Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/80—Mixtures of different zeolites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/084—Y-type faujasite
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
  • C10G11/04—Oxides
  • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
  • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
  • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
  • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
  • C10G11/182—Regeneration
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/60—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the type L, as exemplified by patent document US3216789
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/7007—Zeolite Beta
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/19—Catalysts containing parts with different compositions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0027—Powdering
  • B01J37/0045—Drying a slurry, e.g. spray drying
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/405—Limiting CO, NOx or SOx emissions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/80—Additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/20—C2-C4 olefins

Definitions

• the present invention relates to NO x reduction compositions and the method of use thereof to reduce NO x emissions in refinery processes, and specifically in fluid catalytic cracking (FCC) processes. More particularly, the present invention relates to NO x reduction compositions and the method of use thereof to reduce the content of NO x 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.
• FCCU fluid catalytic cracking unit
• catalyst particles are continuously circulated between a catalytic cracking zone and a catalyst regeneration zone.
• 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.
• Patent 5,382,352 or modify the CO combustion promoter used, e.g., U.S. Patents 4,199,435, 4,812,430, and 4,812,431. Enrichment of air with oxygen in a regenerator operating in partial burn mode has also been suggested, e.g., U.S. Patent 5,908,804. [0009] Additives have also been used in attempts to deal with NO x emissions.
• U.S. Patent Nos. 6,379,536, 6,280,607, 6,129,834 and 6,143,167 disclose the use of NO x removal compositions for reducing NO x emissions from the FCCU regenerator.
• 6,165,933 and 6,358,881 also disclose a NO x reduction composition, which promotes CO combustion during the FCC catalyst regeneration process step while simultaneously reducing the level of NO x emitted during the regeneration step.
• NO x 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. Patent Nos. 4,973,399 and 4,980,052 disclose reducing emissions of NO x 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 NO x 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 NO x 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.
• the FCCU may have insufficient air capacity to bum 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.
• a NO x 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 NO x control performance without substantially changing , or affecting the hydrocarbon conversion or the yield of cracked petroleum products produced during the FCC process.
• FCCU fluid catalytic cracking unit
• FCC fluid catalytic cracking
• novel NO x reduction compositions are provided.
• the compositions comprise a particulate composition containing particles of a NO x reduction zeolite component.
• the NO x reduction zeolite particles are bound with an inorganic binder.
• the binder preferably comprises silica, alumina or silica alumina.
• the NO x reduction zeolite is exchanged with hydrogen, ammonium, alkali metal and combinations thereof.
• the preferred alkali metal is sodium, potassium and combinations thereof.
• novel zeolite containing NO x reduction compositions are provided which are added to a circulating inventory of the catalytic cracking catalyst as a separate admixture of particles to reduce NO x emissions released from the FCCU regenerator during the FCC process.
• novel NO x reduction compositions which comprise a NO x reduction zeolite incorporated as an integral component of an FCC catalyst, preferably, containing a Y-type zeolite active cracking component.
• novel NO x reduction compositions are provided which compositions reduce NO x 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.
• 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 NO x 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 Davis ⁇ n, Columbia, MD and deactivated using the Cyclic Propylene Steaming procedure as described in EXAMPLE 6).
• 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 Davis ⁇ n, Columbia, MD and deactivated using the Cyclic Propylene Steaming procedure as described in EXAMPLE 6).
• NO x will be used herein to represent nitric oxide, nitrogen dioxide (the principal noxious oxides of nitrogen) as well as N 2 O 4 , N2O5 and mixtures thereof.
• the present invention encompasses the discovery that the use of certain zeolite containing NO x 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 NO x emissions released from the FCCU regenerator under FCC process conditions without a substantial change in hydrocarbon feed conversion or the yield of cracked products.
• FCC fluid catalytic cracking
• Compositions of the invention typically comprise a particulate composition containing particles of a NO x reduction zeolite component.
