WO2018201046A1 - Catalyseur de craquage catalytique fluide à faible teneur en coke et à haut rendement en essence et à haute activité - Google Patents

Catalyseur de craquage catalytique fluide à faible teneur en coke et à haut rendement en essence et à haute activité Download PDF

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WO2018201046A1
WO2018201046A1 PCT/US2018/029950 US2018029950W WO2018201046A1 WO 2018201046 A1 WO2018201046 A1 WO 2018201046A1 US 2018029950 W US2018029950 W US 2018029950W WO 2018201046 A1 WO2018201046 A1 WO 2018201046A1
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zeolite
catalyst
contacting
zeolitic
fcc
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PCT/US2018/029950
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English (en)
Inventor
Junmei Wei
Karl Kharas
Christopher Gilbert
Lucas DORAZIO
Xingtao Gao
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Basf Corporation
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    • 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
    • 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
    • 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
    • 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
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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

Definitions

  • the present technology is generally related to petroleum refining catalysts. More specifically, the technology is related to microspherical fluid catalytic cracking (FCC) catalysts including zeolite, and methods of preparing and using such catalysts.
  • FCC microspherical fluid catalytic cracking
  • Catalytic cracking is a petroleum refining process that is applied commercially on a very large scale.
  • Catalytic cracking, and particularly fluid catalytic cracking (FCC) is routinely used to convert heavy hydrocarbon feedstocks to lighter products, such as gasoline and distillate range fractions.
  • FCC processes a hydrocarbon feedstock is injected into the riser section of a FCC unit, where the feedstock is cracked into lighter, more valuable products upon contacting hot catalyst circulated to the riser-reactor from a catalyst regenerator.
  • Such catalysts have taken the form of small particles, called microspheres, containing both an active zeolite component and a non- zeolite component in the form of a high alumina, silica-alumina (aluminosilicate) matrix.
  • the active zeolitic component is incorporated into the microspheres of the catalyst by one of general techniques known in the art, such as those in U.S. Patent No. 4,482,530, or U.S. Pat. No. 4,493,902 incorporated herein by reference in its entirety.
  • Another technique is in situ technique, microspheres are first formed and then zeolite component is then crystallized in the microspheres themselves to provide microspheres containing both zeolitic and non-zeolitic components.
  • the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst, the method including: contacting a zeolitic microsphere material in a crystallization liquor for a time period of from about 6 to about 50 hours. In some embodiments, the contacting is carried out at a temperature of about 180 °F to about 240 °F. In some embodiments, the contacting is carried out with agitation of the crystallization liquor. In further embodiments, the catalyst is isolated. In yet further embodiments, the catalyst is washed with a suitable solvent, such as water.
  • a suitable solvent such as water.
  • the FCC catalyst may be further calcined.
  • the present technology provides a method of treating an FCC catalyst, wherein the zeolitic microsphere material is prepared by a process including: preforming a precursor microsphere comprising a non-zeolitic material and alumina; and in situ crystallizing a zeolite on the pre-formed microsphere to provide the zeolitic microsphere material.
  • the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst including, contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the Y zeolite exhibits less than 0.35% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.
  • FCC fluid catalytic cracking
  • the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst including contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolitic component comprises no more than about 5% zeolite P or zeolite ANA, no more than about 3 % zeolite P or zeolite ANA, no more than about 2% zeolite P or zeolite ANA, or no more than about 1% zeolite P or zeolite ANA.
  • the contacting occurs for a time period such that the Y-zeolite comprises no more than about 4% zeolite P or zeolite ANA.
  • the contacting occurs for a time period such that the Y-zeolite comprises no detectable zeolite P or zeolite ANA.
  • the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst including contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolitic component comprises no more than about 5% zeolite P.
  • the contacting occurs for a time period such that the Y-zeolite comprises no more than about 4% zeolite P, no more than about 3 % zeolite P, no more than about 2% zeolite P, or no more than about 1% zeolite P.
  • the contacting occurs for a time period such that the Y-zeolite comprises no detectable zeolite P.
  • the present technology provides a method of treating a fluid catalytic cracking (FCC) catalyst including contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolite exhibits an increase in stability of at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, or at least about 10%.
