oxide having oxygen storage capability; and (d) a transition metal selected from the Groups IB and IIB of the Periodic Table.
186. The method of claim 176 wherein the additional NOx reduction additive composition is a zinc based catalyst.
187. The method of claim 176 wherein the additional NOx reduction additive composition is an antimony based NOx reduction additive.
188. The method of claim 176 wherein the additional NOx reduction additive composition is a perovskite-spinel NOx reduction additive.
189. The method of claim 176 wherein the additional NOx reduction additive composition is a hydrotalcite containing composition.
190. The method of claim 176 wherein the additional NOx reduction composition comprises (i) an acidic metal oxide, (ii) cerium oxide, (iii) a lanthanide oxide other than ceria, and (iv) optionally, at least one oxide of a transition metal selected from Groups IB and IIB of the Periodic Table, noble metals and mixtures thereof.
US10/909,709 2004-04-15 2004-08-02 Compositions and processes for reducing NOx emissions during fluid catalytic cracking Abandoned US20050232839A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US10/824,913 US7304011B2 (en) 2004-04-15 2004-04-15 Compositions and processes for reducing NOx emissions during fluid catalytic cracking
US10/909,709 US20050232839A1 (en) 2004-04-15 2004-08-02 Compositions and processes for reducing NOx emissions during fluid catalytic cracking

Applications Claiming Priority (17)

Application Number Priority Date Filing Date Title
US10/909,709 US20050232839A1 (en) 2004-04-15 2004-08-02 Compositions and processes for reducing NOx emissions during fluid catalytic cracking
EP20050740343 EP1747062A1 (en) 2004-04-15 2005-04-15 Compositions and processes for reducing no-x emissions during fluid catalytic cracking
BRPI0509938A BRPI0509938B1 (en) 2004-04-15 2005-04-15 compositions and methods to reduce NOx emissions during fluid catalytic cracking
KR20067021354A KR101180175B1 (en) 2004-04-15 2005-04-15 COMPOSITIONS AND PROCESSES FOR REDUCING NOx EMISSIONS DURING FLUID CATALYTIC CRACKING
JP2007508598A JP4974883B2 (en) 2004-04-15 2005-04-15 Compositions and methods for reducing the NOx exhaust in fluid catalytic cracking
MXPA06011795A MXPA06011795A (en) 2004-04-15 2005-04-15 Compositions and processes for reducing nox.
SG200902502-4A SG152232A1 (en) 2004-04-15 2005-04-15 Compositions and processes for reducing nox emissions during fluid catalytic cracking
AU2005233199A AU2005233199B2 (en) 2004-04-15 2005-04-15 Compositions and processes for reducing NOx emissions during fluid catalytic cracking
CN 200580019864 CN1968748B (en) 2004-04-15 2005-04-15 Compositions and processes for reducing NOx emissions during fluid catalytic cracking
PCT/US2005/012982 WO2005099898A1 (en) 2004-04-15 2005-04-15 Compositions and processes for reducing nox emissions during fluid catalytic cracking
CA 2563499 CA2563499C (en) 2004-04-15 2005-04-15 Compositions and processes for reducing nox emissions during fluid catalytic cracking
RU2006140261/04A RU2408655C2 (en) 2004-04-15 2005-04-15 Compositions and methods for reducing nox emissions during catalytic cracking with fluidised catalyst
ARP050101513 AR050581A1 (en) 2004-04-15 2005-04-18 Compositions and processes to reduce NOx emissions during fluid catalytic cracking.
TW94126051A TWI396589B (en) 2004-08-02 2005-08-01 Compositions and processes for reducing nox emissions during fluid catalytic cracking
IL17830906A IL178309A (en) 2004-04-15 2006-09-26 Compositions and processes for reducing nox emissions during fluid catalytic cracking
NO20065266A NO20065266A (en) 2004-04-15 2006-11-15 Compositions and methods feeder reduce NOX emissions below the liquid catalytic cracking
US12/291,379 US7641787B2 (en) 2004-04-15 2008-11-07 Compositions and processes for reducing NOx emissions during fluid catalytic cracking

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US10/824,913 Continuation-In-Part US7304011B2 (en) 2004-04-15 2004-04-15 Compositions and processes for reducing NOx emissions during fluid catalytic cracking

Related Child Applications (2)

Application Number Title Priority Date Filing Date
US10/909,706 Continuation US20050100494A1 (en) 2003-11-06 2004-08-02 Ferrierite compositions for reducing NOx emissions during fluid catalytic cracking
US12/291,379 Continuation US7641787B2 (en) 2004-04-15 2008-11-07 Compositions and processes for reducing NOx emissions during fluid catalytic cracking

Publications (1)

Publication Number Publication Date
US20050232839A1 true US20050232839A1 (en) 2005-10-20

Family

ID=34967218

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/909,709 Abandoned US20050232839A1 (en) 2004-04-15 2004-08-02 Compositions and processes for reducing NOx emissions during fluid catalytic cracking
US12/291,379 Expired - Fee Related US7641787B2 (en) 2004-04-15 2008-11-07 Compositions and processes for reducing NOx emissions during fluid catalytic cracking

Family Applications After (1)

Application Number Title Priority Date Filing Date
US12/291,379 Expired - Fee Related US7641787B2 (en) 2004-04-15 2008-11-07 Compositions and processes for reducing NOx emissions during fluid catalytic cracking

Country Status (14)

