WO2014098820A1 - Catalyseur d'hydrocraquage mésoporeux de type zéolithe y et procédés d'hydrocraquage associés - Google Patents

Catalyseur d'hydrocraquage mésoporeux de type zéolithe y et procédés d'hydrocraquage associés Download PDF

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WO2014098820A1
WO2014098820A1 PCT/US2012/070502 US2012070502W WO2014098820A1 WO 2014098820 A1 WO2014098820 A1 WO 2014098820A1 US 2012070502 W US2012070502 W US 2012070502W WO 2014098820 A1 WO2014098820 A1 WO 2014098820A1
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Prior art keywords
zeolite
catalyst
group
metal
precursor
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PCT/US2012/070502
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English (en)
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Jianxin Jason Wu
Ajit B. Dandekar
Christopher G. Oliveri
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Exxonmobil Research And Engineering Company
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Priority to PCT/US2012/070502 priority Critical patent/WO2014098820A1/fr
Priority to EP12809073.5A priority patent/EP2934745A1/fr
Priority to SG11201504335RA priority patent/SG11201504335RA/en
Priority to CA2894483A priority patent/CA2894483C/fr
Publication of WO2014098820A1 publication Critical patent/WO2014098820A1/fr

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    • 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
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • 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
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B01J29/126—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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • 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
    • B01J35/617—500-1000 m2/g
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
    • 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
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • B01J2229/22—After treatment, characterised by the effect to be obtained to destroy the molecular sieve structure or part 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
    • 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
    • B01J2229/36—Steaming
    • 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
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • 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

Definitions

  • This invention relates to the composition, method of making and use of a hydrocracking catalyst that is comprised of a new Y zeolite which exhibits an exceptionally low small mesoporous peak height around the 40 A (angstrom) range as determined by nitrogen adsorption measurements and shown in the BJH N 2 Desorption Plot.
  • the hydrocracking catalysts herein which comprise this zeolite exhibit improved distillate yield and selectivity as well as improved conversions at lower temperatures than conventional hydrocracking catalysis containing Y zeolites.
  • the hydrocracking reaction is run at relatively low severity or relatively low hydrocracking conversion, so that the higher boiling point hydrocarbons are not cracked too much, as higher conversions typically generate increasing quantities of material boiling in the ranges below naphtha, which low boilmg material tends not to be as commercially useful as the fuel compositions.
  • running at these lower temperatures (severities) tend to reduce the overall product conversions. While maintaining a better selectivity for distillates, overall conversion, as well as overall distillate production can be significantly decreased.
  • hydrocrackmg catalyst that is comprised of a Y zeolite which exhibits an exceptionally low small mesoporous peak height around the 40 A (angstrom) range as measured by nitrogen adsorption and shown in the BJH 2 Desorption Plot.
  • the present invention includes the composition, method of making and use of hydrocracking catalysts incorporating an extra mesoporous Y zeolite (termed herein as ⁇ " zeolite) which has improved mesoporous properties over Y zeolites of the prior art, as well as a method of making the zeolite and its use in associated hydrocracking process.
  • This zeolite is described herein as well as described further in parent application United States Serial Number 12/584,376 entitled “Extra Mesoporous Y Zeolite", which is incorporated in its entirety herein.
  • a hydrocracking catalyst comprised of:
  • Y zeolite with a Large Mesopore Volume of at least about 0.03 cm Vg and a Small Mesopore Peak of less than about 0.15 cnrVg;
  • the zeolite is a Y zeolite with a Large Mesopore V olume of at least about 0,03 ctrrVg and a Small Mesopore Peak of less than about 0.15 cm g.
  • a hydrocracking process for selectively catalytically cracking a hydrocarbon feedstock to form a distillate product comprising:
  • a hydrocracking catalyst comprised of a Y zeolite with a Large Mesopore Volume of at least about 0.03 cm g and a Small Mesopore Peak of less than about 0.15 cm ' Vg; an inorganic matrix; and at least one active metal selected from Group 6 and Group 8/9/10 metals under hydrocracking conditions; and
  • the zeolite has a Large Mesopore Volume of at least about 0.03 cmVg, and a Small Mesopore Peak of less than about 0.15 cm ' Vg.
  • FIGURE 1 is a BJH N 2 Desorption Plot of a USY zeolite from a commercially available ammonium-Y zeolite (prior art).
  • FIGURE 2 is a BJH N 2 Desorption Plot of the USY zeolite of Figure 1 (prior art) after it has been subjected to ion exchange/calcination steps and long- term deactivation steaming at 1400 °F for 16 hours.
  • FIGURE 3 is a BJH N 2 Desorption Plot of an embodiment of an Extra Mesoporous Y (“EMY”) zeolite as utilized in the catalysts of the present invention.
  • EMY Extra Mesoporous Y
  • FIGURE 4 is a BJH N 2 Desorption Plot of an embodiment of an Extra Mesoporous Y (“EMY”) zeolite after it has been subjected to ion- exchange/calcinatiori steps and long-term deactivation steaming at 1400 °F for 16 hours.
  • EY Extra Mesoporous Y
  • FIGURE 5 shows the distillate product yields from the comparative hydrocrackmg testing data from the "batch unit" high-throughput testing of Example 3.
  • FIGURE 6 shows the distillate product selectivities from the comparative hydrocrackmg testing data from the "batch unit" high -through put testmg of Example 3.
  • FIGURE 7 shows the distillate product yields from the comparative hydrocrackmg testing data from the "flow unit" high-throughput testing of Example 3.
  • FIGURE 8 shows the distillate product selectivities from the comparative hydrocracking testing data from the "flow unit" high-throughput testmg of Example 3.
  • FIGURE 9 shows the distillate product yields for four (4) comparative hydroprocessing catalysts with respective platinum (Pt) metal loadings of 0,3 wt%, 0.6 wt%, 1.0 wt% and 2.0 wt%.
  • FIGURE 10 shows the distillate product selectivities for four (4) comparative hydroprocessing catalysts with respective platinum (Pt) metal loadings of 0.3 wt%, 0.6 wt%, 1.0 wt% and 2.0 wt%.
  • the hydrocracking catalyst of the present invention incorporates the use of an Extra Mesoporous Y (“EM Y”) zeolite and its use in hydrocarbon cracking catalysts.
  • EM Y Extra Mesoporous Y
  • This zeolite is described herein as well as described further in United States Serial Number 12/584,376 entitled “Extra Mesoporous Y Zeolite", which is incorporated in its entirety herein.
  • the hydrocracking catalysts herein comprising this new zeolite have been unexpectedly found to exhibit improved rates of heavy oil cracking with improved low temperature conversion rates (i.e., "750°F+ Conversion") as well as improved selectivities of distil late yields (“i.e., 40Q-700°F Yield”) when utilized in the hydrocracking processes of the present invention.
  • an EMY zeolite which is a Y structure zeolite with a suppressed "small mesopore peak" that is commonly found associated within the "small mesopores" (30 to 50 A pore diameters) of commercial Y-type zeolites, while maintaining a substantial volume of pores in the "large mesopores" (greater than 50 to 500 A pore diameters) of the zeolite.
  • International Union of Pure and Applied Chemistry (“TUPAC”) standards defines "mesopores” as having pore diameters greater than 20 to less than 500 Angstroms (A).
  • the standard nitrogen desorption measurements as used herein do not provide pore volume data below about 22 A.
  • the "small mesopore peak" found in Y zeolites are substantially confined between the 30 and 50 A ranges, it is sufficient to define the measurable mesoporous pore diameter range for the purposes of this invention as pore diameters from 30 to 500 Angstroms (A).
  • the terms "Small Mesopore(s)” or “Small Mesoporous” are defined as those pore structures in the zeolite crystal with a pore diameter of 30 to 50 Angstroms (A).
  • the terms "Large Mesopore(s)” or “Large Mesoporous” as utilized herein are defined as those pore structures in the zeolite crystal with a pore diameter of greater than 50 to 500 Angstroms (A).