  • FCC fluid catalytic cracking
  • the process provides for further calcining the zeolitic microsphere material.
  • the present technology is a microspherical FCC catalyst as prepared by the described process.
  • the present technology is a microspherical FCC catalyst, wherein the Y zeolite on the surface of the zeolitic microsphere material exhibits less than about 0.35% strain, less than about 0.34% strain, less than about 0.33% strain, less than about 0.32%) strain, less than about 0.31% strain, or less than about 0.30%> strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data and wherein the catalyst provides at least 10%> lower coke at 92.5% bottoms conversion.
  • the catalyst has a phase composition comprising at least about 30 wt.%) Y-zeolite. In further embodiments, the catalyst has a phase composition comprising at least about 40%, at least about 50%, or at least about 60% Y-zeolite. In additional and alternative embodiments, the phase composition further comprises at least about 30 wt.%) amorphous material.
  • the Y-zeolite is crystallized as a layer on the surface of a porous alumina-containing matrix.
  • the matrix is derived from a kaolin calcined through the exotherm.
  • zeolitic microsphere material that exhibits a mesoporosity that is about 10%> greater than the mesoporosity of a catalyst wherein the zeolitic microspheric material has not been contacted with the crystallization liquor.
  • a zeolitic microsphere material wherein the Y zeolite on the surface of the zeolitic microsphere material exhibits less than about 0.35%) strain, less than about 0.34%> strain, less than about 0.33%> strain, less than about 0.32%) strain, less than about 0.31% strain, or less than about 0.30%> strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.
  • an FCC catalyst wherein the catalyst provides at least 10%> lower coke at 92.5% bottoms conversion.
  • FIG. 1 provides scanning electron microscope images of control, 12 hour, and 24 hour treated samples at the NaY form.
  • FIG. 2 A and 2B are scanning electron microscope images of NaY samples treated for 48 hours.
  • FIG. 3 is a chart of the zeolite surface area of catalyst at the NaY form, after first calcination, after second calcination, or after steaming, each in comparison with the 24 hour contacting or the 48 hour contacting.
  • FIG. 4a and FIG. 4b illustrates gasoline yield and heavy cycle oil yield, respectively, of catalysts as prepared by 12 hour and 24 hour treating method, in comparison with a control sample.
  • FIG. 5 illustrates the heavy cycle oil yield of catalysts as prepared by 12 hour and 24 hour treating method, in comparison with a control sample.
  • the method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material in a crystallization liquor for a time period of from about 6 to about 50 hours. In some embodiments, the time period of contacting may be about 8 to about 36 hours, or about 10, about 12, or about 24 hours. In some embodiments, the method may include contacting in the crystallization liquor at a temperature of about 180 °F to about 240 °F. In some embodiments, the temperature of the crystallization liquor is about 180 °F, about 190 °F, about 200 °F, about 210 °F, about 212 °F, about 220 °F, about 230 °F, or about 240 °F.
  • the microspheres prior to contacting, include zeolite crystallized as a layer on the surface of a porous alumina-containing matrix. In some embodiments, the contacting is carried out after an about 12 to 16 hour crystallization period.
  • the zeolitic microspheric material is prepared by mixing together microspheres, seeding zeolite crystals, sodium silicate, and caustic (NaOH), and water, and stirring the resultant slurry at a temperature of about 210 °F, followed by a 4-6 hours induction period, during which a small amount of zeolite Y is detected.
  • the contacting is carried out after the zeolite is crystallized to greater than 90%, greater than about 95%, or greater than about 98%, or about 100% of the theoretical yield.
  • the contacting is conducted at a temperature at a temperature of about 200 °F to about 220 °F. In some embodiments, the contacting is conducted at about 210 °F. In some embodiments, the contacting is conducted for about 12 to about 24 hours. In specific embodiments, the contacting is stopped by isolation of the FCC catalyst after about 24 hours.
  • the method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the Y zeolite exhibits less than about 0.35% strain, less than about 0.34% strain, less than about 0.33% strain, less than about 0.32%) strain, less than about 0.31% strain, or less than about 0.30%> strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.
  • the Y zeolite prior to the contacting, the Y zeolite exhibits greater than 0.35%> strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.