Country Link
US (2) US20050232839A1 (en)
EP (1) EP1747062A1 (en)
JP (1) JP4974883B2 (en)
KR (1) KR101180175B1 (en)
AR (1) AR050581A1 (en)
AU (1) AU2005233199B2 (en)
BR (1) BRPI0509938B1 (en)
CA (1) CA2563499C (en)
IL (1) IL178309A (en)
MX (1) MXPA06011795A (en)
NO (1) NO20065266A (en)
RU (1) RU2408655C2 (en)
SG (1) SG152232A1 (en)
WO (1) WO2005099898A1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070286782A1 (en) * 2006-06-08 2007-12-13 Chevron U.S.A. Inc. Reduction of oxides of nitrogen in a gas stream using molecular sieve ssz-75
US20080213150A1 (en) * 2005-03-24 2008-09-04 George Yaluris Method for Controlling Nox Emissions in the Fccu
US20090057199A1 (en) * 2005-04-27 2009-03-05 Michael Scott Ziebarth Compositions and Processes for Reducing NOx Emissions During Fluid Catalytic Cracking
US7976697B2 (en) 2005-04-29 2011-07-12 W. R. Grace & Co.-Conn. NOX reduction compositions for use in partial burn FCC processes
EP2739374A1 (en) * 2011-08-05 2014-06-11 Chevron U.S.A., Inc. Reduction of oxides of nitrogen in a gas stream using molecular sieve ssz-23
US9861966B2 (en) 2006-03-22 2018-01-09 Cosmo Oil Co., Ltd. Catalytic cracking catalyst, process for producing the same, and method of catalytic cracking of hydrocarbon oil
WO2018189616A1 (en) * 2017-04-10 2018-10-18 Reliance Industries Limited An fcc catalyst additive and a process for preparation thereof

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7678735B2 (en) * 2005-11-28 2010-03-16 Engelhard Corporation FCC additive for partial and full burn NOx control
GB0609783D0 (en) * 2006-05-17 2006-06-28 Magnesium Elektron Ltd Improved oxygen storage component
US7381676B1 (en) * 2007-01-16 2008-06-03 Exxonmobil Chemical Patents Inc. Catalyst composition and its use thereof in aromatics alkylation
DE102008028760B9 (en) * 2008-06-17 2010-09-30 Zylum Beteiligungsgesellschaft Mbh & Co. Patente Ii Kg Process for the separation of NOx from an epoxy-containing gas stream
US20110230333A1 (en) * 2010-03-16 2011-09-22 Uop Llc Olefin Cracking Catalyst and Manufacturing Process
CN102812109B (en) 2010-03-18 2015-01-07 格雷斯公司 High light olefins fcc catalyst compositions
CN102811812A (en) 2010-03-18 2012-12-05 格雷斯公司 Process for making improved catalysts from clay-derived zeolites
CN102791374B (en) * 2010-03-18 2016-04-13 格雷斯公司 A method for preparing a zeolite modified peptized alumina catalyst
CN102631933B (en) * 2011-02-14 2014-02-26 中国石油化工股份有限公司 Catalyst for removing NO in smoke and preparation method thereof
US8512674B1 (en) 2012-03-01 2013-08-20 Chevron U.S.A. Inc. Preparation of molecular sieve SSZ-23
WO2014121813A1 (en) * 2013-02-05 2014-08-14 Rhodia Operations Precipitated and calcinated composition based on zirconium oxide and cerium oxide
CN104549421B (en) * 2013-10-28 2017-06-23 中国石油化工股份有限公司 Preparation of a catalyst and catalytic cracking
CN106902802A (en) * 2017-03-31 2017-06-30 中石化炼化工程(集团)股份有限公司 Additive and preparation method and application thereof
CN107262106A (en) * 2017-07-03 2017-10-20 中石化炼化工程(集团)股份有限公司 Catalyst and preparation method and application thereof