  • the terms "Mesopore(s)” or “Mesoporous” when utilized herein alone (i.e., not in conjunction with a “small” or “large” adjective) are defined herein as those pore structures in the zeolite crystal with a pore diameter of 30 to 500 Angstroms (A). Unless otherwise noted, the unit of measurement used for mesoporous pore diameters herein is in Angstroms (A).
  • Small Mesopore Volume or "Small Mesoporous Volume” of a material as used herein is defined as the total pore volume of the pores per unit mass in the Small Mesopore range as measured and calculated by ASTM Standard D 4222 "Determination of Nitrogen Adsorption and Desorption isotherms of Catalysts and Catalyst Carriers by Static Volumetric Measurements”; ASTM “ Standard D 4641 “Calculation of Pore Size Distributions of Catalysts from Nitrogen Desorption Isotherms”; and "The Determination of Pore Volume and Area Distributions in Porous Substances, I.
  • the term "Large Mesopore Volume” or “Large Mesoporous Volume” of a material as used herein is defined as the total pore volume of the pores per unit mass in the Large Mesopore range as measured and calculated by ASTM " Standard D 4222 "Determination of Nitrogen Adsorption and Desorption isotherms of Catalysts and Catalyst Carriers by Static Volumetric Measurements”; ASTM Standard D 4641 "Calculation of Pore Size Distributions of Catalysis from Nitrogen Desorption Isotherms”; and "The Determination of Pore Volume and Area. Distributions in Porous Substances, I.
  • LSPVR Large-to-Small Pore Volume Ratio
  • BJH N 2 Desorption Plot is defined as a plot of the change in unit volume of a mesoporous material as a function of the pore diameter of the mesoporous material.
  • the "BJH N? Desorption Plot” is shown as the pore volume calculated as dV/dlogD (in cm ' Vg) vs. the pore diameter (in nanometers) as determined by the ASTM Standard D 4222, ASTM Standard D 4641, and "The Determination of Pore Volume and Area Distributions in Porous Substances, 1.
  • the BJH N 2 Desorption Plot should be generated from approximately 1 5 to 30 data points at approximately equidistant positions on a logarithmic x-axis of the pore diameter (nanometers) between the values of 3 to 50 nanometers (30 to 500 A).
  • the pore volume value on the y-axis of the plot is commonly calculated in industry equipment as an interpolated value of the incremental change in volume, dV (where V is in cm", and dV is in cm " ') divided by the incremental change in the log of the pore diameter, dlogD (where D is in nanometers, and dlogD is unitless) and is adjusted to the unit weight of the sample in grams. Therefore, the "pore volume" (which is the common term utilized in the industry) as shown on the y- axis of the BJH N 2 Desorption Plot may be more appropriately described as an incremental pore volume per unit mass and is expressed herein in the units cnrVg.
  • pore volume value on the y-axis of the BJH N 2 Desorption Plot is not synonymous with the "Small Mesopore Volume” and “Large Mesopore Volume” as described above which are calculated unit pore volumes over a range of pore diameters.
  • these calculations and terms as used herein are familiar to those of skill in the art. Ail measurements and data plots as utilized herein were made with a Micromeritics* Tristar 3000* analyzer.
  • Small Mesopore Peak refers to the property of a zeolite and is defined as the maximum pore volume value calculated as dV/dlogD (y-axis) on a BJH ? Desorption Plot as described above (pore volume vs. pore diameter) between the 30 A and 50 A pore diameter range (x-axis). Unless otherwise noted, the unit of measurement for the small mesopore peak is in cm g.
  • 40 A Peak or "40 A Peak Height” as used herein refers to the property of a catalyst and is defined as the maximum pore volume value calculated as dV/dlogD (y-axis) on a BJH 2 Desorption Plot as described above (pore volume vs. pore diameter) at 40 A pore diameter (x-axis). Unless otherwise noted, the unit of measurement for the 40 A Peak is in cm '/g.
  • the term "Large Mesopore Peak” used herein refers to the property of a zeolite and is defined as the maximum pore volume value calculated as dV/dlogD (y-axis) on a BJH N 2 Desorption Plot as described above (pore volume vs. pore diameter) between the 50 A and 500 A pore diameter range (x-axis). Unless otherwise noted, the unit of measurement for the large mesopore peak is in cm7g. [0030] The term "BET Surface Area” for a. material as used herein is defined as the surface area as determined by ASTM Specification D 3663. Unless otherwise noted, the unit of measurement for surface area is in m g.
  • Unit Cell Size for a material as used herein is defined as the unit cell size as determined by ASTM Specification D 3942. Unless otherwise noted, the unit of measurement used for unit cell size herein is in Angstroms (A).
  • FIG. 1 shows a typical the BJH N 2 Desorption Plot of a typical USY zeolite.
  • the USY exhibits a high volume of pores in the "small mesoporous" range (30 to 50 A pore diameter) as well as a significant "small mesopore peak" in the BJH N 2 Desorption Plot of about 0.20 cm7g or more in this small mesopore range.
  • This high peak in the 30 to 50 A pore diameter range of the BJH N 2 Desorption Plot is a common feature for Y- zeolite materials that possess a significant pore volume in the mesoporous range (30 to 500 A pore diameters). This peak exhibited in the BJH N 2 Desorption Plot of the Y zeolites is termed herein as the "Small Mesopore Peak" of the zeolite and is defined above.
  • this phenomenon occurs due to a "boltlenecking" of some of the mesoporous structures in the zeolite creating an ink-bottle effect wherein a significant amount of the nitrogen inside the internal pore cavities cannot be released during the desorption phase of the test until the partial pressure is reduced below the point associated with this small mesopore peak point.
  • this peak is associated at a point in the desorption branch at a relative nitrogen pressure (P/P 0 ) of about 0.4 to about 0.45.
  • Example 1 According to the details of Example 1 , a conventional USY sample as described above and shown in Figure 1 was further ammonium ion-exchanged three times and then steamed at 1400 °F for 16 hours to determine the resulting pore distribution and surface area stability of the USY zeolite under these hydrothermal conditions.
  • Figure 2 shows the B JH N 2 Desorption Plot of the ion- exchanged USY zeolite after long-term deactivation steaming. As can be seen from Figure 2, the steamed USY ' develops a "large mesopore peak" in the large mesoporous structures (50 to 500 A pore diameter range) of the zeolite.
  • the "small mesopore peak" associated with pores in the 30 to 50 A pore diameter range of the steamed USY is not significantly decreased as compared to the small mesopore peak of the un-steamed USY sample as shown in Figure 1 .
  • the small mesopore peak of the steamed U SY is about 0.19 cnrVg.
  • the hvdrocrackmg catalysts of the present invention utilize a highly stable Y-zeoiite that has a significantly suppressed small mesopore peak in both the as-fabricated and as-steamed conditions while maintaining a high volume of large mesopores (50 to 500 A pore diameter range).
  • a hydrocracking catalyst comprised of a highly stable Y- zeolite that has a significantly suppressed small mesopore peak in both the as- fabricated and as-steamed conditions while maintaining a high ratio of large-to- small mesoporous volume.
  • the zeolite utilized in the hydrocracking catalysts of this invention is termed herein as an "Extra Mesoporous Y" (or ⁇ ") zeolite.
  • an EMY zeolite which can be obtained from a starting material of a conventional Na-Y type zeolite with a sodium oxide (Na 2 0) content of about 10 to 15 wt%.
  • the EMY zeolite precursor is ammonium-exchanged to lower the Na 2 0 content to a desired level for the production of an EMY zeolite, Generally, about one to about three ammonium-exchanges are required to reduce the Na 2 Q content of a. typical Na-Y precursor to a. desired level for the production of an EMY zeolite.