  • the method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the resulting catalyst provides at least 10%) lower coke at 92.5% bottoms conversion.
  • the method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolitic component comprises no more than about 5% zeolite P or zeolite ANA.
  • the contacting occurs for a time period such that the Y-zeolite comprises no more than about 4% zeolite P or zeolite ANA, no more than about 3 % zeolite P or zeolite ANA, no more than about 2% zeolite P or zeolite ANA, or no more than about 1% zeolite P or zeolite ANA.
  • the contacting occurs for a time period such that the Y-zeolite comprises no detectable zeolite P or zeolite ANA.
  • the method of treating a fluid catalytic cracking (FCC) catalyst may include contacting a zeolitic microsphere material comprising Y-zeolite in a crystallization liquor for a time period such that the zeolite exhibits an increase in stability of at least about 5%, at least about 6%, at least about 7%, at least about 8%, at least about 9%, or at least about 10%.
  • the Y zeolite prior to the contacting, the Y zeolite exhibits a stability of about 35%. In some embodiments, the stability is measured after steaming of the FCC catalyst.
  • the contacting is carried out with agitation of the crystallization liquor.
  • the agitation may be stirring by an impeller.
  • the FCC catalyst may be isolated or separated from the crystallization liquor after contacting.
  • the isolation may be carried out by commonly used methods such as filtration.
  • the FCC catalyst may be washed or contacted with water or other suitable liquid to remove residual crystallization liquor.
  • the method may further include mixing the microspheres with an ammonium solution prior to or subsequent to contacting with the crystallization liquor, wherein the microspheres include Y-zeolite in the sodium form prior to the mixing with the ammonium solution.
  • the mixing with the ammonium solution is conducted at acidic pH conditions.
  • the mixing with the ammonium solution is conducted at pH of about 3 to about 3.5.
  • the mixing with the ammonium solution is conducted at a temperature above room
  • the mixing with the ammonium solution is conducted at a temperature of at least about 80 °C to about 100 °C, including increments therein.
  • the ammonium exchanged microspheric material is further ion exchanged with a rare earth ion solution.
  • the rare earth ion are nitrates of lanthanum, cerium, praseodymium, and neodymium.
  • the microspheres are contacted with solutions of lanthanum nitrate.
  • the ion exchange step or steps are carried out so that the resulting catalyst contains less than about 0.5% by weight Na 2 0, or about 0.2%, by weight Na 2 0. After ion exchange, the microspheres are dried.
  • Rare earth levels in the range of 0.1% to 12%) by weight, specifically 1-5% by weight, and more specifically 2-3% by weight are contemplated.
  • the amount of rare earth added to the catalyst as a rare earth oxide will range from about 1 to 5%, typically 2-3 wt.% rare earth oxide (REO).
  • the method may further include conducted an additional sodium exchange of the microspheres with ammonium. The second or additional sodium exchange may be carried out in the same manner as for the first sodium exchange.
  • the FCC catalyst is further calcined.
  • Calcination conditions are commonly known to those of skill in the art.
  • the calcining may be conducted at a temperature of from about 500 °C to about 750 °C.
  • the microspheres include zeolite. In some embodiments of the method, the microspheres include Y-zeolite crystallized as a layer on the surface of a porous alumina-containing matrix. In further embodiments of the method, prior to or subsequent to the contacting, the microspheres are pre-treated to exchange sodium with ammonium ions.
  • the microspheres including Y-zeolite crystallized as a layer on the surface of a porous alumina-containing matrix undergo mixing in an ammonium solution and a first calcination and a second calcination.
  • microspherical FCC catalysts as prepared by any of the methods disclosed herein.
  • the FCC catalyst has a phase composition including at least 35 wt.% Y-zeolite. In some embodiments, the FCC catalyst has a phase composition including at least 60 wt.% Y-zeolite. In some embodiments, the FCC catalyst has a phase composition including at least 65 wt.% Y-zeolite.
  • the FCC catalyst has a phase composition that may also include an amorphous material.
  • amorphous materials include, but are not limited to, silica-alumina.
  • the amorphous material may be derived from the disintegration of crystalline zeolite.
  • the amorphous material may be derived from the disintegration of crystalline Y-zeolite.