• the NO x reduction zeolite particles are bound with an inorganic binder.
• novel NO x reduction compositions may oe a ⁇ e ⁇ 10 e circulating inventory of the catalytic cracking catalyst as a separate particle additive or incorporated as an integral component into the cracking catalyst.
• 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).
• 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.
• 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 NO x reduction composition, except that the NO x 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.
• reduction zeolite component in the present invention include zeolites ha l ving a pore size ranging from about 3 to about 7.2 Angstroms with Si0 2 to Al 2 O 3 molar ratio of less than about 500, preferably less than 250, most preferably less than 100.
• the NO x 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, Pauling ⁇ te, goosecreekite, Natrolite, omega or mixtures thereof.
• 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.
• the NO x reduction zeolite has a surface area of at least 100 ⁇ n 2 /g, preferably at least 200 m 2 /g and most preferably at least 300 m 2 /g.
• the NO x 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.
• 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.
• the NO x 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.
• a stabilizing metal or metal ion
• 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, 3 A, 4A, 5A, and the Lanthanide Series of The Periodic Table, Ag and mixtures thereof.
• the stabilizing metals are selected from the group consisting of Groups 3B, 2A, 2B, 3 A and the Lanthanide Series of the Periodic Table, and mixtures thereof.
• the stabilizing metals are selected from the group consisting of lanthanum, aluminum, magnesium, zinc, and mixtures thereof.
• the metal may be inco ⁇ orated into the pores of the NO x reduction zeolite by any method known in the art, e.g., ion exchange, impregnation or the like.
• the Periodic Table referenced herein above is the Periodic Table as published by the American Chemical Society.
• compositions of « the invention are separate catalyst/additive compositions and comprise a particulate. composition formed by binding particles of a NO ⁇ reduction zeolite component with a suitable inorganic binder.
• the amount of the NO x reduction zeolite component present in the particulate compositions of the invention is at least lO, preferably at least 30, most preferably at least 40 and even more preferably at least 5 O, weight percent based on the total weight of the composition.
• 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 NO x 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.
• 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.
• the binder comprises an alumina sol, e.g., aluminum chlorohydrol.
• 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, yttr ⁇ a, lanthana, ceria, neodymia, samaria, europia, gadolinia, titania, zirconia, praseodymia and mixtures thereof).
• fillers e.g., kaolin clay
• matrix materials e.g., alumina, silica, silica alumina, yttr ⁇ a, lanthana, ceria, neodymia, samaria, europia, gadolinia, titania, zirconia, praseodymia and mixtures thereof.
• the additional materials are used in an amount which does not significantly adversely affect the performance of the compositions to reduce NO x emissions released from the FCCU regener
• 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 NO x 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.
• the composition of the invention will have a mean particle size of greater than 45 ⁇ m.
• the mean particle size is from about 50 to about 200 ⁇ m, most preferably from about 55 to about 150 ⁇ rn, even more preferred from about 60 to about 120 ⁇ m.
• 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.
• DI Davison attrition index
• the particulate NO x reduction compositions of the invention are prepared by forming an aqueous slurry containing the NO x 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 N0 X 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.
• the NO x 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 ⁇ m or less, preferahly 5 ⁇ m or less, most preferably 3 ⁇ m 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.
• the catalyst/additive composition is used in an amount of at least; 0.1 weight percent of the FCC catalyst inventory.
• 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.
• the NO x reduction zeolite is integrated or inco ⁇ orated into the cracking catalyst particles themselves to provide an integral NO x reduction catalyst system.
• the NO x 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.
• the NO x reduction zeolite component, and any optional zeolites, within the cracking catalyst typically are slurried in water.
• the slurry is milled to reduce the mean particle size of solids in the slurry to less than 10 ⁇ m, preferably to less than 5 ⁇ m, most preferably less than 3 ⁇ m.
• 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.
• a water soluble rare-earth salt e.g., rare-earth chlorides, nitrates and the like.