  • the Na 2 Q content of the ammonium-exchanged Na-Y zeolite precursor is brought to about 2.0 to about 5.0 wt% Na 2 Q. More preferably, the Na 2 0 content of the ammonium-exchanged Na-Y zeolite precursor is brought to about 2.3 to about 4.0 wt% a 2 0. In this preferred embodiment, it is believed that the number of ion- exchange steps performed is not essential to the formation of EMY as long as the Na 2 0 content of the EMY precursor is within a desired range. Unless otherwise noted, the Na 2 0 content is as measured on the zeolite precursor prior to high temperature steam calcination and reported on a dry basis.
  • the EMY precursors or the final EMY zeolite may also be rare earth exchanged to obtain a rare earth exchanged EMY or "RE-EMY" zeolite.
  • the zeolites may be rare earth exchanged in accordance with any ion-exchange procedure known in the art. it should also be noted that the weight percentages used herein are based on the dry weight of the zeolite materials.
  • the ammonium-exchanged Na-Y precursor thus obtained is subjected to a very rapid high temperature steam calcination, in this high temperature steam calcination process, the temperature of the steam is from about 1200 to about 1500 °F. More preferably the temperature of the steam is from about 1200 to about 1450 °F, more preferably from about 1250 to about 1450 °F, and even more preferably from about 1300 to about 1450 °F.
  • the zeolite precursor be brought up close to the desired steaming temperature in a very rapid manner.
  • the temperature of the zeolite during the steaming process may be measured by a thermocouple implanted into the bed of the EMY zeolite precursor.
  • the temperature of the zeolite is raised from a standard pre-calcination temperature to within 50 "F (27.8 °C) of the steam temperature during the high temperature steam calcination step in less than about 5 minutes.
  • the temperature of the zeolite is raised from a standard pre- calcination temperature to within 50 °F (27.8 °C) of the steam temperature during the high temperature steam calcination step in less than about 2 minutes.
  • typically the pre-calcination temperature in a Y-type zeolite manufacturing process is from about 50 °F to about 300 °F.
  • Example 2 herein describes the synthesis of one embodiment of an Extra Mesoporous Y (“EMY”) zeolite.
  • Figure 3 shows the BJH N 2 Desorption Plot of the EMY zeolite sample from Example 2 prior to additional ammonium exchange and long-term deactivation steaming.
  • the EM Y zeolite exhibits a very low volume of pores in the "small mesoporous" range (30 to 50 A pore diameter) as well as a very low "small mesopore peak" of about 0.09 cnr /g in this small mesopore range.
  • the pore volumes in each of the ranges, 30 to 50 Angstroms as well as 50 to 500 Angstroms were determined by utilizing the pore volume data from the BJH N? Desorption tests and interpolating the data to the necessary endpoints. This method for calculating the pore volumes is explained in detail in Example 1 and the same method for calculating the pore volumes was utilized throughout all examples herein. The method as described therein defines how to interpret and calculate the pore volume values of the zeolites within each of the defined pore diameter ranges.
  • Figures 1 and 3 reflect the USY and EMY zeolite samples after the high temperature steam calcination step and prior to any subsequent treating.
  • Table 1 the volume of small mesopores is larger in the USY zeolite than in the EMY zeolite.
  • the volume of large mesopores in the EMY zeolite is significantly larger than the volume of large mesopores in the US Y zeolite.
  • an important characteristic of the zeolite is the ratio of the large mesopore volume (“LMV”) to the small mesopore volume (“SMV”) of the subject zeolite.
  • LMV large mesopore volume
  • SMV small mesopore volume
  • LSPVR Large-to-Smali Pore Volume Ratio
  • the Large-to-Smal i Pore Volume Ratio or "LSPVR" of the sample USY zeolite is about 1.01 wherein the LSPVR of the sample EMY zeolite is about 6.79. This is a significant shift in the Large-to- Small Pore Volume Ratio obtained by the present invention.
  • the LSPVR of the EMY is at least about 4.0, more preferably at least about 5.0, and even more preferably, the LSPVR of the EMY is at least about 6.0 immediately after the first high temperature steam calcination step as described herein.
  • the EM Y zeolites of the present invention may be used in processes that are not subject to exposure to high temperature hydrothermal conditions. It can be seen from Table 1, that one of the remarkable aspects of the EMY zeolites of the present invention is that they exhibit very high Large Mesopore Volumes as compared to the comparable USY of the prior art. This characteristic of the EMY ' zeolites of the present invention can be valuable to many commercial processes.
  • the as-fabricated EMY zeolites of the present invention have a Large Mesopore Volume of at least 0.03 cmVg, more preferably at least 0.05 cm ' Vg, and even more preferably at least 0.07 cm g.
  • the term "as-fabricated” or "as-fabricated, zeolite” of the present invention is defined as the zeolite and its properties as obtained directly after the high temperature steam calcination step (i.e., when the EMY zeolite is formed).
  • subsequent additional steps e.g., further ion-exchange
  • the zeolite properties are measured and defined herein as of this "as- fabricated" point in the fabrication process.
  • the "long-term deactivation steaming" referred to herein is general ly utilized as a tool to test the ability of the as-fabricated zeolite to withstand hydrothermal conditions and is not considered as a part of the fabrication of the zeolite.
  • long-term deactivation steaming will tend to increase the Large Mesopore Volume of typical Y zeolites.
  • this unusual aspect of the EMY zeolites of the present invention of possessing such a significantly increased Large Mesopore Volume prior to long-term deactivation steaming can be useful in processes wherein high temperature hydrothermal conditions are not present or even more importantly in processes wherein it is undesired for the fabricated zeolite to be long-term steam deactivated.
  • the as-fabricated EMY ' zeolite possesses higher BET surface areas as compared to the BET ' surface areas after the log-term steam deactivation and the as-fabricated EMY zeolite may be more stable in some applications than that the EMY zeolite obtained after long-term steam deactivation.
  • the EMY zeolite has a Small Mesopore Peak of less about 0.13 cnrVg, and in an even more preferred embodiment, the Smal l Mesopore Peak of the EMY is less than about 0.1 1 cnr g.
  • the Small Mesopore Volume Peak as defined prior is the maximum value (or peak) of the pore volume value (dV/dlogD, y-axis) exhibited on the BJH N2 Desorption Plot in the 30 to 50 Angstroms (A) pore diameter range.
  • the EM Y materials of the present invention exhibit smaller unit cell sizes as compared to similar USY materials that have undergone a single high temperature steam calcination step.
  • the USY zeolite of Example 1 has a unit cell size of about 24.55 A, while the EMY zeolite prepared from similar starting materials has a significantly lower unit cell size of about 24.42 A.
  • these as- fabricated EM Y zeolites exhibit unit cell sizes that are less than 24.45 A.
  • the as-fabricated EMY zeolites exhibit unit cell sizes ranging from about 24.37 to about 24.47 A after the first high temperature steam calcination step as described herein, in even more preferred embodiments, the as-fabricated EMY zeolites have low unit cells size from about 24.40 to about 24.45 A after the first high temperature steam calcination step as described herein.
  • This smaller unit cell size generally results in a more stable zeolite configuration due to the higher framework silica/alumina ratios reflected by the lower unit cel l sizes of EMY zeolite.
  • Figure 2 shows the BJH N 2 Desorption Plot of the ion-exchanged USY zeolite of the prior art after long-term deactivation steaming.
  • Figure 4 shows the BJH 2 Desorption Plot of the ion-exchanged EMY zeolite of an embodiment of the present invention after Song-term deactivation steaming.
  • the Large Mesopore Peak of the EMY zeolite increased desirably from about 0.1 cm " Vg (as shown in Figure 3) to about 0.36 cm " 7g (as shown in Figure 4) after long-term deactivation steaming.
  • the Small Mesopore Peak of the EMY zeolite was not significantly increased.
  • the Small Mesopore Peak of the EMY zeolite remained essentially constant at about 0.10 cm " /g (as shown in Figures 3 and 4).
  • Another benefit of the EMY zeolites of the present invention is surface area stability.
  • the BET surface area for the long-term deactivation steamed EMY zeolite sample was greater than the BET surface area for the USY sample.