  • the FCC catalyst may have a phase composition further including at least about 40 wt.%) amorphous material.
  • the FCC catalyst has a phase composition that may further include mullite. In some embodiments, the phase composition further includes at least about 20 wt.%> mullite. [0050]
  • the FCC catalyst may have a phase composition including zeolite, mullite, and amorphous material. In some embodiments, the FCC catalyst has a phase composition including zeolite, mullite, and amorphous material.
  • the FCC catalyst may have a phase composition including Y-zeolite, mullite, and amorphous material.
  • the FCC catalyst has a phase composition including Y-zeolite, mullite, and amorphous material.
  • the FCC catalyst average particle size may be from about 60 to about 100 micrometers. In some embodiments, the FCC catalyst has an average particle size of about 60 to about 90 micrometers.
  • the zeolite is incorporated into an amorphous binder.
  • the zeolite is Y-zeolite.
  • Suitable binders include, but are not limited to, silica, silica-alumina, alumina, clay (e.g., kaolin) or other known inorganic binders.
  • a transitional alumina such as ⁇ - ⁇ 1 2 03, ⁇ - ⁇ 1 2 0 3 , ⁇ - ⁇ 1 2 0 3 , ⁇ - ⁇ 1 2 0 3 , ⁇ - ⁇ 1 2 0 3 , ⁇ - ⁇ 1 2 0 3; ⁇ - ⁇ 1 2 0 3 , or any combination thereof, is included in the composition.
  • a slurry containing zeolite and one or more binders is made and spray-dried to yield microspheres whose average particle size is from about 60 to about 100 micrometers.
  • the slurry further contains alumina.
  • the slurry further contains clay.
  • the slurry further contains alumina and clay. Any effective binder may be used; particularly effective binders include, but are not limited to, aluminum chlohydrol sol, silica sol, and aluminum phosphates.
  • the Y-zeolite may be produced into high zeolite content microspheres by the in situ procedure described in U.S. Patent No. 4,493,902 ("the '902 Patent"), the teachings of which are incorporated by reference in their entirety.
  • the '902 Patent discloses FCC catalysts including attrition-resistant, high zeolitic content, catalytically active
  • the microspheres containing the two forms of calcined kaolin could also be immersed in an alkaline sodium silicate solution, which is heated, preferably until the maximum obtainable amount of Y faujasite is crystallized in the microspheres.
  • the microspheres composed of kaolin calcined to undergo an exotherm, and the metakaolin is reacted with a caustic enriched sodium silicate solution in the presence of a crystallization initiator (seeds) to convert silica and alumina in the microspheres into synthetic sodium faujasite (Y-zeolite).
  • seeds synthetic sodium faujasite
  • the microspheres are separated from the sodium silicate mother liquor, ion- exchanged with rare earth, ammonium ions or both to form rare earth or various known stabilized forms of catalysts.
  • the technology of the '902 Patent provides means for achieving a desirable and unique combination of high zeolite content associated with high activity, good selectivity and thermal stability, as well as attrition-resistance.
  • the zeolitic microspheric material is separated from the crystallization liquor after completion of crystallization.
  • the synthetic sodium faujasite of the '902 patent is contacted with the crystallization liquor for further 12 to 40 hours at about 200 °F to about 220 °F even after completion of crystallization for to form the Y-zeolite of the FCC catalyst of the present invention.
  • the Y-zeolite may be produced as zeolite microspheres, generally disclosed in U.S. Patent Nos. 6,656,347 (“the '347 Patent”) and 6,942,784 ("the '784 Patent”), both of which are incorporated by reference herein in their entirety.
  • These zeolite microspheres are macroporous, have sufficient levels of zeolite to be very active and are of a unique morphology to achieve effective conversion of hydrocarbons to cracked gasoline products with improved bottoms cracking under short contact time FCC processing.
  • These zeolite microspheres are produced by novel processing, which is a modification of technology described in the '902 Patent.
  • non-zeolite, alumina-rich matrix of the catalyst was derived from an ultrafine hydrous kaolin source having a particulate size such that 90 wt. % of the hydrous kaolin particles were less than 2 microns, and which was pulverized and calcined through the exotherm, then a macroporous zeolite
  • the FCC catalyst matrix useful to achieve FCC catalyst macroporosity was derived from alumina sources, such as kaolin calcined through the exotherm, that have a specified water pore volume, which distinguished over prior art calcined kaolin used to form the catalyst matrix.
