US20090283443A1 - Catalytic composition for hydrotreating of hydrocarbons and method for hydrotreating - Google Patents

Catalytic composition for hydrotreating of hydrocarbons and method for hydrotreating Download PDF

Info

Publication number
US20090283443A1
US20090283443A1 US11/991,378 US99137806A US2009283443A1 US 20090283443 A1 US20090283443 A1 US 20090283443A1 US 99137806 A US99137806 A US 99137806A US 2009283443 A1 US2009283443 A1 US 2009283443A1
Authority
US
United States
Prior art keywords
zeolite
range
aluminum
hydrotreating
pore volume
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/991,378
Other languages
English (en)
Inventor
Ryuzo Kuroda
Masaru Ushio
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Petroleum Energy Center JPEC
JGC Catalysts and Chemicals Ltd
Original Assignee
Petroleum Energy Center PEC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Petroleum Energy Center PEC filed Critical Petroleum Energy Center PEC
Assigned to CATALYSTS & CHEMICALS INDUSTRIES CO., LTD., PETROLEUM ENERGY CENTER reassignment CATALYSTS & CHEMICALS INDUSTRIES CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KURODA, RYUZO, USHIO, MASARU
Assigned to JGC CATALYSTS AND CHEMICALS LTD. reassignment JGC CATALYSTS AND CHEMICALS LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: CATALYSTS & CHEMICALS INDUSTRIES CO., LTD.
Publication of US20090283443A1 publication Critical patent/US20090283443A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • 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
    • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/166—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
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/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
    • B01J35/643—Pore diameter less than 2 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
    • B01J35/64—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
    • B01J35/64—Pore diameter
    • B01J35/651—50-500 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
    • B01J35/64—Pore diameter
    • B01J35/653—500-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Definitions

  • the present invention relates to catalytic compositions for hydrotreating of hydrocarbons and a method of hydrotreating. More specifically, this invention relates to catalytic compositions for hydrotreating hydrocarbons by using aluminum- and titanium-inserted zeolite Y, and a method for hydrotreating hydrocarbons.
  • the zeolite Y shows high hydrocracking capability for high boiling point fractions, high hydrogenating capability, excellent selectivity for middle fractions, and high desulfurizing and high denitrogenating capability.
  • the zeolite provides excellent effects such as a high gasoline yield and a low production rate of coke and hydrogen when the obtained uncracked bottom oil is used as a feed oil for catalytic cracking.
  • the zeolite Y is a solid acid having acidity
  • the zeolite Y is used as solid acid catalyst in hydrotreating or in hydrocracking hydrocarbon oils.
  • ultra-stable zeolite Y (USY) having been subjected to de-aluminum processing is advantageously used.
  • the USY has a unit cell dimension smaller than that of synthetic zeolite Y and also has a high SiO 2 /Al 2 O 3 molar ratio, and therefore the USY has high heat resistance.
  • pore volume of pores in the range from 20 to 600 ⁇ is larger than that of the synthetic zeolite Y.
  • the acidic characteristic of the zeolite Y varies according to the SiO 2 /Al 2 O 3 molar ratio, and since the ultra-stable zeolite Y (USY) having been subjected to de-aluminum processing has a high SiO 2 /Al 2 O 3 molar ratio, therefore the acidity of solid acid is strong, but the acid amount is small.
  • the zeolite Y used for hydrotreating of hydrocarbon oils is required to have a large mesopore volume and a large amount of solid acid.
  • Patent document 1 discloses faujasite-type zeolite having two types of pores, homogeneous micropores and homogeneous mesopores and a method of producing the zeolite.
  • the document describes that the zeolite has the mesopores suited to cracking of residual oils in addition to the micropores, and can advantageously be used for catalytically cracking residual oils.
  • the zeolite is used for hydrotreating of hydrocarbons, the effect of dispersing heavier hydrocarbons is not sufficient because pore volume of pores having the diameter larger than 50 ⁇ is small, and therefore the further improvement has been desired.