  • the EMY retained a. higher percentage of the surface area after the three ammonium ion exchanges and long-term deactivation steaming at 1400 °F for 16 hours. Comparing Table 1 and Table 2, the USY retained about 70% of its original surface area wherein the EMY retained about 95% of its original surface area, indicating the superior hydrostability of the EMY zeolites of the present invention.
  • the EMY zeolite has BET Surface Area of at least 500 m 2 /a as measured either before long-term deactivation steaming at 1400 °F for 16 hours or after long-term deactivation steaming at 1400 °F for 1 6 hours.
  • the "Large-to-Small Pore Volume Ratio" (or "LSPVR") of the EMY is at least about 10.0, more preferably at least about 12.0, and even more preferably, the LSPVR of the EMY is at least about 15.0 after long-term deactivation steaming at 1400 °F for 16 hours.
  • the EMY zeolite is incorporated with a binder material to impart resistance to the temperatures and other conditions employed in the hydrocarbon conversion processes as well as to enable the catalyst to be formed into catalyst particles of suitable size and stability for the hydrocracking process apparatus and process conditions.
  • the EMY zelolite herein is incorporated into a catalyst by the use of a suitable binder material.
  • suitable binder materials include materials selected from metal oxides, zeolites, aluminum phosphates, polymers, carbons, and clays.
  • the binder is comprised of at least one metal oxide, preferably selected from silica, alumina, silica-alumina, amorphous aluminosilicates, boron, titania, and zirconia.
  • the binder is selected from silica, alumina, and silica-alumina.
  • the binder is comprised of pseudoboehmite alumina.
  • the catalysts of invention can contain from 0 to 99 wt% binder materials
  • the binders levels can be about 25 to about 80 wt%, more preferably, from about 35 to 75 wt%, or even from about 50 to about 65 wt% of the overall final hydrocracking catalyst.
  • the hydrocracking catalyst can be less than 80 wt%, more preferably less than 75 wt%, and most preferably less than 65 wt% or even 50 wt% binder materials,
  • the hydrocracking catalyst may contain additional zeolites or molecular sieves.
  • the hydrocracking catalyst further comprises at least one of the following zeolites or molecular sieves.
  • the hydrocracking catalyst further comprises at least one of the following molecular sieves: beta, ZSM-5, ZSM-l l , ZSM-57, MCM-22, W -49.
  • the hydrocracking catalyst comprises at least one of the following molecular sieves: beta, ZSM-5, ZSM-48, mordenite, and zeolite L.
  • the molecular sieves listed above can be present in the as-synthesized form, or alternatively, can be post-modified chemically, thermal ly, or mechanically to create a stabilized form of the material.
  • the hydrocracking catalyst of the invention herein contains the EMY zeolite in an amount of at least 10 wt% , more preferably at leas! at least 25 wt%, and even more preferably at least 35 wt% or even at least 50 wt% based on the finished catalyst, particularly when a binder is utilized.
  • the aggregates of zeolite Y are combined with at least one metal oxide binder (as described prior) and further with at least one hydrogenating metal component, in order to form a catalyst suitable for hydrocracking.
  • hydrogenating metal components can include one or more noble metals or one or more non-noble metals.
  • the aggregates of zeolite Y, binder and additional components may be extruded, spray-dried, or otherwise shaped into a catalyst particle for use in hydroconversion processes described herein.
  • the final catalyst contains an active Group 6 and/or Group 8/9/10 metal. Please note that the designation of Group 6 and Group 8/9/10 herein corresponds to the modern IUPAC designation wherein the columns of the Periodic Table of Elements corresponds to columns numbered 1 through 18.
  • a "Group 6" metal as designated herein corresponds to any metal in Column 6 of the modern IUPAC designated Periodic Table of Elements and which corresponds to the old designation of "Group VIA” as shown in the Periodic Table of Elements, published by the Sargent-Welch Scientific Company, 1979, wherein the Group 6 (old "Group VIA") elements include the column from the periodic table of elements containing Cr, Mo, and W.
  • a "Group 8/9/10" metal as designated herein corresponds to any metal in Columns 8, 9 or 10 of the modern IUPAC designated Periodic Table of Elements and which corresponds to the old designation of "Group VIIIA” as shown in the Periodic Table of Elements, published by the Sargent-Welch Scientific Company, 1979, wherein the Group 8/9/10 (old "Group VIIIA”) elements include the columns from the periodic table of elements containing Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.
  • the hydrocracking catalyst is comprised of at least one Group 6 metal selected from Mo and W, and at least one Group 8/9/10 metal selected from Ni and Co.
  • the Group 6 metal is Mo and the Group 8/9/10 metal is Co.
  • the hydrocracking catalyst is comprised at least one Group 8/9/10 metal selected from Pt, Pd, Rh and Ru (noble metals).
  • the hydrocracking catalyst is comprised at least one Group 8/9/10 metal selected from Pt and Pd.
  • the hydrocracking catalyst is comprised of Pt.
  • the active Group 6 or Group 8/9/10 metals may be incorporated into the catalyst by any technique known in the art. A preferred technique for active metal incorporation into the catalyst herein is the incipient wetness technique.
  • the amount of active metal in the catalyst can be at least 0.1 wt% based on catalyst, or at least 0.15 wt%, or at least 0.2 wt.%, or at least 0.25 wt.%, or at least 0.3 wt.%, or at least 0.5 wt% based on the catalyst.
  • the amount of active metal is preferably from 0.1 to 5 wt%, more preferably from 0.2 to 4 wt%, and even more preferably from 0.25 to 3.5 wt%.
  • the active metal is a combination of a non-noble Group 8/9/10 non-noble metal with a Group 6 metal
  • the combined amount of active metal is preferably from 0.25 wt.% to 40 wt%, more preferably from 0.3 wt% to 35 wt%, and even more preferably from 1 wt% to 25 wt%.
  • non-noble metals and non-noble metal combinations utilized in the hydrocracking catalysts herein can include chromium, molybdenum, tungsten, cobalt, nickel, and combinations thereof, such as cobalt- molybdenum, nickel-molybdenum, nickel-tungsten, cobalt-tungsten, cobalt- nickel-molybdenum, cobalt-nickel-timgsten, nickel-molybdenum-tungsten, and cobalt-molybdenum-tungsten.
  • Non-noble metal components may be pre-sulfided prior to use by exposure to a sulfur-containing gas (such as hydrogen sulfide) or liquid (such as a sulfur-containing hydrocarbon stream, e.g., derived from crade oil and/or spiked with an appropriate organosulfur compound) at an elevated temperature to convert the oxide form to the corresponding sulfide form of the metal.
  • a sulfur-containing gas such as hydrogen sulfide
  • liquid such as a sulfur-containing hydrocarbon stream, e.g., derived from crade oil and/or spiked with an appropriate organosulfur compound
  • the present invention also includes a. method of making the hydrocracking catalysis described herein.
  • a preferred method of making an embodiment of the catalysts herein comprises the steps of mixing a binder precursor selected from a.
  • the binder precursor is a colloidal silica, silica gel, a silica sol, or a combination thereof.
  • the binder precursor is a colloidal alumina, alumina gel, a alumina sol, or a combination thereof,
  • Most preferred embodiments of the low mesoporous peak catalysts and method of making the low mesoporous peak catalysts of the present invention include combinations of some or all of the most preferred embodiments of the EMY zeolites and catalysts described herein,
  • the hydrocracking catalyst materials herein can be formed into a paste utilizing the components as described herein as well as are exemplified as described in the examples herein.
  • the paste can then be extraded into catalyst pellets.
  • the extruded catalyst pellets are further dried as about 150 to about 300°F (66 to about 149°C) and then are further air calcined at about 600 to about 1200°F (316 to about 649°C).
  • the hydrocracking catalyst can formed by spray drying the catalyst mixture at a temperature from about 250°F to about 650°F (121 to about 343°C), which can then be further optionally air dried and calcined.
  • the active metals are preferably added to the formed catalyst pellets after drying and/or calcining.
  • the active metals are added to the formed catalyst pellets by incipient wetness technique.
