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
  • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
• • 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
  • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
  • B01J29/068—Noble metals
• • 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
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/74—Iron group metals
  • B01J23/745—Iron
• • 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
  • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
  • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
  • B01J29/67—Noble metals
• • 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
  • B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
  • B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
  • B01J29/68—Iron group metals or copper
• • 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
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • 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
  • 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
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
• • 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
  • B01J29/08—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
  • 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

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 their method of use to reduce the content of gas phase reduced nitrogen species in FCC regenerator off gases released from a fluid catalytic cracking unit (FCCU) regenerator operating in a partial or incomplete combustion mode.
• FCC fluid catalytic cracking
• Yet another combustion mode of operating an FCCU which can also be considered as an "incomplete burn” mode, is nominally in full burn with relatively low amounts of excess oxygen and/or inefficient mixing of air with coked catalyst.
• large sections of the regenerator may be under reducing conditions even if the overall regenerator is nominally oxidizing. Under these conditions, reduced nitrogen species and increased amounts of CO may be found in the regenerator off gas along with NO x . These reduced nitrogen species can be converted to NO x in a downstream CO boiler before being emitted into the atmosphere.
• NO x is controlled in the presence of a platinum- promoted CO combustion promoter in a full burn combustion mode regenerator by the addition of iridium or rhodium on the combustion promoter in lesser amounts than the amount of platinum.
• U.S. Patent Nos. 4,980,052 and 4,973,399 disclose copper-loaded zeolite additives useful for reducing emissions of NO x from the regenerator of an FCCU unit operating in full CO-burning mode.
• compositions for reducing gas phase reduced nitrogen species e.g. ammonia, and NO x generated during a partial or incomplete combustion catalytic cracking process.
• the compositions generally comprise (i) an acidic metal oxide containing substantially no zeolite, (ii) an alkali metal, alkaline earth metal and mixtures thereof, (iii) an oxygen storage component and (iv) a noble metal component, preferably rhodium or iridium, and mixtures thereof.
• U.S. Patent 5,021,144 discloses reducing ammonia in an FCCU regenerator operating in a partial burn combustion mode by adding a significant excess (e.g., at least two times) of the amount of a carbon monoxide (CO) combustion or oxidation promoter sufficient to prevent afterburn combustion in the dilute phase of the regenerator.
• a significant excess e.g., at least two times
• CO carbon monoxide
• U.S. Patent 4,755,282 discloses a process for reducing the content of ammonia in a regeneration zone off gas of an FCCU regenerator operating in a partial or incomplete combustion mode.
• the process requires passing a fine sized, i.e. 10 to 40 microns, ammonia decomposition catalyst to either the regeneration zone of an FCCU, or an admixture with the off gas from the regeneration zone of the FCCU, at a predetermined make-up rate such that the residence time of the decomposition catalyst relative to the larger FCC catalyst particles will be short in the dense bed of the regenerator due to rapid elutriation of the fine sized ammonia decomposition catalyst particles.
• the fine sized elutriated decomposition catalyst particles are captured by a third stage cyclone separator and recycled to the regenerator of the FCCU.
• the decomposition catalyst may be a noble group metal dispersed on an inorganic support.
• CO combustion promoters typically comprise an additive comprising 300 to 1000 ppm platinum on alumina, or a much smaller amount of platinum, e.g., amounts which typically achieve from about 0.1 to about 10 ppm in the total cracking catalyst inventory, incorporated directly into all or part of the cracking catalyst.
• combustion promoters can be effectively used to prevent or control afterburn in FCC units, the use of combustion promoters is not desirable in many of the FCC units operated in partial burn or incomplete combustion mode.
• a combustion promoter can consume oxygen to convert CO, oxygen which otherwise would have been used to convert coke to CO, thereby increasing coke left on the regenerated catalyst (CRC).
• CRC regenerated catalyst
• Increased amounts of CRC on the cracking catalyst returned to the riser will decrease the catalyst activity, and may reduce conversion and product yields. Any increase in the conversion of CO will also increase the heat released in the regenerator, a consequence of the larger heat of combustion for the reaction of CO to CO 2 compared to the heat of combustion for the reaction of carbon to CO.
• the essence of the present invention resides in the discovery of particulate compositions which are capable of being circulated throughout an FCCU along with the cracking catalyst inventory to minimize the content of gas phase reduced nitrogen species, e.g. NH 3 and HCN, and NO x present in the off gas of the FCCU regenerator when the FCCU regenerator is operated in a partial or incomplete burn mode.
• gas phase reduced nitrogen species e.g. NH 3 and HCN
• NO x reduction compositions of the invention exhibit low CO combustion activity, i.e., the compositions do not significantly affect CO combustion, simultaneously with high efficiencies for the oxidation of gas phase reduced nitrogen species to N 2 when the compositions are present in a FCCU regenerator operating under partial or incomplete burn mode.