Citations (96)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634140A (en) * 1968-09-20 1972-01-11 Asea Ab Fuel cell device utilizing air as oxidant
US3894940A (en) * 1973-11-15 1975-07-15 Grace W R & Co Hydrocarbon cracking catalysts with promoter mixtures
US4199435A (en) * 1978-12-04 1980-04-22 Chevron Research Company NOx Control in cracking catalyst regeneration
US4428827A (en) * 1983-01-24 1984-01-31 Uop Inc. FCC Sulfur oxide acceptor
US4434147A (en) * 1981-10-05 1984-02-28 Chevron Research Company Simultaneous sulfur oxide and nitrogen oxide control in FCC units using cracking catalyst fines with ammonia injection
US4495304A (en) * 1980-07-29 1985-01-22 Atlantic Richfield Company Catalyst for conversion of hydrocarbons
US4495305A (en) * 1980-07-29 1985-01-22 Atlantic Richfield Company Catalyst for conversion of hydrocarbons
US4513091A (en) * 1983-02-14 1985-04-23 Mobil Oil Corporation Hydrothermal zeolite activation
US4521298A (en) * 1980-07-18 1985-06-04 Mobil Oil Corporation Promotion of cracking catalyst octane yield performance
US4522937A (en) * 1982-11-29 1985-06-11 Atlantic Richfield Company Preparative process for alkaline earth metal, aluminum-containing spinels
US4582815A (en) * 1984-07-06 1986-04-15 Mobil Oil Corporation Extrusion of silica-rich solids
US4642178A (en) * 1980-07-29 1987-02-10 Katalistiks, Inc. Process for conversion of hydrocarbons
US4654316A (en) * 1984-08-09 1987-03-31 The British Petroleum Company P.L.C. Selective dealumination of zeolites
US4728635A (en) * 1986-04-07 1988-03-01 Katalistiks International Inc. Alkaline earth metal spinels and processes for making
US4735927A (en) * 1985-10-22 1988-04-05 Norton Company Catalyst for the reduction of oxides of nitrogen
US4747935A (en) * 1986-03-26 1988-05-31 Union Oil Company Of California Process for the catalytic cracking of feedstocks containing nitrogen
US4758418A (en) * 1980-07-29 1988-07-19 Union Carbide Corporation Process for combusting solid sulfur-containing material
US4797266A (en) * 1986-08-07 1989-01-10 Shell Oil Company Method of preparation of a combined ZSM-5-ferrierite aluminosilicate
US4798813A (en) * 1986-07-04 1989-01-17 Babcock-Hitachi Kabushiki Kaisha Catalyst for removing nitrogen oxide and process for producing the catalyst
US4810369A (en) * 1987-05-07 1989-03-07 Union Oil Company Of California Process for the catalytic cracking of feedstocks containing high levels of nitrogen
US4812430A (en) * 1987-08-12 1989-03-14 Mobil Oil Corporation NOx control during multistage combustion
US4812431A (en) * 1987-08-12 1989-03-14 Mobil Oil Corporation NOx control in fluidized bed combustion
US4818509A (en) * 1984-03-23 1989-04-04 Mobil Oil Corporation Continuous process for manufacturing crystalline zeolites in continuously stirred backmixed crystallizers
US4826799A (en) * 1988-04-14 1989-05-02 W. R. Grace & Co.-Conn. Shaped catalyst and process for making it
US4830840A (en) * 1987-03-13 1989-05-16 Uop Process for removing sulfur oxide and nitrogen oxide
US4853203A (en) * 1986-11-21 1989-08-01 Institut Francais Du Petrole Ferrierites; their process of manufacture
US4855115A (en) * 1986-07-29 1989-08-08 Mitsubishi Petrochemical Co. Ltd. Process for removing nitrogen oxides from exhaust gases
US4895994A (en) * 1988-04-14 1990-01-23 W. R. Grace & Co.-Conn. Shaped catalysts and processes
US4898662A (en) * 1987-12-09 1990-02-06 Mobil Oil Corp. Catalytic cracking process using high equilibrium activity additive catalyst
US4898846A (en) * 1986-03-21 1990-02-06 W. R. Grace & Co.-Conn. Cracking catalysts with octane enhancement
US4904627A (en) * 1987-03-13 1990-02-27 Uop Alkaline earth metal spinel/kaolin clays and processes for making
US4946581A (en) * 1987-01-13 1990-08-07 Akzo N.V. Cracking process employing a catalyst composition and absorbent which contain an anionic clay
US4988432A (en) * 1989-12-28 1991-01-29 Mobil Oil Corporation Reducing NOx emissions with antimony additive
US4988654A (en) * 1989-12-29 1991-01-29 Chevron Research Company Dual component cracking catalyst with vanadium passivation and improved sulfur tolerance
US5002654A (en) * 1989-12-28 1991-03-26 Mobil Oil Corporation Reducing NOx emissions with zinc catalyst
US5002653A (en) * 1989-12-29 1991-03-26 Chevron Research Company Catalytic cracking process with vanadium passivation and improved
US5011272A (en) * 1984-12-21 1991-04-30 Canon Kabushiki Kaisha Compact zoom lens
US5017538A (en) * 1988-04-18 1991-05-21 Toyota Jidosha Kabushiki Kaisha Catalyst for purifying exhaust gas and a method of producing the same
US5037538A (en) * 1990-02-26 1991-08-06 Mobil Oil Corporation Catalytic cracking process with isolated catalyst for conversion of NO.sub.x
US5102530A (en) * 1986-03-21 1992-04-07 W. R. Grace & Co.-Conn. Cracking catalysts with octane enhancement
US5114898A (en) * 1990-01-18 1992-05-19 Board Of Trustees Operating Michigan State University Layered double hydroxide sorbents for the removal of SOx from flue gas and other gas streams
US5114691A (en) * 1990-01-18 1992-05-19 Board Of Trustees Operating Michigan State University Process using sorbents for the removal of SOx from flue gas
US5130012A (en) * 1991-01-24 1992-07-14 Mobil Oil Corporation Process and apparatus for reducing NOx emissions from high-efficiency FFC regenerators
US5190736A (en) * 1991-10-18 1993-03-02 Mobil Oil Corporation Synthesis of crystalline ZSM-35
US5206196A (en) * 1990-12-18 1993-04-27 Tosoh Corporation Catalyst for purifying exhaust gas
US5208198A (en) * 1990-12-18 1993-05-04 Tosoh Corporation Catalyst for purifying exhaust gas
US5240690A (en) * 1992-04-24 1993-08-31 Shell Oil Company Method of removing NH3 and HCN from and FCC regenerator off gas
US5286693A (en) * 1991-11-06 1994-02-15 Nippon Oil Co., Ltd. Method of producing catalyst for converting hydrocarbons
US5294332A (en) * 1992-11-23 1994-03-15 Amoco Corporation FCC catalyst and process
US5320822A (en) * 1991-11-20 1994-06-14 The Dow Chemical Company Process of growing crystalline microporous solids in a fluoride-containing, substantially non-aqueous growth medium
US5382352A (en) * 1992-10-20 1995-01-17 Mobil Oil Corporation Conversion of NOx in FCC bubbling bed regenerator
US5413699A (en) * 1993-10-14 1995-05-09 Mobil Oil Corporation FCC process with fines tolerant SCR reactor
US5413977A (en) * 1992-02-27 1995-05-09 Union Oil Company Of California Catalyst containing zeolite beta and a layered magnesium silicate
US5422333A (en) * 1992-08-25 1995-06-06 Idemitsu Kosan Company Limited Exhaust gas purifying catalyst
US5427989A (en) * 1993-03-11 1995-06-27 Nissan Motor Co., Ltd. Catalysts for the purification of exhaust gas
US5433933A (en) * 1989-12-21 1995-07-18 Toyota Jidosha Kabushiki Kaisha Method of purifying oxygen-excess exhaust gas
US5503818A (en) * 1993-11-01 1996-04-02 Csir Aluminosilicate catalyst, a process for the manufacture thereof and a process for the skeletal isomerization of linear olefins
US5510306A (en) * 1993-12-29 1996-04-23 Shell Oil Company Process for isomerizing linear olefins to isoolefins
US5599520A (en) * 1994-11-03 1997-02-04 Garces; Juan M. Synthesis of crystalline porous solids in ammonia
US5614453A (en) * 1991-09-11 1997-03-25 Uop Catalyst containing zeolite beta and a pillared clay
US5627125A (en) * 1994-07-01 1997-05-06 Monsanto Company Process for preparing carboxylic acid salts and methods for making such catalysts and catalysts useful in such process
US5705053A (en) * 1995-08-30 1998-01-06 Mobil Oil Corporation FCC regenerator NOx reduction by homogeneous and catalytic conversion
US5716514A (en) * 1995-08-30 1998-02-10 Mobil Oil Corporation FCC NOx reduction by turbulent/laminar thermal conversion
US5741468A (en) * 1994-12-28 1998-04-21 Kabushiki Kaisha Riken Exhaust gas cleaner and method for cleaning exhaust gas
US5744686A (en) * 1995-09-20 1998-04-28 Uop Process for the removal of nitrogen compounds from an aromatic hydrocarbon stream
US5785947A (en) * 1991-12-18 1998-07-28 Chevron U.S.A. Inc. Preparation of zeolites using organic template and amine
US5879645A (en) * 1994-11-03 1999-03-09 Korea Research Institute Of Chemical Technology Method for removing nitrogen oxides in exhaust gas by selective catalytic reduction and catalyst for reduction of nitrogen oxides
US5908806A (en) * 1995-06-07 1999-06-01 Asec Manufacturing Copper-silver zeolite catalysts
US5908804A (en) * 1994-09-30 1999-06-01 The Boc Group, Inc. Reduction of emissions from FCC regenerators
US6017508A (en) * 1995-10-24 2000-01-25 The Dow Chemical Company Process of modifying the porosity of aluminosilicates and silicas, and mesoporous compositions derived therefrom
US6033641A (en) * 1996-04-18 2000-03-07 University Of Pittsburgh Of The Comonwealth System Of Higher Education Catalyst for purifying the exhaust gas from the combustion in an engine or gas turbines and method of making and using the same
US6040259A (en) * 1996-05-29 2000-03-21 Exxon Chemical Patents Inc. Metal-containing zeolite catalyst, preparation thereof and use for hydrocarbon conversion
US6090271A (en) * 1997-06-10 2000-07-18 Exxon Chemical Patents Inc. Enhanced olefin yields in a catalytic process with diolefins
US6190538B1 (en) * 1998-08-03 2001-02-20 Shell Oil Company Process for the preparation of a catalyst composition
US6214211B1 (en) * 1998-04-21 2001-04-10 Idemitsu Kosan Co., Ltd Catalytic cracking catalyst
US20010002426A1 (en) * 1994-11-23 2001-05-31 Mohr Gary David Hydrocarbon conversion process using a zeolite bound zeolite catalyst
US20020013228A1 (en) * 2000-06-20 2002-01-31 Takeshi Matsumoto Exhaust gas purifying catalyst and method for purifying exhaust gas
US20020016259A1 (en) * 2000-06-28 2002-02-07 Tatsuya Yoshikawa Exhaust gas purifying catalyst
US20020022573A1 (en) * 2000-06-22 2002-02-21 Hiroshi Tanada Exhaust gas purifying catalyst
US20020022574A1 (en) * 2000-07-17 2002-02-21 Hiroshi Tanada Exhaust gas purifying catalyst
US6358881B1 (en) * 1995-05-05 2002-03-19 W. R. Grace & Co.-Conn. Reduced NOx combustion promoter for use in FCC processes
US20020038051A1 (en) * 2000-02-18 2002-03-28 Degussa-Huls Ag Raney copper
US20020037808A1 (en) * 1999-07-31 2002-03-28 Degussa-Huels Aktiengesellschaft Fixed bed catalysts
US6376708B1 (en) * 2000-04-11 2002-04-23 Monsanto Technology Llc Process and catalyst for dehydrogenating primary alcohols to make carboxylic acid salts
US20020049132A1 (en) * 1998-11-03 2002-04-25 Deng-Yang Jan Process for preparing attrition resistant zeolitic layered catalyst composition
US6379536B1 (en) * 1995-05-05 2002-04-30 W. R. Grace & Co.-Conn. NOx reduction compositions for use in FCC processes
US6380119B1 (en) * 1997-06-06 2002-04-30 Basf Aktiengesellschaft Method for regenerating a zeolitic catalyst
US6395403B2 (en) * 1999-05-06 2002-05-28 W. R. Grace & Co. Conn Promoted porous catalyst
US20020082460A1 (en) * 1997-12-03 2002-06-27 Johannes P. Verduijn Coated zeolite catalysts and use for hydrocarbon conversion
US6413898B1 (en) * 1999-12-28 2002-07-02 Corning Incorporated Zeolite/alumina catalyst support compositions and method of making the same
US20020094932A1 (en) * 1999-12-29 2002-07-18 Faber Margaret K. Zeolite/Alumina catalyst support compositions and method of making the same
US20020094314A1 (en) * 2000-11-27 2002-07-18 National Institute Of Advanced Industrial Science And Technology Method for the reduction and removal of nitrogen oxides
US20030019794A1 (en) * 2001-04-13 2003-01-30 Schmidt Stephen Raymond Process for sulfur removal from hydrocarbon liquids
US20030040425A1 (en) * 2001-08-21 2003-02-27 Sud-Chemie Prototech Inc. Method for washcoating a catalytic material onto a monolithic structure
US6528031B1 (en) * 1998-12-31 2003-03-04 Korea Research Institute Of Chemical Technology Method for preparing noble metal-supported zeolite catalyst for catalytic reduction of nitrogen oxide
US20030073566A1 (en) * 2001-10-11 2003-04-17 Marshall Christopher L. Novel catalyst for selective NOx reduction using hydrocarbons