  • the embodiments of the hydrocracking catalysts described herein are utilized in processes for conversion of heavy hydrocarbon feedstocks into lighter, more valuable hydrocarbon products (such, as gasolme, kerosene, and diesel products).
  • the catalysts herein have been unexpectedly found to possess very high selectiviti.es toward diesel production (i.e., increased yield volumes) when utilized under hydrocracking conditions.
  • increased diesel production is a main focus of refineries in the United States (and even more particularly in the markets of Europe and Asia), as the vehicle pool is ever shifting more toward higher mileage diesel powered vehicles as compared to less efficient gasoline powered engines.
  • the hydrocarbon feedstock to be hydrocracked may include, in whole or in part, a gasoii (e.g., light, medium, heavy, vacuum, and/or atmospheric) having an initial boiling point above about 400°F (204°C), a T50 boiling point (i.e., the point at which approximately 50 percent by weight boils, or becomes or is gaseous, under atmospheric pressure) of at least about 600°F (316°C), and an end boiling point of at least about 750°F (399°C).
  • a gasoii e.g., light, medium, heavy, vacuum, and/or atmospheric
  • T50 boiling point i.e., the point at which approximately 50 percent by weight boils, or becomes or is gaseous, under atmospheric pressure
  • the hydrocracking catalysts of invention are particularly useful in maximizing diesel production (400°F to 700°F, i.e. 204- 371°C, boiling range products) from higher boiling point feedstocks.
  • the hydrocarbon feedstock contains at least 25 wt%, more preferably at least 50 wt%, and even more preferably, at least 75 wt% hydrocarbons with boiling points above 750°F (399°C).
  • the feedstock can include one or more of thermal oils, residual oils, cycle stocks, whole top erodes, partial crudes, tar sand oils, shale oils, synthetic fuels, heavy hydrocarbon fractions derived from the destructive hydrogenation of coal, tar, pitches, and/or asphalts, hydrotreated feedstocks derived therefrom, and the like.
  • the distillation of higher boiling petroleum fractions above about 750°F (399°C) can generally be carried out under vacuum (i.e., at subatmospheric pressure), typically to avoid thermal cracking.
  • the boiling temperatures utilized herein are thus conveniently expressed in terms of the boiling point corrected to atmospheric pressure.
  • resid compositions and/or deeper cut gasoils such as with relatively high metals contents, can be cracked using catalysts employing the aggregated zeolite materials of the invention.
  • a hydrocarbon feedstock is contacted with embodiments of the hydrocracking catalysts disclosed and described herein under hydrocracking conditions.
  • diesel product i.e., hydrocarbon with boiling points in the range of 400 to 700°F, also referred to as the "400-700°F Yield” or “Distillate Yield
  • the "Distillate Selectivity" of a hydrocracking catalyst is also high.
  • the “Distillate Selectivity” is defined as the Distillate Yield divided by the "700°F+ Conversion" (or simply “conversion”) herein.
  • the "700°F+ Conversion" is the wt% of the hydrocarbon product from the process that boils below 700°F divided by the wt% of the hydrocarbon feed from the process that boils above 700°F,
  • the Distillate Selectivity is an important measurement since although a high 700°F+ Conversion is desired, it is desired that a high amount of the converted product is in the distillate range and not cracked into lighter, less valuable products. As such, the Distillate Selectivity is an important measurement of the catalysts' performance. [0078J
  • the contacting of the hydrocarbon feedstock with the Y-containing hydrocracking catalysts is typically performed in a hydrocracker reactor in the presence of excess hydrogen gas.
  • the hydrocracking process may contain one or more reactor stages in series, but most preferably, there are either one or two reactor stages, but each stage may contain one or more reactor vessels. In preferred embodiments of the present invention, there are at least two reactor stages, with the first reactor stage being operated at a total pressure of at least 250 psig, more preferably at least 500 psig, higher than the second reactor stage. Even more preferably, hydrocracking process comprises an intermediate vapor separation between the first reactor stage and the second reactor stage in which at least a portion of the hydrogen gas from the first reactor stage effluent is removed. In more preferred embodiments, at least a portion of the hydrogen gas removed in the intermediate vapor separation step is recycled to the first reactor stage.
  • Preferred hydrocracking operating conditions herein include a reaction temperature from about 550°F (about 288°C) to about 80Q°F (about 427°C); a total pressure from about 300 psig (about 2.1 MPag) to about 3000 psig (about 20.7 MPag), more preferably from about 700 psig (about 4.8 MPag) to about 2500 psig (about 17.2 MPag); an LHSV from about 0.1 hr ⁇ !
  • a hydrogen treat gas rate from about 500 scf/hbf (about 85 NnrVnr) to about 10000 scf bbl (about 1700 NrnVm 3 ), preferably from about 750 scf/bbl (about 130 Nm'/nr) to about 7000 scf/bbl (about 1200 Nm7m r ), more preferably from about 1000 scf/bbl (about 170 NmVm 3 ) to about 5000 scf/bbl (about 850 NmV).
  • Figures 5 and 6 herein show the results of the "batch unit” testing described in Example 4 including the four (4) EMY hydrocracking catalyst samples of the present invention (Catalyst Samples 1 -4) compared with the seven (7) USY reference catalysts from Example 3.
  • the Distillate Yields are shown for all eleven (1 1) catalysts.
  • the "Distillate Yield” is the weight percentage of the hydrocarbon product from the testing that boils in the range of from 400-700°F.
  • three of the four EMY hydrocracking catalysis of invention show Distillate Yields at are above the best performing reference hydrocracking catalysts.
  • Figures 7 and 8 herein show the results of the "flow unit” testing described in Example 4 of the four (4) EM Y hydrocracking catalyst samples of the present invention (Catalyst Samples 1 -4).
  • the resulting product was an ultra-stable Y (USY) zeolite, and was analyzed with a Micromeritics* Tristar 3000* analyzer to determine the pore size distribution characteristics by nitrogen adsoi lioiT/desorption at 77,35°K.
  • a calculated Cumulative Pore Volume (em ' Vg) is associated with a range of Pore Diameter (nm) as the test incrementally desorbs the nitrogen from the test sample.
  • An Incremental Pore Volume is then calculated for each of these ranges.
  • a pore volume within a certain range (for example a range from 50 to 500 A, which is equivalent to 5 to 50 nm as presented in Table 4) can be calculated by subtracting the Cumulative Pore Volume at 50 nm from the Cumulative Pore Volume at 5 nm.
  • the Cumulative Pore Volume at a specific pore size can be calculated by interpolating the data within the range. This method was utilized for all of the Examples herein.
  • the Cumulative Pore Volume associated with 50 ran was calculated by interpolating the amount of the Incremental Pore Volume (highlighted) associated with the difference between 62.8 nm and 50.0 nm in the 62.8 to 41.5 nm pore diameter range as shown in the table (highlighted) and adding this amount to the Cumulative Pore Volume (highlighted) from the prior range.
  • the calculation for the Cumulative Pore Volume associated with 50 nm pore diameter was calculated from the data in Table 4 above as follows:
  • the total Pore Volume associated with the pore diameter ranges of 5 nm to 50 nm (50 A to 500 A) of the USY of this example is thus equal to the difference in the Cumulative Pore Volumes associated with 5 nm and 50 nm respectfully as follows:
  • the USY zeolite sample exhibited a BET surface area of 81 1 m /g, and a unit cell size of 24.55 angstroms.
  • a sample of the prepared USY zeolite above was further subjected to an ammonium ion-exchange consisting of adding 80 grams of the zeolite into 800 mi of NH 4 N0 3 (1.M) solution at 70 °C and agitating for 1 hour, followed by filtration on a funnel and washing the filter cake with 1000 ml of de-ionized water.
  • the water rinsed zeolite cake was dried on the funnel by pulling air through, then in an oven at 120°C in air for over 2 hours, Chemical analysis of the dried zeolite by I CP showed 0.48 wt% Na 2 0 (dry basis). A Na 2 0 content of about 0.50 wt% was targeted.