  • Patent document 2 discloses novel zeolite having a large number of mesopores and providing excellent solid acid catalyst.
  • the novel zeolite has the aluminum-silicon atomic ratio (Al/Si) in the range from 0.01 to 0.2, and volume percentage of mesopore volume of pores having the particle diameters in the range from 50 to 1000 ⁇ in the range from 30 to 50%.
  • the mesopore volume is 0.14 cc/g or more, and a percentage of 4-coordinate aluminum atoms against the total aluminum atoms is 25% or more, which indicates that the zeolite has a large mesopore volume.
  • Patent document 2 discloses a method of producing novel zeolite including a step of immersing ultra-stable zeolite Y (USY) having a large mesopore volume as a feed material in an aqueous solution of sodium aluminate for reaction to insert aluminum atoms into the zeolite frame, and the conditions for reaction include a concentration of aluminum in the aqueous solution in the range from 0.03 to 0.1 mole/I, pH of the aqueous solution in the range from 11 to 12, the reaction temperature in the range from 10 to 40° C., and the reaction time in the range from 1 to 200 hours.
  • USY ultra-stable zeolite Y
  • Japanese Patent Publication No. 3341011 discloses a catalyst carrier made from zeolite in which ultra-fine particles of an oxide of a metal belonging to the titanium group are introduced in the mesopores for forming a complex and an atomic ratio of aluminum and silicon included in the zeolite (Al/Si) is in the range from 0.01 to 0.1, and catalyst in which a metal having the hydrogenating capability is carried on the catalyst carrier.
  • Patent document 3 also discloses a method of preparing the catalyst carrier, and the method uses zeolite having mesopores as a feed material and includes the steps of contacting an aqueous solution of salt of titanium group to the zeolite at the pH of 0.8 to 2, washing the zeolite with water, drying the zeolite and then sintering the zeolite at a temperature in the range from 400 to 600° C.
  • ultra-fine particles of metallic oxide of the titanium group with a diameter in the range from 5 to 10 nm are present on inner surface of the mesopores of the zeolite, and furthermore 6-coordinate aluminum removed from the frame structure is present in the zeolite.
  • a first object of the present invention is to solve the aforementioned problems and provide catalytic composition for hydrotreating of hydrocarbons by using aluminum- and titanium-inserted zeolite Y with specific characteristics and a method for hydrotreating thereof, in which the zeolite Y shows high hydrocracking capability for high boiling point fractions, high hydrogenating capability and high desulfurizing and high denitrogenating capability when used in hydrotreating of hydrocarbons such as DAO.
  • a second object of the present invention is to provide catalytic composition for hydrotreating of hydrocarbons by using aluminum- and titanium-inserted zeolite Y with specific characteristics and a method for hydrotreating thereof, in which the zeolite Y provides excellent effects such as a high gasoline yield and a low production rate of hydrogen and coke when the obtained uncracked bottom oil is used as a feed oil for catalytic cracking.
  • a third object of the present invention is to provide catalytic composition for hydrotreating of hydrocarbons by using aluminum- and titanium-inserted zeolite Y with specific characteristics and a method for hydrotreating thereof, in which the zeolite Y provides excellent effects such as high hydrocracking capability for high boiling point fractions, high hydrogenating capability, high desulfurizing and high denitrogenating capability, and a high yield of gasoline, kerosene or light oil fractions.
  • the inventors of the present invention have studied for achieving the aforementioned objects, and have found catalytic composition for hydrotreating of hydrocarbons by using aluminum- and titanium-inserted zeolite Y with specific characteristics of the improved acidic characteristics and pore structure, and the catalytic composition shows excellent effects for hydrotreating for hydrocarbon oils containing high boiling point fractions (high molecular hydrocarbons) such as deasphalted oil (DAO), and as a result the inventors have accomplished the present invention.