• the zeolite containing compositions of the invention are incorporated as an integral component of an FCC catalyst, preferably, containing a Y-type zeolite active cracking component.
• the present invention also provides a process for reducing the content of gas phase reduced nitrogen species released from the regenerator of an FCCU operated in a partial or incomplete mode of combustion without significantly affecting CO combustion.
• the process comprises contacting the off gas of an FCCU regenerator operated in a partial or incomplete combustion mode under FCC catalytic conditions with an amount of the compositions of the invention effective to oxidize the gas phase reduced nitrogen species to molecular nitrogen.
• the invention also provides a process for reducing NO x emissions from an FCC process operated in a partial or incomplete combustion mode using the compositions of the invention.
• FCCU regenerator operating in partial or incomplete combustion mode during an FCC process.
• Another advantage of this invention is to provide a process for the reduction of the content of NO x in the off gas of an FCCU regenerator operating in a partial or incomplete combustion mode by the reduction of NO x being emitted in the off gas released from the regenerator, prior to passage of the gas to the CO boiler where the NO x remains untreated and is eventually released into the environment.
• Yet another advantage of this invention is to provide improved partial or incomplete combustion FCC processes using the compositions of the invention.
• FIG. 2 is a graphic representation of the effectiveness of Additives D, E, F, G, H and I, as prepared in EXAMPLES 4, 5, 6, 7, 8 and 9 respectively, to reduce NO formation during NH 3 conversion in a Regenerator Test Unit ("RTU").
• RTU Regenerator Test Unit
• the present invention encompasses the discovery that the use of certain zeolite containing additive compositions is very effective to reduce NO x by oxidizing gas phase reduced nitrogen species released from the FCCU regenerator under FCC process conditions to N 2 , so as to prevent the formation of NO x in a downstream CO boiler.
• Compositions of the invention accomplish NO x reduction without a substantial change in hydrocarbon feed conversion or the yield of cracked products.
• the zeolite containing particles are bound with an inorganic binder.
• the novel 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.
• Zeolites useful in the present invention include zeolites having a pore size of less than 7.2 Angstroms, preferably ranging from about 2 to about 7.1 Angstroms, most preferably ranging from about 3.5 to about 6.5 Angstroms with a SiO 2 to Al 2 O 3 molar ratio of less than about 500, preferably less than 250, most preferably less than 100.
• the 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-35, ZSM-57, ZSM-61, ZK-5, NaJ, Nu-87, Cit-1, SSZ-35, SSZ-48, SSZ- 44, SSZ-23, Dachiardite, Merlinoite, Lovdarite, Levyne, Laumontite, Epistilbite, Gmelonite, Gismondine, Cancrinite, Brewsterite, Stilbite, Paulingite, goosecreekite, Natrolite, omega, ferrierite or mixtures thereof.
• the NO x reduction zeolite component is a zeolite selected from the group consisting of ferrierite, beta, MCM-49, mordenite, MCM-56, zeolite Rho, errionite, chabazite, clinoptilolite, MCM-22, Offretite, A, ZSM-12, ZSM-23, omega and mixtures thereof.
• the NO x reduction zeolite component is ferrierite.
• the zeolite component 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 IB, 2A, 3B, 4B, 5B, 6B, 7B, 2B 3 A, 4A, 5 A and the Lanthanide Series of The Periodic Table, nickel, iron cobalt and mixtures thereof.
• the stabilizing metals are selected from the group consisting of Groups IB, 3B, 2A, 2B, 3 A and the Lanthanide Series of the Periodic Table, iron and mixtures thereof.
• the particulate NO x reduction compositions of the invention contain 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 zeolite component based on the total weight of the NO x reduction composition.
• the binder comprises an alumina sol, e.g., aluminum chlorohydrol.
• the amount of binder material present in the particulate 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.
• Particulate NO x reduction 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 ⁇ m.
• the mean particle size is from about 50 to about 200 ⁇ m, most preferably from about 55 to about 150 ⁇ m, 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 50, preferably less than 20, most preferably less than 15.
• the particulate compositions of the invention are prepared by forming an aqueous slurry containing the zeolite, optional zeolite components, the inorganic binder, and optional matrix materials, in an amount sufficient to provide at least 10.0 weight percent of 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 9O 0 C to about 32O 0 C for up to about 24 hours.
• 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 32O 0 C to about 900 0 C from about 0.5 to about 12 hours.
• 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.
• ammonia or ammonium salt e.g., ammonium sulfate, nitrate, chloride, carbonate, phosphate and the like
• an inorganic or organic acid e.g., sulfuric, nitric, phosphoric, hydrochloric, acetic, formic and the like
• particulate NO x reduction compositions useful in the process of the present invention are prepared by impregnating the base zeolite containing material with an aqueous solution of at least one noble metal salt, e.g. nitrate, chloride, carbonate and sulfate salts, amine complexes, and the like, in an amount sufficient to provide at least 0.1 parts per million of noble metal, measured as the metal, in the final catalyst/additive composition and thereafter drying the impregnated particles to remove volatiles, e.g. typically at about 100 0 C to 250 0 C for up to about 24 hours.