• the NO x reduction zeolite component, optional additional zeolites, the cracking catalyst zeolite, any matrix materials, a rare-e;arth 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.
• 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.
• the NO x reduction zeolite component When integrated into the FCC catalyst particles, the NO x reduction zeolite component typically represents at least 0.1 weight percent of the FCC catalyst particle.
• the amount of the NO x 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 NO * , 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.
• the inorganic binder materials include, but are not limited to, alumina, silica, silica alumina, aluminum phosphate and the like, and mixtures thereof.
• the binder is selected from the gro ⁇ p consisting of alumina, silica, silica alumina.
• the amount of binder material present in the integrated catalyst composition is less than 50 weight percent based on the total weight ot the catalyst composition.
• 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 integra-1 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 ⁇ m,. more preferably from about 50 ⁇ m to about 150 ⁇ m.
• 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.
• the FCC cracking catalyst contains a Y-type zeolite.
• the NO x 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 NO x reduction z eolite be present in that amount sufficient to provide in the total catalyst inventory a ratio of NO x reduction zeolite to Y-type zeolite of less than 2, preferably less than 1.
• the additional zeolite component may be any zeolite which does not adversely affect the NO x reduction performance or cause a substantial change in hydrocarbon conversion or cracked product yields during the FCC process.
• 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 ttiat does not significantly adversely affect the performance of the NO x reduction zeolite compositions to reduce NO x emissions and substantially maintain the hydrocarbon conversion and product yields of the cracking catalyst relative to the use of the cracking catalyst without the NO x reduction catalyst/additive composition. Typically, .
• the additional zeolite component is used in an amount ranging from about 1 to abc»i ⁇ t 80, preferably from about 10 to about 70, weight percent of the catalyst/additrve. composition.
• the additional zeolite component is preferably used in an amount ranginj from about 0.1 to about 60, most preferably from about 1 to about 40, weight percent of the catalyst composition.
• the FCC process involves the cracking of hea"vy 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 ⁇ m, preferably from about 60 to about 120 ⁇ m.
• 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.
• 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.
• the FCC catalyst is a catalyst comprising a Y-type zeolite active cracking component.
• 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.
• 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.
• 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 NO x 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.
• cracked products e.g., gasoline and light olefins
• NO x reduction of 90% or greater is readily achievable using the compositions and method of the invention without significantly affecting the cracked products yields pr fee conversion.
• the extent of NO x 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.
• the effectiveness of the process of the invention may be expected to vary from unit to unit.
• NO x reduction compositions of the invention also prevent a significant increase in the production of coke during the FCC process.
• NO x reduction compositions of the invention may be used alone or in combination with one or more additional NO x reduction component to achieve NO x reduction more efficiently than the use of either of the compositions alone.
• the additional NO x 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 NO x reduction compositions of the invention include noble metal containing NO x reduction compositions such as disclosed and described in U.S.
• 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).
• a noble metal component preferably Pt, Pd, Rh, Ir, Os, Ru, Re and mixtures thereof.
• 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.
• non-zeolitic materials suitable for use in combination with the NO x reduction compositions of the invention include a low NO , CO combustion promoter as disclosed and described in U.S. Patent Nos. 6,165,933 and 6,358,881, the entire disclosure of these patents being herein inco ⁇ orated by reference.
• the low NO 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.
• the NO x 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 CeO 2 ; 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 NO x reduction compositions of the invention include NO x reduction compositions as disclosed and described in U.S. Patent Nos.
• the NO x 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.
• the acidic oxide support contains at least 50 weight percent alumina and preferably contains silica alumina.
• Ceria is the preferred oxygen storage oxide.
• the NO x 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 Ce0 2 ; 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 NO x reduction materials suitable for use in combination with the NO x 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. Patent Nos. 4,963,520, 4,957,892,.
• 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.