  • hydrocarbon oils containing high boiling point fractions high molecular hydrocarbons
  • DAO deasphalted oil
  • the present invention relates to catalytic composition for hydrotreating of hydrocarbons in which a metal component for hydrogenation is carried on a carrier comprising of aluminum- and titanium-inserted zeolite Y with the following characteristics (a)-(g) and a porous inorganic oxide:
  • unit cell dimension (UD) is in a range from 24.25 to 24.60 ⁇ ;
  • crystallinity is 95% or more;
  • specific surface area (SA) is 500 m 2 /g or more;
  • total pore volume of a group of pores having a diameter of 600 ⁇ or less (PVt) is in a range from 0.45 to 0.70 ml/g;
  • pore volume of a group of pores having a diameter in a range from 100 to 600 ⁇ (PVm) is in a range from 0.10 to 0.40 ml/g;
  • pore volume of a group of pores having a diameter in a range from 35 to 50 ⁇ (PVs) is in a range from 0.03 to 0.15 ml/g;
  • percentage of 4-coordinate aluminum atoms against total aluminum atoms in the zeolite is 60 atom % or more.
  • the present invention relates to catalytic composition for hydrotreating of hydrocarbons in which the aluminum- and titanium-inserted zeolite Y has the following characteristics:
  • a third invention of the present invention relates to a method for hydrotreating of hydrocarbons having high boiling point fractions by using the catalytic composition for hydrotreating of hydrocarbons.
  • the aluminum- and titanium-inserted zeolite Y with specific characteristics included in the catalytic composition for hydrotreating of hydrocarbons in the present invention is the zeolite Y with de-aluminum processing which aluminum and titanium are inserted a frame thereof, and the aluminum and titanium inserted into the frame are supposed to be inserted into an outer surface of the frame of the zeolite Y. For that reason, the aluminum- and titanium-inserted zeolite Y has more solid acidic sites than the zeolite Y with de-aluminum processing, because more amounts of the aluminum and titanium exist in the outer surface of the frame.
  • the catalytic composition for hydrotreating of hydrocarbons of the present invention shows excellent effects for high hydrocracking capability for high boiling point fractions, high hydrogenating capability and high desulfurizing and high denitrogenating capability by using for hydrotreating of hydrocarbon oils containing high boiling point fractions such as DAO.
  • the high boiling point fractions of the obtained uncracked bottom oil are suitable for a feed oil for catalytic cracking because of a high yield of gasoline, kerosene or light oil fractions, and a low production rate of hydrogen and coke when they are used as a feed oil for catalytic cracking.
  • FIG. 1 is a view showing an 27 Al MAS NMR spectrum of the Na-zeolite Y (Na-Y);
  • FIG. 2 is a view showing an 27 Al MAS NMR spectrum of the ultra-stable zeolite Y (USY-12);
  • FIG. 3 is a view showing 27 Al MAS NMR spectrums of the aluminum- and titanium-inserted zeolite Y (Ti.USY-12AC);
  • FIG. 4 is a view showing IR spectrums of the USY-12 and Ti.USY-12AC.
  • FIG. 5 is a view showing pore distributions in the USY-12AC and USY-12ACTi.
  • Aluminum and titanium-inserted zeolite Y as used herein means zeolite Y with aluminum and titanium inserted in a frame structure of the zeolite Y having been subjected to processing for removing aluminum. Description is provided below for the aluminum and titanium-inserted zeolite Y according to the present invention.
  • the unit cell dimension (UD) of the aluminum and titanium-inserted zeolite Y is in the range from 24.25 to 24.60 ⁇ .
  • the zeolite Y with the unit cell dimension (UD) less than 24.25 ⁇ has a high SiO 2 /Al 2 O 3 molar ratio in the frame structure and includes only a small amount of a solid acid which is an activation point of cracking of hydrocarbons, and therefore the cracking activity of a catalytic composition for hydrotreating including the zeolite tends to decline during use.
  • the zeolite Y with the unit cell dimension (UD) more than 24.60 ⁇ has low heat resistance, and a frame structure of zeolite is broken during hydrotreating, and the cracking activity of the catalytic composition for hydrotreating including the zeolite declines.
  • the unit cell dimension (UD) of the aluminum and titanium-inserted zeolite Y according to the present invention is preferably in the range from 24.30 to 24.50 ⁇ .