  • the dried zeolite was subjected to long-term deactivation steaming at 1400 °F for 16 hours, 100% steam, to determine its hydrof hernial stability.
  • the USY zeolite after long-term deactivation steaming exhibited a BET surface area of 565 m 2 /g, and a unit cell size of 24.27 angstroms.
  • Extra Mesoporous Y (“EMY”) zeolite was prepared as follows:
  • Example 2 The same commercial ammonium-exchanged Y zeolite (CBV-300*) with a low sodium content (Si0 2 Al 2 0 molar ratio :::: 5.3, a 2 0 3.15 wt% on dry basis) as in Example 1 was placed in a horizontal quartz tube, which was inserted into a horizontal oven pre-equiiibrated at 1400°F in 100% steam at atmospheric pressure. Utilizing this procedure, the temperature of the zeolite precursor was raised to within 50 °F of the high temperature steam calcination temperature (i.e., to 1350 °F) within 5 minutes. The steam was let to pass through the zeolite powders.
  • CBV-300* commercial ammonium-exchanged Y zeolite with a low sodium content (Si0 2 Al 2 0 molar ratio :::: 5.3, a 2 0 3.15 wt% on dry basis) as in Example 1 was placed in a horizontal quartz tube, which was inserted into
  • the tube was removed from the horizontal oven and resulting EMY zeolite powders were collected.
  • the starting material i.e., the EMY precursor zeolite
  • the starting Y zeolite may first require ammonium-exchange or methods as known in the art to reduce the sodium content of the EMY zeolite precursor to acceptable levels prior to high temperature steam calcination to produce the EMY zeolite.
  • the resulting EMY zeolite was analyzed by a. Micromeritics* Tristar 3000 ® analyzer as used in Example 1.
  • the BJH method as described in the specification was applied to the N 2 adsoi tion/desorption isotherms to obtain the pore size distribution of the zeolite, and a plot of dV/dlogD vs. Average Pore Diameter is shown in Figure 3.
  • the following properties of this EMY zeolite were obtained:
  • the EMY zeolite sample exhibited a BET' surface area of 61.9 m'7g, and a unit cell size of 24.42 angstroms.
  • a sample of the EMY zeolite above was further subjected to an ammonium ion exchange consisting of adding 1.00 grams of the EMY ' zeolite into 1000 mi of NH 4 N0 3 (1M) solution at 70°C and agitating for 1 hour, followed by filtration on a funnel and washing the filter cake with 1000 ml of de-ionized water.
  • the water rinsed zeolite cake was dried on the funnel by pulling air through, then in an oven at 120°C in air for over 2 hours.
  • the ammonium ion exchange was repeated using 60 g of the washed EM Y zeoli te in 600 mi of NH 4 N() 3 ( ⁇ ) soluti on at 70°C and agitating for 1 hour, followed by filtration on a funnel and washing the filter cake with 1000 ml of de-ionized water.
  • the water rinsed zeolite cake was dried on the funnel by pulling air through, then in an oven at 120°C in air for over 2 hours.
  • Chemical analysis of the dried zeolite by ICP showed 0.64 wt% Na 2 0 (dry basis). A Na 2 0 content of about 0.50 wt% was targeted.
  • This zeolite was then subjected to long-term deactivation steaming at 1400 U F for 16 hours, 100% steam, to determine its hydrothermal stability. ⁇ * 7
  • the active metal (i.e., Pt) loadings differed, with some of the catalysts with 0.6 wt% Pt loading, and some with 2 wt% Pt loading. Although the metal loadings differed between some of the catalysts, it is believed that this slight difference in the metal loadings does not have any significant effect on the comparative data (i.e., conversions, distil late yields, or distillate selectiviti.es) provided in the testing herein.
  • an EMY hydrocracking catalyst was prepared by the following method.
  • the EMY zeolite utilized in this catalyst sample started with a commercial USY zeolite made by Zeolyst ⁇ under the name CBV-SOO *1 .
  • the 200g of the zeolite was steamed for one hour in 100% steam in a horizontal steamer.
  • the steamed zeolite was placed in a beaker.
  • a 3pH buffered I N NH 4 NO 3 ion- exchange solution (5 ml/gm) was added to the beaker and the contents stirred for 1 hour at ambient temperature.
  • the zeolite sample was filtered and then the ion- exchange procedure was repeated for a second time with a fresh buffered solution.
  • the zeolite sample was filtered and then the ion-exchange procedure was repeated for a third time with a fresh buffered solution.
  • the zeolite sample was filtered and rinsed thoroughly with deionized (DI) water and vacuum dried.
  • the resulting zeolite was the dried for approximately 6 hours at 250°F.
  • the resulting zeolite was then steamed for 16 hours in 100% steam.
  • the resulting zeolite then underwent three (3) more ion-exchange procedures (same as prior) and then was filtered and rinsed thoroughly with deionized (DI) water and vacuum dried.
  • the resulting zeolite was the dried for approximately 6 hours at 250°F.
  • the resulting zeolite was then calcined for approximately 6 hours at 1000"F in air. Approximately 30g of the resu lting zeolite was placed in a beaker and underwent two (2) more ion-exchange procedures (same as prior) and then was filtered and rinsed thoroughly with deionized (DI) water and vacuum dried. The resulting zeolite was the dried at 250°F. The resulting zeolite was then calcined for approximately 6 hours at 1000°F in air.
  • DI deionized
  • EM Y zeolite About 65 parts of the resulting EM Y zeolite was mixed with about 35 parts of Versal ⁇ 300 pseudoboehmite alumina binder (basis: calcined at ⁇ 538°C) in a SimpsonTM muller. Tetraethylammonium Hydroxide (TEA OH) was added to a sufficient quantity of water to produce a 2% solution, and was added to produce an extrudable paste on a -2" (-5, 1 cm) diameter Bonnot ⁇ extruder.
  • TEA OH Tetraethylammonium Hydroxide
  • the extrudate was then impregnated via incipient wetness to -2.0 wt% Pt using tetraammineplatiniimnitrate, dried in a hotpack oven at ⁇ 121°C overnigh (for about 3 hours), fol lowed by calcination in air for about 3 hours at ⁇ 680°F (-405°C) to form Catalyst Sample 1.
  • the starting USY undergoes at least one, preferably more than one ion exchange, followed by steam calcination, followed by at least one, preferably more than one ion exchange, followed by air calcining at a temperature of from about 800°F to about 120Q°F, or more preferably, at a temperature of at least 1000°F.
  • the zeolite nay be further subjected to at least one additional ion- exchange, followed by a second air calcining at a temperature of from about 800°F to about 1200°F, or more preferably, at a temperature of at least 10G0°F.
  • the starting zeolite is a low sodium USY with a sodium content preferably less than about 0.1 wt%, or even more preferably less than about 0.05 wt%.
  • the steam calcination temperature is from about 1200 to 1500 l T, or preferably at least 12Q0°F, more preferably at least 1300°F, even more preferably at least 1400°F, and the temperature of the zeolite precursor is raised to within 50°F of the steam calcination temperature within 5 minutes (i.e., very fast steam calcination temperature ramp rate).
  • an EMY hydrocracking catalyst was prepared by the following method.
  • the EMY zeolite utilized in this catalyst sample started with a commercial USY zeolite made by Zeolyst ⁇ under the name CBV-SOO *1 .
  • the 200g of the zeolite was steamed for one hour in 100% steam in a horizontal steamer.
  • the steamed zeolite was placed in a beaker.
  • a 3pH buffered I N NH 4 NO 3 ion- exchange solution (5 ml/gm) was added to the beaker and the contents stirred for 1 hour at ambient temperature.
  • the zeolite sample was filtered and then the ion- exchange procedure was repeated for a second time with a fresh buffered solution.
  • the zeolite sample was filtered and then the ion-exchange procedure was repeated for a third time with a fresh buffered solution.
  • the zeolite sample was filtered and rinsed thoroughly with deionized ⁇ DI) water and vacuum dried.
  • the resulting zeolite was the dried for approximately 6 hours at 250°F.