Family Cites Families (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2892801A (en) 1955-12-13 1959-06-30 Gen Electric Catalysts
US3036973A (en) 1958-11-21 1962-05-29 Hoffmann La Roche Racemization catalyst and process for the manufacture thereof
US3184417A (en) 1960-12-29 1965-05-18 Gen Aniline & Film Corp Method of preparing a copper modified nickel catalyst composition
US3129252A (en) 1960-12-29 1964-04-14 Gen Aniline & Fihn Corp Purification of butynediol
US3364136A (en) 1965-12-10 1968-01-16 Mobil Oil Corp Novel cyclic catalytic process for the conversion of hydrocarbons
US3617488A (en) 1969-12-19 1971-11-02 Sigmund M Csicsery Hydrotreating catalyst comprising clay-type aluminosilicate component and a crystalline zeolitic molecular sieve component, and process using said catalyst
US4290878A (en) 1978-12-08 1981-09-22 Chevron Research Company NOx control in platinum-promoted complete combustion cracking catalyst regeneration
JPH0153717B2 (en) 1980-07-29 1989-11-15 Atoranchitsuku Ritsuchifuiirudo Co
US4472267A (en) 1980-07-29 1984-09-18 Atlantic Richfield Company Catalyst and process for conversion of hydrocarbons
US4957892A (en) 1980-07-29 1990-09-18 Uop Process for combusting solid sulfur containing material
US4471070A (en) 1982-11-29 1984-09-11 Atlantic Richfield Company Preparative process for alkaline earth metal, aluminum-containing spinels
US4472532A (en) 1982-11-29 1984-09-18 Atlantic Richfield Company Preparative process for alkaline earth metal, aluminum-containing spinels
US4476245A (en) 1982-11-29 1984-10-09 Atlantic Richfield Company Preparative process for alkaline earth metal, aluminum-containing spinels
US4778664A (en) 1986-03-10 1988-10-18 The Dow Chemical Company Process for the removal of NO from fluid streams using a water soluble polymeric chelate of a polyvalent metal
US4708786A (en) 1986-03-26 1987-11-24 Union Oil Company Of California Process for the catalytic cracking of nitrogen-containing feedstocks
US4790982A (en) 1986-04-07 1988-12-13 Katalistiks International, Inc. Metal-containing spinel composition and process of using same
US4985384A (en) * 1986-08-25 1991-01-15 W. R. Grace & Co-Conn. Cracking catalysts having aromatic selectivity
US4880521A (en) * 1987-05-07 1989-11-14 Union Oil Company Of California Process for the cracking of feedstocks containing high levels of nitrogen
US4957718A (en) 1987-11-24 1990-09-18 Uop Process for reducing emissions of sulfur oxides and composition useful in same
US5371055A (en) 1988-07-07 1994-12-06 W. R. Grace & Co.-Conn. Increasing metal-tolerance of FCC catalyst by sulfur oxide removal
GB8820358D0 (en) 1988-08-26 1988-09-28 Shell Int Research Process for catalytic cracking of hydrocarbon feedstock
US4973399A (en) * 1989-11-03 1990-11-27 Mobil Oil Corporation Catalytic cracking of hydrocarbons
US4980052A (en) 1988-12-05 1990-12-25 Mobil Oil Corporation Catalytic cracking of hydrocarbons
US4889615A (en) 1988-12-06 1989-12-26 Mobil Oil Corporation Additive for vanadium capture in catalytic cracking
GB8904409D0 (en) 1989-02-27 1989-04-12 Shell Int Research Process for the conversion of a hydrocarbonaceous feedstock
US5145815A (en) 1989-08-10 1992-09-08 Uop Regeneration of zeolitic molecular sieves with sulfur oxide absorption on soda-lime bed
CA2024154C (en) 1989-08-31 1995-02-14 Senshi Kasahara Catalyst for reducing nitrogen oxides from exhaust gas
JPH07106300B2 (en) 1989-12-08 1995-11-15 財団法人産業創造研究所 Nitrogen oxide removal method in the combustion exhaust gas
US5260240A (en) 1989-12-29 1993-11-09 Chevron Research And Technology Company Process for the demetallization of FCC catalyst
US5350501A (en) * 1990-05-22 1994-09-27 Union Oil Company Of California Hydrocracking catalyst and process
CA2044893C (en) 1990-06-20 1998-11-03 Senshi Kasahara Transition metal-containing zeolite having high hydrothermal stability, production method thereof and method of using same
US5236877A (en) * 1990-12-04 1993-08-17 W. R. Grace & Co.-Conn. Dual zeolite fluid cracking catalyst composition for improved gasoline octane
US5173278A (en) 1991-03-15 1992-12-22 Mobil Oil Corporation Denitrification of flue gas from catalytic cracking
US5260043A (en) 1991-08-01 1993-11-09 Air Products And Chemicals, Inc. Catalytic reduction of NOx and carbon monoxide using methane in the presence of oxygen
JP3086015B2 (en) 1991-08-07 2000-09-11 トヨタ自動車株式会社 Exhaust gas purifying catalyst
US5174980A (en) 1991-10-04 1992-12-29 Mobil Oil Corp. Synthesis of crystalline ZSM-35
US5171553A (en) 1991-11-08 1992-12-15 Air Products And Chemicals, Inc. Catalytic decomposition of N2 O
US5547648A (en) 1992-04-15 1996-08-20 Mobil Oil Corporation Removing SOx, NOX and CO from flue gases
US5268089A (en) 1992-06-24 1993-12-07 Mobil Oil Corporation FCC of nitrogen containing hydrocarbons and catalyst regeneration
US5316661A (en) 1992-07-08 1994-05-31 Mobil Oil Corporation Processes for converting feedstock organic compounds
US5364517A (en) 1993-02-19 1994-11-15 Chevron Research And Technology Company Perovskite-spinel FCC NOx reduction additive
US5372706A (en) 1993-03-01 1994-12-13 Mobil Oil Corporation FCC regeneration process with low NOx CO boiler
US5407652A (en) 1993-08-27 1995-04-18 Engelhard Corporation Method for decomposing N20 utilizing catalysts comprising calcined anionic clay minerals
DE69519243D1 (en) 1994-02-15 2000-12-07 Tokyo Gas Co Ltd The method and catalyst for purification of exhaust gases containing NOx
US6538169B1 (en) * 2000-11-13 2003-03-25 Uop Llc FCC process with improved yield of light olefins
US6858556B2 (en) * 2002-02-25 2005-02-22 Indian Oil Corporation Limited Stabilized dual zeolite single particle catalyst composition and a process thereof
US6660683B1 (en) * 2002-10-21 2003-12-09 W.R. Grace & Co.-Conn. NOx reduction compositions for use in FCC processes
US20050100494A1 (en) * 2003-11-06 2005-05-12 George Yaluris Ferrierite compositions for reducing NOx emissions during fluid catalytic cracking
US7304011B2 (en) * 2004-04-15 2007-12-04 W.R. Grace & Co. -Conn. Compositions and processes for reducing NOx emissions during fluid catalytic cracking