  • Crystallinity in the zeolite Y described above is required to be 95% or more. When the crystallinity is lower than 95%, the catalytic composition for hydrotreating including the zeolite Y does not provide desired effects.
  • the crystallinity of the zeolite Y is preferably in the range from 100 to 150%. The crystallinity is calculated through the following equation:
  • H is a total peak height on each of the (331), (511), (440), (533), (642) and (555) planes for X-ray diffraction of the zeolite Y above
  • H 0 is a peak height for each of the same planes for X-ray diffraction of zeolite Y procurable from the market (produced by Union Carbide; SK-40). The calculation is based on the assumption that the crystallinity of the zeolite Y procurable from the market is 100.
  • a specific surface area of the zeolite Y described above (when measured by means of the BET method of nitrogen adsorption) is 500 m 2 /g or more. When the specific surface area (SA) is less than 500 m 2 /g, the solid acid sites effective for the hydrotreating reaction can not be obtained, and the catalytic composition for hydrotreating including the zeolite can not provide the desired effects.
  • a specific surface area (SA) of the zeolite is preferably in the range from 550 to 800 m 2 /g.
  • a total pore volume (PVt) of a group of pores each having a diameter of 600 ⁇ or less is in the range from 0.45 to 0.70 ml/g.
  • the catalytic composition for hydrotreating including the zeolite can not provide the desired effects.
  • the total pore volume (PVt) is lager than 0.70 ml/g, sometimes a crystallinity of the zeolite may decrease.
  • the total pore volume (PVt) is preferably in the range from 0.50 to 0.65 ml/g.
  • the total pore volume (PVt) of pores each having a diameter in the range described above was obtained from a pore distribution obtained by calculating and analyzing data for adsorption and desorption of nitrogen by means of the B.J.H method.
  • a pore volume (PVm) of a group of pores each having a diameter in the range from 100 to 600 ⁇ is in the range from 0.10 to 0.40 ml/g.
  • the pore volume (PVm) is smaller than 0.10 ml/g, the effect of diffusing hydrocarbons having high molecular weights is not sufficient, and the catalytic composition for hydrotreating of hydrocarbons including the zeolite can not sufficiently crack high molecular weight hydrocarbons such as DAO.
  • the pore volume (PVm) is more than 0.40 ml/g, a crystallinity of the zeolite may disadvantageously decrease, and sometimes the catalytic compositions for hydrotreating of hydrocarbons using the zeolite can not provide the desired effects.
  • the pore volume (PVm) is preferably in the range from 0.15 to 0.35 ml/g.
  • the pore volume (PVs) of a group of pores each having a diameter in the range from 35 to 50 ⁇ is in the range from 0.03 to 0.15 ml/g.
  • the pore volume (PVs) is preferably in the range from 0.05 to 0.10 ml/g.
  • An aluminum atom constituting a frame structure of zeolite Y is a 4-coordinate atom, while an aluminum atom outside the frame structure of the zeolite Y is a 6-coordinate one.
  • a percentage of 4-coordinate aluminum atoms against total aluminum atoms (4-coordinate aluminum atoms and 6-coordinate aluminum atoms) in the zeolite Y with aluminum and titanium inserted therein is required to be 60 atomic percent or more.
  • the catalytic composition for hydrotreating of hydrocarbons including the zeolite can not provide the desired effect, for instance, in the cracking capability of high-boiling point fractions such as DAO.
  • the percentage of 4-coordinate aluminum atoms against total aluminum atoms in the zeolite with aluminum and titanium inserted therein is preferably 70 atomic percent or more.
  • the percentage of 4-coordinate aluminum in the zeolite was obtained from the 27 Al MAS NMR spectrum measured by the nuclear magnetic resonance instrument (NMR) VXR-400 produced by VARIAN Corp.
  • An amount of titania (TiO 2 ) included in the zeolite Y with aluminum and titanium inserted therein is preferably in the range from 0.5 to 15 weight %.