  • the resulting zeolite was then steamed for 16 hours in 100% steam.
  • the resulting zeolite then underwent three (3) more ion-exchange procedures (same as prior) and then was filtered and rinsed thoroughly with deionized (DI) water and vacuum dried.
  • DI deionized
  • zeolite Approximately 30g of the resulting zeolite was placed in a beaker and underwent two (2) more ion-exchange procedures (same as prior) and then was filtered and rinsed thoroughly with deionized (DI) water and vacuum dried. The resulting zeolite was the dried at 250°F. The resulting zeolite was then calcined for approximately 6 hours at 1000°F in air.
  • DI deionized
  • the starting USY undergoes at least one, preferably more tha one ion exchange, followed by steam calcination, followed by at least one, preferably more than one ion exchange, followed by air calcining at a temperature of from about 800°F to about 12Q0°F, or more preferably, at a temperature of at least 1 000°F
  • the starting zeolite is a low sodium USY with a sodium content preferably less than about 0.1 wt%, or even more preferably less than about 0.05 wt%.
  • the steam calcination temperature is from about 1200 to 1500°F, or preferably at least 1200°F, more preferably at least 1300°F, even more preferably at least 14G0"F, and the temperature of the zeolite precursor is raised to within 50°F of the steam calcination temperature within 5 minutes (i.e., very fast steam calcination temperature ramp rate).
  • an EMY hydrocracking catalyst was prepared by the following method.
  • the EMY zeolite utilized in this catalyst sample started with a commercial USY zeolite made by Zeolyst *1 under the name CBV-300*.
  • the 20()g of the zeolite was steamed for one hour in 100% steam in a horizontal steamer.
  • the steamed zeolite was placed in a beaker.
  • a 3pH buffered IN NH 4 N0 3 ion- exchange solution (5 ml/gm) was added to the beaker and the contents stirred for 1 hour at ambient temperature.
  • the zeolite sample was filtered and then the ion- exchange procedure was repeated for a second time with a fresh buffered solution.
  • the zeolite sample was filtered and then the ion-exchange procedure was repeated for a third time with a fresh buffered solution,
  • the zeolite sample was filtered and rinsed thoroughly with deionized (Dl) water and vacuum dried.
  • the resulting zeolite was the dried for approximately 6 hours at 250°F.
  • the resulting zeolite was then steamed for 16 hours in 100% steam.
  • the resulting zeolite then washed in a 1.5M oxalic acid solution for approximately 2 hours at 176°F and then was filtered and rinsed thoroughly with deionized (Dl) water and vacuum dried.
  • the oxalic acid wash was then repeated and the zeolite was filtered and rinsed thoroughly with deionized (Dl) water and vacuum dried.
  • the resulting zeolite was the dried for approximately 6 hours at 250°F.
  • the resulting zeolite was then calcined for approximately 6 hours at 1000°F in air.
  • Approximately 30g of the resulting zeolite was placed in a beaker and underwent two (2) more ion- exchange procedures (same as prior) and then was filtered and rinsed thoroughly with deionized (Dl) water and vacuum dried.
  • the resulting zeolite was the dried at 250°F.
  • the resulting zeolite was then calcined for approximately 6 hours at 1000°F in air.
  • the starting USY undergoes at least one, preferably more than one ion exchange, followed by steam calcination, followed an acid wash, followed by air calcining at a temperature of from about 800°F to about 1200°F, or more preferably, at a temperature of at least 1000°F.
  • the zeolite may be further subjected to at least one additional ion-exchange, followed by a second air calcining at a temperature of from about 800°F to about 1200°F, or more preferably, at a temperature of at least 1000°F.
  • the starting zeolite is a low sodium USY with a sodium content preferably less than about 0.1 wt%, or even more preferably less than about 0.05 wt%.
  • the steam calcination temperature is from about 1200 to 1500°F, or preferably at least 120G°F, more preferably at least 1300°F, even more preferably at least 1400°F, and the temperature of the zeolite precursor is raised to within 50°F of the steam calcination temperature within 5 minutes (i.e., very fast steam calcination temperature ramp rate).
  • the acid wash is comprised of a carboxylic acid; more preferably, the acid wash is comprised of oxalic acid.
  • an EMY hydrocracking catalyst was prepared by the following method.
  • the EMY zeolite utilized in this catalyst sample started with a commercial USY zeolite made by Zeolyst *1 under the name CBV-300*.
  • the 200g of the zeolite was steamed for one hour in 100% steam in a horizontal steamer.
  • the steamed zeolite was placed in a beaker.
  • a 3pH buffered IN NH 4 NO 3 ion- exchange solution (5 ml/gm) was added to the beaker and the contents stirred for 1 hour at ambient temperature.
  • the zeolite sample was filtered and then the ion- exchange procedure was repeated for a second time with a fresh buffered solution.
  • the zeolite sample was filtered and then the ion-exchange procedure was repeated for a third time with a fresh buffered solution.
  • the zeolite sample was filtered and rinsed thoroughly with deionized (DI) water and vacuum dried.
  • the resulting zeolite was the dried for approximately 6 hours at 250°F.
  • the resulting zeolite was then steamed for 16 hours in 100% steam.
  • the resulting zeolite then underwent three (3) more ion-exchange procedures (same as prior) and then was filtered and rinsed thoroughly with deionized (Dl) water and vacuum dried.
  • the resulting zeolite was the dried for approximately 6 hours at 250°F.
  • the resulting zeolite was then steamed for 16 hours at 1400°F in 100% steam.
  • the starting USY undergoes at least one, preferably more than one ion exchange, followed by steam calcination, followed by at least one, preferably more than one ion exchange, followed by air calcining at a temperature of from about 800°F to about 120Q°F, or more preferably, at a temperature of at least 1000°F.
  • the zeolite may be further subjected to at least one additional ion- exchange, followed by another steam calcination step at a temperature of at least 1400°F.
  • the starting zeolite is a low sodium USY with a sodium content preferably less than about 0.1 wt%, or even more preferably less than about 0.05 wt%.
  • at least one steam calcination step preferably the first steam calcination step, the steam calcination temperature is from about 1200 to 1500°F, or preferably at least ] 200°F, more preferably at least 1300°F, even more preferably at least 1400°F, and the temperature of the zeolite precursor is raised to within 5Q°F of the steam calcination temperature within 5 minutes (i.e., very fast steam calcination temperature ramp rate).
  • the starting zeolite undergoes a steam calcination step prior to the first ion exchange step.
  • the reference USY zeolite utilized in this catalyst sample was a commercial USY zeolite made by Zeolyst ⁇ under the name CBV-901 *. Here the zeolite was utilized in the reference hydrocracking catalyst in the as-purchased state.
  • the hydrocracking catalyst was prepared from the zeolite in essentially the same manner as EMY sample catalysts preps 1 -4 (as well as reference Catalyst Sample preps 6-11). That is, about 65 parts of the CBV-901 * zeolite was mixed with about 35 parts of Versa 300 pseudoboehmite alumina binder utilizing the same procedure as described for Catalyst Sample 1 to form the extrudate.
  • the reference USY zeolite utilized in this catalyst sample was a commercial USY zeolite made by Tosoh* under the name HSV-360 1 *. Here the zeolite was utilized in the reference hydrocracking catalyst in the as-purchased state.
  • the hydrocracking catalyst was prepared from the zeolite in essentially the same manner as EMY sample catalysts preps 1 -4 (as well as reference Catalyst Sample preps 5 and 7-1 1), That is, about 65 parts of the HSV-36Q 18 zeolite was mixed with about 35 parts of Versa! 1 * 300 pseudoboehmite alumina binder uti lizing the same procedure as described for Catalyst Sample 1 to form the extrudate.
  • the reference USY zeolite utilized in this catalyst sample was a commercial USY zeolite made by Zeolyst *1 under the name CBV-720*'. Here the zeolite was utilized in the reference hydrocracking catalyst in the as-purchased state.