  • the water pore volume was derived from an Incipient Slurry Point (ISP) test, which is described in the patent.
  • microsphere catalysts of '347 and '784 Patents which were formed is unique relative to the in situ microsphere catalysts formed previously.
  • Use of a pulverized, ultrafine hydrous kaolin calcined through the exotherm yields in-situ zeolite microspheres having a macroporous structure in which the macropores of the structure are essentially coated or lined with zeolite subsequent to crystallization.
  • Macroporosity as defined herein means the catalyst has a macropore volume in the pore range of greater than 50 ⁇ , of at least 0.07 cc/gm mercury intrusion, or at least about 0.10 cc/gm mercury intrusion. This catalyst is optimal for FCC processing, including the short contact time processing in which the hydrocarbon feed is contacted with a catalyst for times of about 3 seconds or less.
  • the described catalyst exhibits a mesoporosity that is about 10% greater than the mesoporosity of a catalyst wherein the zeolitic microspheric material has not been contacted with the crystallization liquor.
  • zeolitic catalysts described in the '347 patent and the '784 patent is not restricted to macroporous catalysts having a non-zeolite matrix derived solely from kaolin.
  • any alumina source which has the proper combinations of porosity and reactivity during zeolite synthesis and can generate the desired catalyst macroporosity and morphology can be used.
  • the desired morphology includes a matrix which is well dispersed throughout the catalyst, and the macropore walls of matrix are lined with zeolite and are substantially free of binder coatings.
  • the FCC catalyst includes an alkali metal ion-exchanged zeolite. In some embodiments, the FCC catalyst includes a lanthanum-exchanged zeolite. In some embodiments, the FCC catalyst includes a lanthanum-exchanged zeolite crystallized in situ in a porous kaolin matrix. In some embodiments, the zeolite is crystallized as a layer on the surface of a porous alumina-containing matrix. In further embodiments, the matrix is derived from a kaolin calcined through the exotherm.
  • the FCC catalyst includes an alkali metal ion-exchanged Y-zeolite. In some embodiments, the FCC catalyst includes a lanthanum-exchanged Y- zeolite. In some embodiments, the FCC catalyst includes a lanthanum-exchanged Y- zeolite crystallized in situ in a porous kaolin matrix. In some embodiments, the Y-zeolite is crystallized as a layer on the surface of a porous alumina-containing matrix. In further embodiments, the matrix is derived from a kaolin calcined through the exotherm.
  • the Y-zeolite has a unit cell parameter of less than or equal to 24.70 A.
  • the unit cell size after second calcination is 24.50-24.65A.
  • the unit cell size after steaming is 24.28-24.35A.
  • the Y-zeolite on the surface of the zeolitic microsphere material exhibits after steaming less than about 0.35% strain, less than about 0.34% strain, less than about 0.33% strain, less than about 0.32% strain, less than about 0.31% strain, or less than about 0.30% strain as determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data.
  • Catalysts were evaluated after deactivation and blending with inert microspheres in an Advanced Catalytic Evaluation (ACE) micro-scale fixed fluidized bed (FFB) reactor. Cracking tests were conducted at 1020° F, constant 60 s time on stream (CTOS), and 575 s stripping on standard gas oil (4350) injected at 1.2 g/min for 60 s, where the space velocity was varied by changing the percentage of active catalyst contained in a 9 g charge of active/inert blend. The oil injector height was 2.125" so the bed height had to be maintained constant to prevent systematic bias in the results. This was done by choosing the ratios of active component, a high density inert and low density inert to maintain constant ABD in the blends.
  • ACE Advanced Catalytic Evaluation
  • FFB micro-scale fixed fluidized bed
  • Catalyst performance was also evaluated using a Circulating Riser pilot Unit (CRU).
  • the riser inlet and outlet temperatures were 65 ⁇ C (1185° F) and 531° C (988° F), the catalyst/oil (C/O) ratio was about 6 and the riser superficial velocity about 3.4 ft/s, and the riser residence time was 2.0 seconds.