• noble metal salt e.g. nitrate, chloride, carbonate and sulfate salts, amine complexes, and the like
• the amount of the NO x reduction composition used ranges from about 0.01 to about 50 weight percent, preferably from about 0.05 to about 30 weight percent, most preferably from about 0.1 to about 20 weight percent of the FCC catalyst inventory.
• the separate particles may be added to the FCCU in any conventional manner, e.g., with make-up catalyst to the regenerator or other convenient method.
• compositions of the invention are integrated into the FCC catalyst particles themselves, any conventional FCC catalyst particle component may be used in combination with the compositions of the invention.
• the NO x reduction composition of the invention typically represents at least about 0.005 wt%, preferably at least about 0.01 wt%, most preferably at least about 0.05 wt%, of the total FCC catalyst composition.
• the amount of the invention compositions used ranges from about 0.005 to about 50 wt%, more preferable from about 0.01 to about 30 weight percent, most preferably from about 0.05 to about 20 wt%, of the total FCC catalyst composition.
• the NO x reducing zeolite component When incorporated as an integral component of the FCC catalyst composition, typically represents at least 0.005 wt% of the total FCC catalyst composition. Preferably, the amount of the NO x reducing zeolite used ranges from about 0.005 to about 50 wt%, most preferably from about 0.05 to about 20 wt%, of the total FCC catalyst composition [0062]
• the integrated FCC catalyst will typically comprise 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 group 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 of the catalyst composition.
• the amount of binder material present in the integrated catalyst composition ranges from about 5 to about 45 weight percent, most preferably from about 10 to about 30 weight percent and even more preferably from about 15 to about 25 weight percent, based on the total weight of the composition.
• the matrix materials optionally present in the integrated catalyst compositions of the present invention include, but are not limited to alumina, silica-alumina, rare earth oxides such as lanthana, transition metal oxides such as titania, zirconia, and manganese oxide, Group HA oxides such as magnesium and barium oxides, clays such as kaolin, and mixtures thereof.
• the matrix or fillers may be present in the integral catalyst in the amount of less than 50 weight percent based on the total weight of the composition.
• the matrix and fillers, if any, are present in an amount ranging from about 1 to about 45 weight present 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 ⁇ 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 noble metal component is at least one metal selected from the group consisting of platinum, palladium iridium, rhodium, osmium, or ruthenium, rhenium, and mixtures thereof.
• the noble metal component is selected from the group consisting of iridium, rhodium, osmium, ruthenium, rhenium and mixtures thereof.
• the noble metal component is rhodium, iridium and mixtures thereof.
• the amount of the noble metal component useful in the present invention, calculated as the metal is at least 0.1 parts per million, preferably at least 0.5 parts per million, most preferably at least 1.0 part per million.
• the amount of the noble metal component ranges from about 0.1 parts per million to about 1.0 wt%, preferably from about 0.5 parts per million to about 5,000 parts per million, most preferably from about 1.0 part per million to about 2,500 parts per million, based on the total weight of the NO x reduction composition.
• the noble metal component may be added as a component of the the NO x reduction composition using any method known in the art, e.g., ion exchange, impregnation and the like.
• the noble metal component may be added to the NO x reducing zeolite prior to incorporation into the NO x reduction composition.
• the noble metal component may be added to particles incorporating the NO x reducing zeolite to form a particulate NO x reduction composition as described herein above, or to integral catalyst particles comprising the NO x reducing composition and components of the FCC cracking catalyst.
• Suitable sources of the noble metal and the optional stabilizing component include aqueous solutions of nitrate, chloride, carbonate and sulfate salts, amine complexes, and the like. The salts or complexes are used in an amount sufficient to provide at least 0.1 parts per million of the noble metal, measured as the metal, in the final composition.
• the catalytic cracking of these relatively high molecular weight hydrocarbon feedstocks result 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;
• 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.
• Typical FCC processes are conducted at reaction temperatures of 48O 0 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, which, when catalytically cracked, provide a gasoline or a gas oil product. Synthetic feeds having boiling points of about 204 0 C to about 816 0 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 phase of the regeneration zone.
• an under-stoichiometric quantity of oxygen is provided to operate the regeneration zone in a partial or incomplete combustion mode.
• compositions in accordance with the invention during the catalyst regeneration step dramatically reduces the emissions of gas phase reduced nitrogen species in the FCCU regenerator effluent.