  • the hydrocracking catalyst was prepared from the zeolite in essentially the same manner as EMY sample catalysts preps 1 -4 (as well as reference Catalyst Sample preps 5-6 and 8-11). That is, about 65 parts of the CBV-720*' zeolite was mixed with about 35 parts of Versa!* 300 pseudoboehmite alumina binder uti lizing the same procedure as described for Catalyst Sample 1 to form the extrudate. [00151] The extrudate was then impregnated to an active metal loading of - ⁇ .6 wt.% Pt using essentially the same procedure as described for Catalyst Sample 1 to form Catalyst Sample 7.
  • the reference USY zeolite utilized in this catalyst sample was a commercial USY zeolite made by Tosoh " under the name 11SV-390HUA .
  • the zeolite was utilized in the reference hydrocracking catalyst in the as-purchased state.
  • the hydrocracking catalyst was prepared from the zeolite in essentially the same mariner as EMY sample catalysts preps 1 -4 (as well as reference Catalyst Sample preps 5-7 and 9-1 1). That is, about 65 parts of the HSV- 390HUA* zeolite was mixed with about 35 parts of Versa! w 300 pseudoboehmite alumina binder utilizing the same procedure as described for Catalyst Sample 1 to form the extrudate.
  • a USY reference catalyst was prepared by the following method.
  • the reference USY zeolite utilized in this catalyst sample was a commercial USY zeolite made by Zeolyst" 5 ' under the name CBV-760*. Here the zeolite was utilized in the reference hydrocracking catalyst in the as-purchased state.
  • the hydrocracking catalyst was prepared from the zeolite in essentially the same manner as EMY sample catalysts preps 1 -4 (as well as reference Catalyst Sample preps 5-8 and 10-1 1). That is, about 65 parts of the CBV-760 ⁇ zeolite was mixed with about 35 parts of Versa! " ' 300 pseudoboehmite alumina binder utilizing the same procedure as described for Catalyst Sample 1 to form the extrudate.
  • the reference USY zeolite utilized in this catalyst sample was a commercial USY zeolite made by Zeolyst *1 under the name CBV-780*'. Here the zeolite was utilized in the reference hydrocracking catalyst in the as-purchased state.
  • the hydrocracking catalyst was prepared from the zeolite in essentially the same manner as EMY sample catalysts preps 1 -4 (as well as reference Catalyst Sample preps 5-9 and 1 ). That is, about 65 parts of the CBV-780 ® zeolite was mixed with about 35 parts of Versa!'* 300 pseudoboehmite alumina binder utilizing the same procedure as described for Catalyst Sample 1 to form the extrudate.
  • the reference USY zeolite utilized in this catalyst sample was a commercial USY zeolite made by Tosolr' under the name HSV-SSSHUA "8' .
  • HSV-SSSHUA HSV-SSSHUA
  • the hydrocracking catalyst was prepared from the zeolite in essentially the same manner as EMY sample catalysts preps 1 -4 (as well as reference Catalyst Sample preps 5-10). That is, about 65 parts of the HSV-3H5H 1 A zeolite was mixed with about 35 parts of Versa 300 pseudoboehmite alumina binder uti lizing the same procedure as described for Catalyst Sample 1 to form the extrudate.
  • the feedstock utilized in the testing was a typical hydrocracking hydrocarbon feedstock boi ling substantially in the range of about 700 to about 1 100°F (371 to 593°C), with a density a 70°C of 0,8326 g/cm 3 , a sulfur content of 43 ppni, and a nitrogen content of ⁇ 10 ppm.
  • Figures 5 and 6 graphically show the results of the batch unit testing of the samples for both Distillate Yield ( Figure 5) and Distillate Selectivity ( Figure 6).
  • the feedstock utilized in the testing was a typical hydrocracking hydrocarbon feedstock boiling substantially in the range of about 700 to about 1 100°F (371 to 593°C), with a density at 70°C of 0,8412 g/cm 3 , a sulfur content of 178 ppm, and a nitrogen content of ⁇ 10 ppm.
  • the reaction products were retrieved during various points in the process and analyzed.
  • Figures 7 and 8 graphically show the results of the flow unit testing of the samples for both Distillate Yield ( Figure 7) and Distillate Selectivity ( Figure 8).

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Abstract

Cette invention concerne la composition, le procédé de production et l'utilisation d'un catalyseur d'hydrocraquage qui est constitué d'une nouvelle zéolithe Y qui présente un pic mésoporeux, déterminé par des mesures d'adsorption d'azote, exceptionnellement bas autour de la plage des 40 A (angström). Les catalyseurs d'hydrocraquage selon l'invention manifestent un rendement de distillat et une sélectivité améliorés ainsi que des taux de conversion améliorés à des températures plus basses que les catalyseurs d'hydrocraquage classiques contenant des zéolithes Y. Les catalyseurs d'hydrocraquage selon l'invention sont particulièrement utiles dans les procédés d'hydrocraquage ci-décrits, notamment pour la conversion de charges d'hydrocarbures lourds tels que les gazoles et les queues de tours sous vide et une maximisation associée et/ou une sélectivité améliorée du rendement de distillat obtenu à partir desdits procédés d'hydrocraquage.
PCT/US2012/070502 2012-12-19 2012-12-19 Catalyseur d'hydrocraquage mésoporeux de type zéolithe y et procédés d'hydrocraquage associés WO2014098820A1 (fr)

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PCT/US2012/070502 WO2014098820A1 (fr) 2012-12-19 2012-12-19 Catalyseur d'hydrocraquage mésoporeux de type zéolithe y et procédés d'hydrocraquage associés
EP12809073.5A EP2934745A1 (fr) 2012-12-19 2012-12-19 Catalyseur d'hydrocraquage mésoporeux de type zéolithe y et procédés d'hydrocraquage associés
SG11201504335RA SG11201504335RA (en) 2012-12-19 2012-12-19 Mesoporous zeolite -y hydrocracking catalyst and associated hydrocracking processes
CA2894483A CA2894483C (fr) 2012-12-19 2012-12-19 Catalyseur d'hydrocraquage mesoporeux de type zeolithe y et procedes d'hydrocraquage associes

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016069073A1 (fr) * 2014-10-31 2016-05-06 Chevron U.S.A. Inc. Catalyseur d'hydrocraquage de distillat moyen contenant une zéolite nanoporeuse stabilisée de type y à haut volume de nanopores
JP2018500151A (ja) * 2014-10-31 2018-01-11 シェブロン ユー．エス．エー． インコーポレイテッド 高い酸点分布を有する安定化ｙゼオライトを高含有する中間留分水素化分解触媒
WO2022101327A1 (fr) 2020-11-12 2022-05-19 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'un catalyseur d'hydrocraquage

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016069073A1 (fr) * 2014-10-31 2016-05-06 Chevron U.S.A. Inc. Catalyseur d'hydrocraquage de distillat moyen contenant une zéolite nanoporeuse stabilisée de type y à haut volume de nanopores
JP2018500151A (ja) * 2014-10-31 2018-01-11 シェブロン ユー．エス．エー． インコーポレイテッド 高い酸点分布を有する安定化ｙゼオライトを高含有する中間留分水素化分解触媒
JP2018500152A (ja) * 2014-10-31 2018-01-11 シェブロン ユー．エス．エー． インコーポレイテッド 高いナノ細孔の安定化ｙゼオライトを含有する中間留分水素化分解触媒
JP2020182947A (ja) * 2014-10-31 2020-11-12 シェブロン ユー．エス．エー． インコーポレイテッド 高い酸点分布を有する安定化ｙゼオライトを高含有する中間留分水素化分解触媒
JP2020182946A (ja) * 2014-10-31 2020-11-12 シェブロン ユー．エス．エー． インコーポレイテッド 高いナノ細孔の安定化ｙゼオライトを含有する中間留分水素化分解触媒
WO2022101327A1 (fr) 2020-11-12 2022-05-19 Shell Internationale Research Maatschappij B.V. Procédé de préparation d'un catalyseur d'hydrocraquage

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