  • CRU Circulating Riser pilot Unit
  • disclosed herein are methods to produce gasoline in an FCC system, wherein the methods include using an FCC catalyst described herein.
  • methods to improve gasoline yield in an FCC system wherein the methods include using an FCC catalyst described herein.
  • the methods include using an FCC catalyst described herein.
  • the catalyst may provide at least 10% lower coke at 92.5% bottoms conversion.
  • Example 1 Preparation of NaY intermediate.
  • a microsphere was prepared containing 40 parts of hydrous clay, 60 parts of clay calcined beyond 1050°C. To this mixture, 8 parts of sodium silicate (on the basis of the silicate mass) was added.
  • the slurry for spray dried microspheres was formed by mixing two component slurry in a Cowles mixer. The material was spray dried with in-line injection of sodium silicate as described in patent US 6,942,784. The microsphere was calcined at 1500 °F for 2h before crystallization. The microsphere was crystalized for 12-16 hours to form zeolite Y by the conventional procedures. See e.g., U.S. pat. 4,493,902. The crystalized material was separated from crystallization mother liquor by filtration. The crystallized material was dried in an oven at 100°C overnight, then following the procedure described in
  • Seeds 0.001 to 0.004, The growth rates are optimized by altering Si0 2 /Na 2 0 for a 12-16 hour termination time. After the crystallization, the zeolite-containing microspheres or powder are filtered and washed, and then ion exchanged.
  • NaY can be ion exchanged with ammonium nitrate between two and five times (typically twice) at 82 °C (180 °F), rare earth (RE) exchanged at 82° C and pH of 3 for a rare earth loading on the zeolitic component equivalent to 3% Na, followed by first calcination at temperatures between 950° F and 1450 °F (typically 621 °C, 1150 °F; covered with 25% moisture for 2 hours), then ion exchanged with ammonium nitrate three or four more times at 82 °C (180 F), and then normally calcined again, typically at 1150 °F.
  • the pH is kept constant at 3 using nitric acid or ammonium hydroxide during these ion exchanges.
  • Example 2 Preparation of treated samples, Investigation of Zeolite
  • Rietveld refinement Rietveld analysis of the steamed product reveals little change in volume-averaged Y zeolite crystallite size, but shows a decrease in Y zeolite strain. Results of the Rietveld analysis are shown in Table 1. Strain was determined from the LY parameter from a GSAS Rietveld refinement of X-ray diffraction data. For example, the General Structure Analysis System (GSAS) manual provides for calculation of as determined from profile function 2 parameter LY as follows:
  • Table 1 Rietveld refinement and strain calculation of control, 12-hour, and 24- hour contact samples. volume-averaged
  • Table 2 Properties of Control, 12 hour, and 24 hour mother liquor treated samples before and after steaming.
  • HgPV provides the mercury pore volume in cc/g
  • MSA provides the matrix surface area
  • ZSA provides the zeolite surface area
  • SUCS provides the steamed unit cell size in angstroms.
  • the BET method provides a
  • the matrix surface area is calculated using the t- plot method from the BET surface area; zeolite surface area is obtained by difference.
  • FIG. 1 shows scanning electron microscope images of control, 12 hour, and 24 hour treated samples at the NaY form.
  • FIG. 1 shows that the zeolite crystal size after contacting is 2-3 times as bigger as the control. Without being bound by theory, it is believed that the zeolite surface area at NaY stage of treated samples is lower than control because some metastable zeolite may dissolve in mother liquor during hot contacting, then recrystallized to form bigger zeolite crystal.
  • FIG. 3 provides a chart of the zeolite surface area of catalyst at the NaY form in comparison with the 24 hour contacting or the 48 hour contacting. As seen in FIG. 3, the NaY surface area was reduced after 24 and 48h contacting. The 48 hour contacting reduced surface area at NaY by 27%. Without being bound by theory, it is believed that the reduction in zeolite surface area reduction after 48 hour contacting is apparently due to zeolite P formation. Thus, unlike 24 hour contacting, 48 hour contacting did not improve zeolite stability.