Patent Citations (99)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634140A (en) * 1968-09-20 1972-01-11 Asea Ab Fuel cell device utilizing air as oxidant
US3894940A (en) * 1973-11-15 1975-07-15 Grace W R & Co Hydrocarbon cracking catalysts with promoter mixtures
US4199435A (en) * 1978-12-04 1980-04-22 Chevron Research Company NOx Control in cracking catalyst regeneration
US4521298A (en) * 1980-07-18 1985-06-04 Mobil Oil Corporation Promotion of cracking catalyst octane yield performance
US4758418A (en) * 1980-07-29 1988-07-19 Union Carbide Corporation Process for combusting solid sulfur-containing material
US4495304A (en) * 1980-07-29 1985-01-22 Atlantic Richfield Company Catalyst for conversion of hydrocarbons
US4495305A (en) * 1980-07-29 1985-01-22 Atlantic Richfield Company Catalyst for conversion of hydrocarbons
US4642178A (en) * 1980-07-29 1987-02-10 Katalistiks, Inc. Process for conversion of hydrocarbons
US4434147A (en) * 1981-10-05 1984-02-28 Chevron Research Company Simultaneous sulfur oxide and nitrogen oxide control in FCC units using cracking catalyst fines with ammonia injection
US4522937A (en) * 1982-11-29 1985-06-11 Atlantic Richfield Company Preparative process for alkaline earth metal, aluminum-containing spinels
US4428827A (en) * 1983-01-24 1984-01-31 Uop Inc. FCC Sulfur oxide acceptor
US4513091A (en) * 1983-02-14 1985-04-23 Mobil Oil Corporation Hydrothermal zeolite activation
US4818509A (en) * 1984-03-23 1989-04-04 Mobil Oil Corporation Continuous process for manufacturing crystalline zeolites in continuously stirred backmixed crystallizers
US4582815A (en) * 1984-07-06 1986-04-15 Mobil Oil Corporation Extrusion of silica-rich solids
US4654316A (en) * 1984-08-09 1987-03-31 The British Petroleum Company P.L.C. Selective dealumination of zeolites
US5011272A (en) * 1984-12-21 1991-04-30 Canon Kabushiki Kaisha Compact zoom lens
US4735927A (en) * 1985-10-22 1988-04-05 Norton Company Catalyst for the reduction of oxides of nitrogen
US4898846A (en) * 1986-03-21 1990-02-06 W. R. Grace & Co.-Conn. Cracking catalysts with octane enhancement
US5102530A (en) * 1986-03-21 1992-04-07 W. R. Grace & Co.-Conn. Cracking catalysts with octane enhancement
US4747935A (en) * 1986-03-26 1988-05-31 Union Oil Company Of California Process for the catalytic cracking of feedstocks containing nitrogen
US4728635A (en) * 1986-04-07 1988-03-01 Katalistiks International Inc. Alkaline earth metal spinels and processes for making
US4798813A (en) * 1986-07-04 1989-01-17 Babcock-Hitachi Kabushiki Kaisha Catalyst for removing nitrogen oxide and process for producing the catalyst
US4855115A (en) * 1986-07-29 1989-08-08 Mitsubishi Petrochemical Co. Ltd. Process for removing nitrogen oxides from exhaust gases
US4797266A (en) * 1986-08-07 1989-01-10 Shell Oil Company Method of preparation of a combined ZSM-5-ferrierite aluminosilicate
US4853203A (en) * 1986-11-21 1989-08-01 Institut Francais Du Petrole Ferrierites; their process of manufacture
US4952382A (en) * 1987-01-13 1990-08-28 Akzo N.V. Process for removing sulfur oxides with an absorbent which contain an anionic clay
US4946581A (en) * 1987-01-13 1990-08-07 Akzo N.V. Cracking process employing a catalyst composition and absorbent which contain an anionic clay
US4904627A (en) * 1987-03-13 1990-02-27 Uop Alkaline earth metal spinel/kaolin clays and processes for making
US4830840A (en) * 1987-03-13 1989-05-16 Uop Process for removing sulfur oxide and nitrogen oxide
US4810369A (en) * 1987-05-07 1989-03-07 Union Oil Company Of California Process for the catalytic cracking of feedstocks containing high levels of nitrogen
US4812431A (en) * 1987-08-12 1989-03-14 Mobil Oil Corporation NOx control in fluidized bed combustion
US4812430A (en) * 1987-08-12 1989-03-14 Mobil Oil Corporation NOx control during multistage combustion
US4898662A (en) * 1987-12-09 1990-02-06 Mobil Oil Corp. Catalytic cracking process using high equilibrium activity additive catalyst
US4826799A (en) * 1988-04-14 1989-05-02 W. R. Grace & Co.-Conn. Shaped catalyst and process for making it
US4895994A (en) * 1988-04-14 1990-01-23 W. R. Grace & Co.-Conn. Shaped catalysts and processes
US5017538A (en) * 1988-04-18 1991-05-21 Toyota Jidosha Kabushiki Kaisha Catalyst for purifying exhaust gas and a method of producing the same
US5433933A (en) * 1989-12-21 1995-07-18 Toyota Jidosha Kabushiki Kaisha Method of purifying oxygen-excess exhaust gas
US5002654A (en) * 1989-12-28 1991-03-26 Mobil Oil Corporation Reducing NOx emissions with zinc catalyst
US4988432A (en) * 1989-12-28 1991-01-29 Mobil Oil Corporation Reducing NOx emissions with antimony additive
US5002653A (en) * 1989-12-29 1991-03-26 Chevron Research Company Catalytic cracking process with vanadium passivation and improved
US4988654A (en) * 1989-12-29 1991-01-29 Chevron Research Company Dual component cracking catalyst with vanadium passivation and improved sulfur tolerance
US5114898A (en) * 1990-01-18 1992-05-19 Board Of Trustees Operating Michigan State University Layered double hydroxide sorbents for the removal of SOx from flue gas and other gas streams
US5114691A (en) * 1990-01-18 1992-05-19 Board Of Trustees Operating Michigan State University Process using sorbents for the removal of SOx from flue gas
US5037538A (en) * 1990-02-26 1991-08-06 Mobil Oil Corporation Catalytic cracking process with isolated catalyst for conversion of NO.sub.x
US5206196A (en) * 1990-12-18 1993-04-27 Tosoh Corporation Catalyst for purifying exhaust gas
US5208198A (en) * 1990-12-18 1993-05-04 Tosoh Corporation Catalyst for purifying exhaust gas
US5130012A (en) * 1991-01-24 1992-07-14 Mobil Oil Corporation Process and apparatus for reducing NOx emissions from high-efficiency FFC regenerators
US5614453A (en) * 1991-09-11 1997-03-25 Uop Catalyst containing zeolite beta and a pillared clay
US5190736A (en) * 1991-10-18 1993-03-02 Mobil Oil Corporation Synthesis of crystalline ZSM-35
US5286693A (en) * 1991-11-06 1994-02-15 Nippon Oil Co., Ltd. Method of producing catalyst for converting hydrocarbons
US5320822A (en) * 1991-11-20 1994-06-14 The Dow Chemical Company Process of growing crystalline microporous solids in a fluoride-containing, substantially non-aqueous growth medium