  • the amount of titania (TiO 2 ) is smaller than 0.5 weight %, a yield of gasoline, kerosene or light oil may decrease.
  • the amount of titania (TiO 2 ) is larger than 15 weight %, the cracking activity may decrease.
  • the amount of titania (TiO 2 ) is preferably in the range from 1 to 10 weight %.
  • the amount of titania (TiO 2 ) in the zeolite is measured with a fluorescent X-ray analyzer.
  • the zeolite Y with aluminum and titanium inserted therein according to the present invention should preferably have the characteristics (h) and (i) described below in addition to those described above.
  • a ratio of the pore volume (PVm) of a group of pores each having a diameter in the range from 100 to 600 ⁇ , to the total pore volume (PVt) of a group of pores each having a diameter of 600 ⁇ or less should preferably be 0.30 or more.
  • the (PVm/PVt) ratio should more preferably be in the range from 0.30 to 0.50.
  • the ratio (PVm/PVs) of the pore volume (PVm) of a group of pores each having a diameter in the range from 100 to 600 ⁇ , to the pore volume (PVs) of a group of pores each having a diameter in the range from 35 to 50 ⁇ is preferably 2.5 or more.
  • the ratio (PVm/PVs) is more preferably in the range from 2.5 to 4.5.
  • the zeolite Y with aluminum and titanium inserted therein described above is prepared as described below.
  • the zeolite is heated in a steam atmosphere to prepare an ultra-stable zeolite Y (USY) with the unit cell dimension (UD) in the range from 24.25 to 24.60 ⁇ . Then, the USY is processed with an acidic aqueous solution containing titanium such as an aqueous solution of titanyl sulfate at pH 1.5 or below. Furthermore, the USY is filtered, washed, and dried to prepare the zeolite with aluminum removed from the frame structure and also with titanium inserted to the frame structure (Al-removed and titanium-inserted zeolite Y).
  • USY ultra-stable zeolite Y
  • UD unit cell dimension
  • the titanium-inserted zeolite Y is suspended in an acidic aqueous solution or a neutral aqueous solution such materials as sulfuric acid, ammonium sulfate, and ammonium acetate with the pH preferably in the range from 4 to 7 and the suspension is heated at a temperature in the range from 100 to 200° C. for 3 to 30 hours. Then the suspension is filtered, washed, and dried to obtain aluminum removed from the suspension, and a portion of the recovered aluminum is re-inserted into a frame structure of the zeolite to prepare the zeolite Y with aluminum and titanium inserted therein.
  • an acidic aqueous solution or a neutral aqueous solution such materials as sulfuric acid, ammonium sulfate, and ammonium acetate with the pH preferably in the range from 4 to 7 and the suspension is heated at a temperature in the range from 100 to 200° C. for 3 to 30 hours.
  • the suspension is filtered, washed, and dried to obtain aluminum removed from the suspension
  • the zeolite Y with aluminum removed and with titanium inserted is suspended in the acidic or neutral aqueous solution, so that a reduction of crystallinity never occurs in the USY. Furthermore the zeolite is heated at the temperature in the range from 100 to 200° C. for 3 to 30 hours, so that the removed aluminum out of the frame structure of the zeolite can easily be re-inserted into the zeolite frame, and the zeolite Y having the porous structure can be obtained.
  • the USY prepared by the method described above is suspended in an acidic or neutral aqueous solution of such materials as sulfuric acid, ammonium sulfate, or ammonium acetate with the pH preferably in the range from 4 to 7 is suspended, and the suspension is heated at a temperature from 100 to 200° C. for 3 to 30 minutes. Then the suspension is filtered and washed, and a portion of aluminum removed from the zeolite Y is again inserted into the frame structure of the zeolite.
  • an acidic or neutral aqueous solution of such materials as sulfuric acid, ammonium sulfate, or ammonium acetate with the pH preferably in the range from 4 to 7 is suspended, and the suspension is heated at a temperature from 100 to 200° C. for 3 to 30 minutes. Then the suspension is filtered and washed, and a portion of aluminum removed from the zeolite Y is again inserted into the frame structure of the zeolite.