• the metal containing spinel comprises magnesium as said first metal and aluminum as said second metal, and the atomic "rat ⁇ o'ormagnesram to-aiumimmrin 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.
• non-zeolitic materials useful in combination with the NO x reduction additives of the invention include, but are not limited to, zinc based catalysts such as disclosed and described in U.S. Patent No. 5,002,654; antimony based NO x reduction additives such as described and disclosed in U.S. Patent No. 4,988,432; perovskite- spinel NO x reduction additives such as described and disclosed in U.S. Patent Nos. 5,364,517 and 5,565,181; hydrotalcite catalyst and additive compositions such as described and disclosed, for example, in U.S. Patent Nos.
• NO x reduction compositions of the invention in combination with NO x removal compositions as disclosed and described in PCT International Publication Number WO 03/046112 Al and PCT International Publication No. W0 2004/033091 Al, the entire disclosures of which are herein inco ⁇ orated by reference.
• NO x 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.
• the additional non-zeolitic NO x reduction compositions are used in an amount sufficient to provide increased NO x reduction when compared to the use of the catalyst/additive compositions alone.
• the additional non-zeolitic compositions are used in an amount up to about 50 weight percent of the FCC catalyst inventory.
• 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 'NO x reduction composition may be blended with the FCC catalyst inventory as a separate particle additive. • Alternatively, the. additional NO x reduction composition may be inco ⁇ orated into the FCC catalyst as an integral component of the catalyst.
• 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.,.'SO x reduction additives, gasoline-sulfur reduction additives, CO combustion promoters, additives for the production of light olefins, and the like.
• additives conventionally used in the FCC process, e.g.,.'SO x reduction additives, gasoline-sulfur reduction additives, CO combustion promoters, additives for the production of light olefins, and the like.
• 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 inco ⁇ orate expressly herein by reference or otherwise, any number falling within such range, including any subset of numbers within any range so recited.
• a composition containing 40% beta and 40% clay bound with 20% silica sol was prepared as follows.
• An aqueous slurry containing 21% beta (Si ⁇ 2tAl2 ⁇ 3 28) was milled in a Drais mill.
• the milled beta slurry (5670g) was combined with 1200g Natka clay (dry basis) and 6000g silica sol binder (10% solids).
• the silica sol binder was prepared from sodium silicate and acid alum.
• the catalyst slurry was then spray dried in a Bowen spray drier.
• the resulting spray dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a a2 ⁇ level of less than 0.1 wt%.
• the properties of the catalyst are shown in
• a composition containing 40% mordenite and 40% clay bound with 20% silica sol was prepared as follows. An aqueous slurry containing 21%
• the milled mordenite slurry (3850 g) was combined with 800g Natka clay (dry basis) and 4000g 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 Na2 ⁇ level of less than 0.1 wt%.
• the properties -of the catalyst are shown in Table 1.
• a composition containing 40% Zeolite L and 40% clay bound with 20% silica sol was prepared as follows.
• An aqueous slurry containing 25% Zeolite L (Si ⁇ 2/Al2 ⁇ 3 6) was milled in a Drais mill.
• the milled Zeolite L slurry (5050g) was combined with 1200g Natka clay (dry basis) and 6000g silica sol binder (10% solids).
• the silica sol binder was prepared from sodium silicate and acid alum.
• the catalyst slurry was then spray dried in a Bowen spray drier.
• the resulting spray dried product was washed with ammonium sulfate solution, followed by water to give a catalyst with a Na2 ⁇ level of less than 0.1 wt%.
• the properties of the catalyst are shown in Table 1.
• a composition containing 40% MCM-56 and 40% clay bound with 20% silica sol was prepared as follows.
• An aqueous slurry containing 21.8% MCM-56 (Si ⁇ 2/Al2 ⁇ 3 19) was milled in a Drais mill. The milled MCM-56 slurr
• 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.
• a commercial FCC feed was used having the properties as shown in Table 3 below.
• 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

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