US5785947A (en) * 1991-12-18 1998-07-28 Chevron U.S.A. Inc. Preparation of zeolites using organic template and amine
US5413977A (en) * 1992-02-27 1995-05-09 Union Oil Company Of California Catalyst containing zeolite beta and a layered magnesium silicate
US5240690A (en) * 1992-04-24 1993-08-31 Shell Oil Company Method of removing NH3 and HCN from and FCC regenerator off gas
US5422333A (en) * 1992-08-25 1995-06-06 Idemitsu Kosan Company Limited Exhaust gas purifying catalyst
US5382352A (en) * 1992-10-20 1995-01-17 Mobil Oil Corporation Conversion of NOx in FCC bubbling bed regenerator
US5294332A (en) * 1992-11-23 1994-03-15 Amoco Corporation FCC catalyst and process
US5427989A (en) * 1993-03-11 1995-06-27 Nissan Motor Co., Ltd. Catalysts for the purification of exhaust gas
US5413699A (en) * 1993-10-14 1995-05-09 Mobil Oil Corporation FCC process with fines tolerant SCR reactor
US5503818A (en) * 1993-11-01 1996-04-02 Csir Aluminosilicate catalyst, a process for the manufacture thereof and a process for the skeletal isomerization of linear olefins
US5510306A (en) * 1993-12-29 1996-04-23 Shell Oil Company Process for isomerizing linear olefins to isoolefins
US5627125A (en) * 1994-07-01 1997-05-06 Monsanto Company Process for preparing carboxylic acid salts and methods for making such catalysts and catalysts useful in such process
US5908804A (en) * 1994-09-30 1999-06-01 The Boc Group, Inc. Reduction of emissions from FCC regenerators
US5599520A (en) * 1994-11-03 1997-02-04 Garces; Juan M. Synthesis of crystalline porous solids in ammonia
US5879645A (en) * 1994-11-03 1999-03-09 Korea Research Institute Of Chemical Technology Method for removing nitrogen oxides in exhaust gas by selective catalytic reduction and catalyst for reduction of nitrogen oxides
US20010002426A1 (en) * 1994-11-23 2001-05-31 Mohr Gary David Hydrocarbon conversion process using a zeolite bound zeolite catalyst
US5741468A (en) * 1994-12-28 1998-04-21 Kabushiki Kaisha Riken Exhaust gas cleaner and method for cleaning exhaust gas
US6379536B1 (en) * 1995-05-05 2002-04-30 W. R. Grace & Co.-Conn. NOx reduction compositions for use in FCC processes
US6358881B1 (en) * 1995-05-05 2002-03-19 W. R. Grace & Co.-Conn. Reduced NOx combustion promoter for use in FCC processes
US5908806A (en) * 1995-06-07 1999-06-01 Asec Manufacturing Copper-silver zeolite catalysts
US5705053A (en) * 1995-08-30 1998-01-06 Mobil Oil Corporation FCC regenerator NOx reduction by homogeneous and catalytic conversion
US5716514A (en) * 1995-08-30 1998-02-10 Mobil Oil Corporation FCC NOx reduction by turbulent/laminar thermal conversion
US5744686A (en) * 1995-09-20 1998-04-28 Uop Process for the removal of nitrogen compounds from an aromatic hydrocarbon stream
US6017508A (en) * 1995-10-24 2000-01-25 The Dow Chemical Company Process of modifying the porosity of aluminosilicates and silicas, and mesoporous compositions derived therefrom
US6033641A (en) * 1996-04-18 2000-03-07 University Of Pittsburgh Of The Comonwealth System Of Higher Education Catalyst for purifying the exhaust gas from the combustion in an engine or gas turbines and method of making and using the same
US6040259A (en) * 1996-05-29 2000-03-21 Exxon Chemical Patents Inc. Metal-containing zeolite catalyst, preparation thereof and use for hydrocarbon conversion
US20020082159A1 (en) * 1997-06-06 2002-06-27 Basf Aktiengesellschaft Method for regenerating a zeolitic catalyst
US6380119B1 (en) * 1997-06-06 2002-04-30 Basf Aktiengesellschaft Method for regenerating a zeolitic catalyst
US6090271A (en) * 1997-06-10 2000-07-18 Exxon Chemical Patents Inc. Enhanced olefin yields in a catalytic process with diolefins
US20020082460A1 (en) * 1997-12-03 2002-06-27 Johannes P. Verduijn Coated zeolite catalysts and use for hydrocarbon conversion
US6214211B1 (en) * 1998-04-21 2001-04-10 Idemitsu Kosan Co., Ltd Catalytic cracking catalyst
US6190538B1 (en) * 1998-08-03 2001-02-20 Shell Oil Company Process for the preparation of a catalyst composition
US20020049132A1 (en) * 1998-11-03 2002-04-25 Deng-Yang Jan Process for preparing attrition resistant zeolitic layered catalyst composition
US6528031B1 (en) * 1998-12-31 2003-03-04 Korea Research Institute Of Chemical Technology Method for preparing noble metal-supported zeolite catalyst for catalytic reduction of nitrogen oxide
US6395403B2 (en) * 1999-05-06 2002-05-28 W. R. Grace & Co. Conn Promoted porous catalyst
US20020037808A1 (en) * 1999-07-31 2002-03-28 Degussa-Huels Aktiengesellschaft Fixed bed catalysts
US6413898B1 (en) * 1999-12-28 2002-07-02 Corning Incorporated Zeolite/alumina catalyst support compositions and method of making the same
US20020094932A1 (en) * 1999-12-29 2002-07-18 Faber Margaret K. Zeolite/Alumina catalyst support compositions and method of making the same
US20020038051A1 (en) * 2000-02-18 2002-03-28 Degussa-Huls Ag Raney copper
US6376708B1 (en) * 2000-04-11 2002-04-23 Monsanto Technology Llc Process and catalyst for dehydrogenating primary alcohols to make carboxylic acid salts
US20020013228A1 (en) * 2000-06-20 2002-01-31 Takeshi Matsumoto Exhaust gas purifying catalyst and method for purifying exhaust gas
US20020022573A1 (en) * 2000-06-22 2002-02-21 Hiroshi Tanada Exhaust gas purifying catalyst
US20020016259A1 (en) * 2000-06-28 2002-02-07 Tatsuya Yoshikawa Exhaust gas purifying catalyst
US20020022574A1 (en) * 2000-07-17 2002-02-21 Hiroshi Tanada Exhaust gas purifying catalyst
US20020094314A1 (en) * 2000-11-27 2002-07-18 National Institute Of Advanced Industrial Science And Technology Method for the reduction and removal of nitrogen oxides
US20030019794A1 (en) * 2001-04-13 2003-01-30 Schmidt Stephen Raymond Process for sulfur removal from hydrocarbon liquids
US6558533B2 (en) * 2001-04-13 2003-05-06 W.R. Grace & Co.-Conn Process for sulfur removal from hydrocarbon liquids
US20030040425A1 (en) * 2001-08-21 2003-02-27 Sud-Chemie Prototech Inc. Method for washcoating a catalytic material onto a monolithic structure
US20030073566A1 (en) * 2001-10-11 2003-04-17 Marshall Christopher L. Novel catalyst for selective NOx reduction using hydrocarbons