  • the aluminum-inserted zeolite Y is processed with a titanium containing aqueous solution such as an aqueous solution of titanium lactate or an aqueous solution of titanyl sulfate, and the zeolite is filtered, washed, and dried to obtain the zeolite Y with aluminum and titanium inserted therein.
  • a titanium containing aqueous solution such as an aqueous solution of titanium lactate or an aqueous solution of titanyl sulfate
  • porous inorganic oxides comprising the catalytic composition for hydrotreating according to the present invention
  • those generally used for preparing a catalytic composition for hydrotreating or for hydrocracking may be used.
  • the porous inorganic compositions available in the present invention include alumina, silica, titania, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphor-alumina, silica-alumina-boria, phosphor-alumina-boria, phosphor-alumina-silica, silica-alumina-titania, and silica-alumina-zirconia.
  • a porous and inorganic oxide including alumina as a main component can advantageously be used for carrying out the present invention.
  • Any known metallic component used in the hydrotreating can be used as a metallic component of a catalytic composition for hydrotreating according to the present invention, and there can be enlisted, for instance, metals belonging to Group 8 and/or Group 6A in the periodic table.
  • the preferable metallic components include combinations of molybdenum or tungsten belonging to Group 6A and a cobalt or nickel belonging to Group 8, or metals belonging to Platinum Group.
  • a content of the zeolite Y with aluminum and titanium inserted therein can be changed according to the necessity.
  • the content is preferably in the range from 2 to 80 weight % (namely a content of the porous inorganic oxide in the range from 98 to 20 weight %), more preferably in the range from 20 to 70 weight % (namely a content of the porous inorganic oxide in the range from 80 to 30 weight %) when calculated as a weight of the carrier (a combination of the zeolite Y with aluminum and titanium inserted therein and the porous inorganic oxide).
  • An amount of metallic components in a catalytic composition for hydrotreating according to the present invention may be the same as that in the ordinary composition for hydrotreating.
  • the content as calculated as oxide of molybdenum, tungsten, cobalt, nickel or the like is in the range from 5 to 30 weight %, and when calculated as a content of a metal belonging to Platinum Group is in the range from 0.01 to 2 weight %.
  • the catalytic composition for hydrotreating of hydrocarbons according to the present invention is produced, for instance, by mixing the zeolite Y with aluminum and titanium inserted therein described above with a precursor of a porous inorganic oxide, molding the mixture to a desired form by means of any known method, drying and sintering to produce the carrier, impregnating metallic components for hydrogenation by any known method, and drying and sintering the metal-impregnated carrier.
  • the catalytic composition for hydrotreating according to the present invention is produced by mixing metallic components for hydrogenation into a combination of the zeolite Y with aluminum and titanium inserted therein and a precursor of a porous inorganic oxide, molding the mixture to a desired form, and then drying and sintering the mixture.
  • the precursor for porous inorganic oxide as used herein indicates any material that can be used to prepare a porous inorganic oxide comprising the catalytic composition for hydrotreating by being mixed with other component for hydrotreating.
  • a temperature for sintering is preferably in the range from 400 to 650° C.
  • the catalytic composition for hydrotreating of hydrocarbons according to the present invention can be used for hydrotreating of any hydrocarbon oil, and especially can advantageously be used for hydrotreating of a hydrocarbon containing high boiling point fractions.
  • high boiling point fraction indicates a hydrocarbon containing fractions, which can be obtained at a boiling point of 560° C. or more (560° C. + ) by 30 weight % or more.
  • the ordinary conditions for hydrotreating may be employed also in the present invention, and the conditions include a temperature in the range from 300 to 500° C., a hydrogen pressure in the range from 4 to 30 MPa, a liquid space velocity in the range from 0.1 to 10 hr ⁇ 1 .