  • Example 3 Catalytic Properties in ACETM reactor. Catalysts were evaluated after deactivation and blending with inert microspheres in an Advanced Catalytic
  • the zeolite surface area of treated samples after first calcination is much higher than the control. Without being bound by theory, it is also believed that metastable zeolite in the control may collapse during the first calcination, leaving non-framework alumina in catalyst, which is considered to be coke formation sites. However, in the treated samples, the metastable zeolite dissolves in the crystallization liquor to participate the
  • Example 4 Catalytic Properties in CRU unit. FCC catalysts described above was scaled up and tested in a circulating riser unit (CRU). All samples were prepared in the 25-gal pilot plant reactor and worked up. Samples were also steamed at 1450 °F (about 788 °C) for 24 hours using a fluid-bed steamer. Catalyst performance in the CRU was evaluated on Garyville feed. The riser inlet and outlet temperatures were 651° C (1 185° F) and 531° C (988° F), the catalyst/oil (C/O) ratio was about 6 and the riser superficial velocity about 3.4 ft/s, and the riser residence time was 2.0 seconds.
  • CRU circulating riser unit
  • Results from the CRU tests are shown in Table 3 and FIG. 5.
  • CRU test results indicated that the catalyst performance of 24 hour treated sample is very similar to 12 hour treated. Both 12 hour and 24 hour treated samples demonstrated about 10% lower coke at 92.5 % bottoms conversion and 1% higher absolute bottoms conversion at 5% coke.

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Abstract

L'invention concerne un procédé de traitement d'un catalyseur de craquage catalytique fluide microsphérique. Ce procédé comprend la mise en contact dans une liqueur de cristallisation de zéolite pendant 12 à 24 heures. Le catalyseur de craquage catalytique fluide microsphérique comprend de la zéolite et fournit des propriétés de craquage d'hydrocarbures supérieures par rapport à des catalyseurs non traités ou sans contact.
PCT/US2018/029950 2017-04-28 2018-04-27 Catalyseur de craquage catalytique fluide à faible teneur en coke et à haut rendement en essence et à haute activité WO2018201046A1 (fr)

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WO2021059197A1 (fr) * 2019-09-25 2021-04-01 Basf Corporation Catalyseurs scr de cu-cha ayant une contrainte de réseau spécifique et des caractéristiques de taille de domaine
WO2021222536A1 (fr) * 2020-04-29 2021-11-04 Basf Corporation Cristallisation in situ d'un catalyseur fcc à teneur en zéolithe ultra-faible

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US20040220046A1 (en) * 2000-09-22 2004-11-04 Stockwell David M. Structurally enhanced cracking catalysts
US20040235642A1 (en) * 2003-05-19 2004-11-25 Mingting Xu Enhanced FCC catalysts for gas oil and resid applications
CN102125872A (zh) * 2011-01-17 2011-07-20 湖南聚力催化剂股份有限公司 用FCC废催化剂合成含NaY沸石多孔微球材料的方法
US20150174559A1 (en) * 2013-12-19 2015-06-25 Basf Corporation Phosphorus-Modified FCC Catalysts
CN104888840A (zh) * 2015-01-14 2015-09-09 任丘市华北石油科林环保有限公司 一种高骨架硅铝比原位晶化fcc重油转化助剂的制备方法

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US20040220046A1 (en) * 2000-09-22 2004-11-04 Stockwell David M. Structurally enhanced cracking catalysts
US20040235642A1 (en) * 2003-05-19 2004-11-25 Mingting Xu Enhanced FCC catalysts for gas oil and resid applications
CN102125872A (zh) * 2011-01-17 2011-07-20 湖南聚力催化剂股份有限公司 用FCC废催化剂合成含NaY沸石多孔微球材料的方法
US20150174559A1 (en) * 2013-12-19 2015-06-25 Basf Corporation Phosphorus-Modified FCC Catalysts
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021059197A1 (fr) * 2019-09-25 2021-04-01 Basf Corporation Catalyseurs scr de cu-cha ayant une contrainte de réseau spécifique et des caractéristiques de taille de domaine
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WO2021222536A1 (fr) * 2020-04-29 2021-11-04 Basf Corporation Cristallisation in situ d'un catalyseur fcc à teneur en zéolithe ultra-faible

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