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080213150A1 (en) * 2005-03-24 2008-09-04 George Yaluris Method for Controlling Nox Emissions in the Fccu
US7780935B2 (en) 2005-03-24 2010-08-24 W. R. Grace & Co.-Conn. Method for controlling NOx emissions in the FCCU
US20090057199A1 (en) * 2005-04-27 2009-03-05 Michael Scott Ziebarth Compositions and Processes for Reducing NOx Emissions During Fluid Catalytic Cracking
US7918991B2 (en) 2005-04-27 2011-04-05 W. R. Grace & Co.-Conn. Compositions and processes for reducing NOx emissions during fluid catalytic cracking
US7976697B2 (en) 2005-04-29 2011-07-12 W. R. Grace & Co.-Conn. NOX reduction compositions for use in partial burn FCC processes
US9861966B2 (en) 2006-03-22 2018-01-09 Cosmo Oil Co., Ltd. Catalytic cracking catalyst, process for producing the same, and method of catalytic cracking of hydrocarbon oil
US20070286782A1 (en) * 2006-06-08 2007-12-13 Chevron U.S.A. Inc. Reduction of oxides of nitrogen in a gas stream using molecular sieve ssz-75
EP2739374A1 (en) * 2011-08-05 2014-06-11 Chevron U.S.A., Inc. Reduction of oxides of nitrogen in a gas stream using molecular sieve ssz-23
EP2739374A4 (en) * 2011-08-05 2015-03-25 Chevron Usa Inc Reduction of oxides of nitrogen in a gas stream using molecular sieve ssz-23
WO2018189616A1 (en) * 2017-04-10 2018-10-18 Reliance Industries Limited An fcc catalyst additive and a process for preparation thereof