  • NaY-type zeolite Na-Y having the characteristics as shown in Table 3 and showing the 27 Al MAS NMR spectrum as shown in FIG. 1 was suspended in 90 liters of warm water at a temperature of 60° C. 2.56 Kg of ammonium sulfate, which was equivalent in the mole number, was added to the zeolite, and was ion-exchanged at a temperature of 70° C. for one hour with agitation.
  • H-Y type zeolite (NH 4 65 Y) was sintered for one hour in saturated steam atmosphere at a temperature of 660° C. in a rotary steaming device to obtain H-Y type zeolite (HY-5).
  • This zeolite HY-5 was suspended in 90 liters of warm water at 60° C.
  • 7.92 Kg of ammonium sulfate, which was equivalent of 3 mole times of the zeolite, was added to the solution, and the mixture solution was agitated for one hour at a temperature of 90° C. for ion-exchanging, filtered, and the filtrate was washed with 90 liters of deionized water at 60° C.
  • the filtrate was dried for 20 hours at a temperature of 130° C., and was pulverized to obtain the zeolite Y (NH 4 85 Y) ion-exchanged by 85%.
  • the zeolite NH 4 85 Y was sintered in saturated steam atmosphere for one hour at a temperature of 700° C. in a rotary steaming device to obtain about 8 Kg of ultra-stable zeolite Y (USY-5).
  • Characteristics of the USY-12 are shown in Table 3, and the 27 Al MAS NMR spectrum was shown in FIG. 2 .
  • the peak at 60 ppm shows the presence of a zeolite frame-structured 4-coordinate aluminum atom, while a peak at 0 ppm indicates the presence of a 6-coordinate aluminum atom outside the zeolite frame structure.
  • Ti.USY-12 shows a peak of the 27 Al MAS NMR spectrum at 0 ppm, which indicates the presence of 6-coordinate aluminum atom outside the frame structure of the zeolite.
  • Characteristics of the zeolite Ti.USY-12AC is shown in Table 3, and the 27 Al MAS NMR spectrum is shown in FIG. 3 .
  • the peak for 6-coordinate aluminum (at 0 ppm) indicating the presence of aluminum outside the zeolite frame structure decrease as compared to the USY-12
  • the peak for 4-coordinate aluminum (at 60 ppm) indicating the presence of aluminum atoms in the zeolite frame structure increase, which indicates that aluminum outside the zeolite frame structure was inserted into the frame of the zeolite Y in the Ti.USY-12AC.
  • IR spectrums for the USY-12 and Ti.USY-12AC are shown in FIG. 4 .
  • a peak caused by Si—O—Ti asymmetric stretching vibration appear at 970 cm ⁇ 1 in the MFI type titanosilicate and at 945 cm ⁇ 1 in the HY type zeolite in proportion to an amount of introduced TiO 2 .
  • the peak at about 970 cm ⁇ 1 was not confirmed in the USY-12, but the peak was clearly confirmed in the Ti.USY-12AC. From this case, it can be determined that titanium was inserted into the frame structure of the zeolite Y.
  • Characteristics of the USY-12ACTi are shown in Table 3, and pore distribution of the USY-12ACTi is shown in FIG. 5 .
  • the IR spectrum of the zeolite (USY-12ACTi) was measured, and a peak of about 970 cm ⁇ 1 was identified like in Example for reference 3 to indicate that titanium was inserted into a frame structure of the zeolite Y.
  • the aluminum sulfate solution was added at a constant rate with a rotary pump in the sodium aluminate solution to adjust the pH from 7.1 to 7.3 over 10 minutes.
  • the obtained suspended slurry was agitated and aged for 1 hour at 60° C.
  • the aged slurry was dehydrated with a flat plate filter, and the filtrate was washed with 150 liters of ammonia aqueous solution with the concentration of 0.3 weight %.
  • the cake-like slurry after washing was diluted with ion-exchanged water to adjust the concentration to 10 weight % calculated as a concentration of Al 2 O 3 .
  • pH of the slurry was adjusted to 10.5 with ammonia water with the concentration of 15 weight %.
  • the slurry was removed into an aging tank with a circulator and was aged for 10 hours under agitation at 95° C.