• gas phase reduced nitrogen species By removing the gas phase reduced nitrogen species from the effluent of the FCCU regenerator, significant reduction of NO x emissions from the CO boiler is achieved. In some cases, NO x reduction up to 90% is readily achievable using the compositions and method of the invention.
• the extent of reduced nitrogen species and 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, the amount of oxygen used 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, the presence of other catalytic additives that may affect the chemistry and operation of the regenerator, and the design and operation of the CO boiler which impacts the conversion of reduced nitrogen species to NO x and the formation of thermal NO x .
• NO x reduction compositions of the invention also prevent a significant increase in the production of coke during the FCC process, e.g., less than 20%, preferably less than 10%, relative to the production of coke absent the NOx reduction composition.
• Additive C was prepared using ferrierite which contained Na and K cations (about 1.02 % Na 2 O and 7.08% K 2 O).
• An aqueous slurry was prepared which contained 41% solids.
• the solids in the slurry consisted of 75% ferrierite (sodium and potassium content not included) and 25% alumina from an aluminum chlorohydrol solution (23% solids).
• the slurry was milled to an average particle size of less than 2.5 ⁇ m and then spray- dried.
• the spray dried product was calcined for about 1 hour at about 425 0 C and then washed with sufficient amount of an aqueous ammonium sulfate solution (30% (NH 4 ⁇ SO 4 ) to reduce the sodium and potassium content.
• the washed product was then flash-dried and stored.
• the final product had the properties shown in Table 2.
• Additive E was prepared by talcing a sample of 80 g of Additive C and impregnating the sample to a target of 200 ppm Ir by incipient wetness using a dilute solution of 0.029 g of pentamine chloro iridium (III) dichloride (49.9% Ir in the salt) and 61 g DI water. The impregnated catalyst was dried at 120 °C overnight and calcined for 2 hours at 649 °C.
• Additive F was prepared by taking a sample of 80 g of Additive C and impregnating the sample to a target of 200 ppm Pt by incipient wetness using a dilute solution of 0.503 g platinum tetramine nitrate solution (2.9% Pt) and 61 g of DI water. The impregnated catalyst was dried at 120 °C overnight and calcined for 2 hours at 649 °C.
• Additive G was prepared by taking a sample of 109 g of Additive C and impregnating the sample to a target of 100 ppm Pd by incipient wetness using 0.118 g of a palladium nitrate solution (8.46% Pd) and 83 g of DI water. The impregnated catalyst was dried at 120 0 C overnight and calcined for 2 hours at 649 °C.
• Additive H was prepared by taking a sample of 109 g of Additive C and impregnating the sample to a target of 100 ppm Ru by incipient wetness using 0.667 g of a ruthenium nitrosyl nitrate solution (1.5% Ru) and 83 g DI water. The impregnated catalyst was dried at 120 0 C overnight and calcined for 2 hours at 649 0 C.
• Additive I was prepared by taking a sample of 109 g of Additive A and impregnating the sample to a target of 100 ppm Rh and 50 ppm Ir by incipient wetness using 0.083 g of rhodium nitrate solution (12.11% Rh), 0.010 g of pentamine chloro iridium (III) dichloride (49.9% Ir in the salt) and 83 g DI water. The impregnated catalyst was dried at 120 0 C overnight and calcined for 2 hours at 649 °C. EXAMPLE 10
• each additive was blended at 0.5 wt% level with a commercially available FCC catalyst (OCTACAT®-DCH, obtained from Grace Davison), which had been deactivated for 4 hours at 816 °C in a fluidized bed reactor with 100% stream.
• OCTACAT®-DCH commercially available FCC catalyst
• the cracking catalyst alone, or the additive/cracking catalyst blend was fed to the RTU reactor operating at 700 0 C.
• the gas feed to the RTU was a mixture of NH 3 and CO containing approximately 500 ppm NH 3 , 5000-5500 ppm CO, and various amounts of O 2 added as 4% O 2 in N 2 , with the balance being nitrogen.
• the total gas feed rate excluding the O 2 containing gas feed was 1000-1100 seem. All additives were effective in converting NH 3 in excess of 99%. As observed in Figure 2, all Additives are also effective in minimizing the conversion of NH 3 to NO. However, Additives D, E and I are the most effective in minimizing conversion of NH 3 to NO. No other nitrogen oxides (e.g., NO 2 or N 2 O) were detected, indicating the conversion to molecular nitrogen of any NH 3 not converted to NO.
• SUPERNOVA® DMR+ obtained from Grace Davison.
• the cracking catalyst was hydro thermally deactivated in a fluidized bed reactor with 100% steam for 4 h at 816 0 C. After stabilization of the unit, the baseline NO emissions data were collected using an online Lear-Siegler SO 2 /NO Analyzer (SM8100A). Subsequently, a blend of 100 g of catalyst was added to the DCR consisting of 95.25 g of the hydrothermally deactivated

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