Also Published As

Publication number Publication date
RU2408655C2 (en) 2011-01-10
IL178309A (en) 2011-07-31
WO2005099898A1 (en) 2005-10-27
RU2006140261A (en) 2008-05-27
JP2007532764A (en) 2007-11-15
BRPI0509938B1 (en) 2016-03-08
AU2005233199B2 (en) 2011-06-09
JP4974883B2 (en) 2012-07-11
US20090068079A1 (en) 2009-03-12
MXPA06011795A (en) 2007-01-16
KR101180175B1 (en) 2012-09-05
BRPI0509938A (en) 2007-09-25
NO20065266A (en) 2007-01-15
IL178309D0 (en) 2007-02-11
US7641787B2 (en) 2010-01-05
SG152232A1 (en) 2009-05-29
CA2563499A1 (en) 2005-10-27
AR050581A1 (en) 2006-11-08
EP1747062A1 (en) 2007-01-31
AU2005233199A1 (en) 2005-10-27
KR20070004842A (en) 2007-01-09
CA2563499C (en) 2014-05-27

Similar Documents

Publication Publication Date Title
AU2004304919C1 (en) Mixed metal oxide sorbents
ES2246250T3 (en) Gasoline desulfurization in the fluid bed catalytic cracking.
KR100998819B1 (en) NOx Reduction Composition for Use in FCC Processes
JP5492378B2 (en) Additives for metal contaminants removed
US4423019A (en) Process for removing sulfur oxides from a gas
KR101250698B1 (en) Catalyst for light olefins and lpg in fluidized catalytic units
US5456821A (en) Catalytic conversion with improved catalyst
US6852214B1 (en) Gasoline sulfur reduction in fluid catalytic cracking
EP0609971A1 (en) Sulfur reduction in FCC gasoline
US4369108A (en) Process for removing sulfur oxides from a gas
US7485595B2 (en) Molecular sieve-containing catalyst for cracking hydrocarbons and a method for preparing the same
US4836993A (en) Process for removing sulfur oxides from a gas
US4369130A (en) Composition for removing sulfur oxides from a gas
US4290878A (en) NOx control in platinum-promoted complete combustion cracking catalyst regeneration
US4466884A (en) Process for cracking high metals content feedstocks using a cracking catalyst mixture containing antimony and/or tin
US4199435A (en) NOx Control in cracking catalyst regeneration
NL1013966C2 (en) Reducing sulfur in gasoline at geflu&#39;diseerd catalytic cracking.
US5037538A (en) Catalytic cracking process with isolated catalyst for conversion of NO.sub.x
US4151121A (en) Hydrocarbon conversion catalyst containing a co-oxidation promoter
US5002653A (en) Catalytic cracking process with vanadium passivation and improved
CA2561971C (en) Catalyst compositions comprising metal phosphate bound zeolite and methods of using same to catalytically crack hydrocarbons
CA2392923C (en) A catalytic cracking process using a modified mesoporous aluminophosphate material
AU773403B2 (en) High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith
JP2609502B2 (en) Metal passivators / SOx control composition for FCC
US4405443A (en) Process for removing sulfur oxides from a gas