  • the slurry was dehydrated with a flat plate filter, and was set in a double-armed kneader with a steam jacket to adjust a content of water to a prespecified value and then cooled to prepare an adulterant of aluminum.
  • 1.0 Kg of the aluminum adulterant calculated as a weight of Al 2 O 3 and 1.0 Kg of ultra-stable zeolite Y (USY-12) prepared in Example for reference 2 were set and kneaded at a raised temperature in a double-armed kneader with a steam jacket to adjust the water content to a prespecified value. Then the adulterant was cooled and further kneaded for 10 minutes. The obtained adulterant was molded to column-like pellets with a diameter of 1.8 mm with an extrusion molding machine, and the product was dried at 110° C. for 16 hours. The dried pellets were sintered for 3 hours at 550° C. in an electric oven to prepare a carrier.
  • the solution was impregnated in the carrier described above. Impregnation was performed by setting 1000 g of the carrier in a rotary blender capable of being vacuum-deaerated and left there for 5 minutes being deaerated with a vacuum pump. A quantity of the prepared solution for impregnation was adjusted to match a water absorption coefficient of the carrier. Operation of the vacuum pump was added after the solution was added, and then was further rotated for 20 minutes so that the solution for impregnation was fully impregnated in the carrier. The impregnated sample was taken out and set in a rotary drier with a temperature rising program, and the temperature was changed from 40° C. to 250° C. over 1 hour for drying the sample. The dried sample was set in an electric oven and was sintered for 1 hour at 550° C. to obtain a catalyst A. Characteristics of the catalyst A is as shown in Table 4.
  • 1.0 Kg of aluminum adulterant prepared in Comparative Example 1 calculated as a weight of Al 2 O 3 and 1.0 Kg of zeolite Y with aluminum and titanium inserted therein (Ti.USY-12AC) prepared in Example for reference 3 were kneaded and heated in a double-armed kneader with a steam jacket to adjust the water content to a prespecified value, and then was cooled and kneaded for 10 minutes.
  • the obtained adulterant was processed like in Comparative Example 1 to prepare a catalyst B. Characteristics of the catalyst B is as shown in Table 4.
  • Hydrocracking of DAO was performed with the catalysts A to D in a fixed bed flow reactor to measure cracking, desulfurizing, and denitrogenating activities of each catalyst. Characteristics of the DAO and reaction conditions are as shown below.
  • Reaction temperature (° C.) 380 Liquid space velocity (hr ⁇ 1 ) 0.50 Hydrogen/oil ratio (Nm 3 /kl) 500 H 2 partial pressure (MPa) 13
  • the product oil was set in an evaporator to measure contents of fractions boiling at a temperature of 375° C. or more (375° C. + ) and those boiling at a temperature of 560° C. or more (560° C. + ), and assessed reduction rate of fractions to the amount of feed oil at cracking activities of the catalysts. Assuming that the reduction rate of the fractions (375° C. + ) and that of the fractions (560° C. + ) are 100 in case of catalyst A (Comparative Example 1) at 380° C. respectively, relative values of reduction rates with the catalysts B to D were obtained as cracking activities of the catalysts, and the values are as shown in Table 1. Also characteristics of the product oil obtained in the reaction are as shown in Table 1.
  • Tests for assessing characteristics of product oils in relation to the adaptability to catalytic cracking were performed according to the ASTM-MAT method (using a small size activity testing device) by using product oils which were fractions having the boiling point of 375° C. or higher (375° C. + ) as feed oils and also using the commercially available catalyst FCC catalyst (produced by Catalysts & Chemicals Industries Co., Ltd.). Results of the testing are shown in Table 2.
  • Catalyst Comp. Comp. Catalyst Unit Ex. 1 Ex. 1 Ex. 2 Ex. 2 Al 2 O 3 wt % 43.1 42.2 42.0 44.2 SiO 2 wt % 36.2 35.2 35.8 35.1 MoO 3 wt % 16.0 16.6 16.2 16.1 NiO wt % 4.50 4.63 4.50 4.52 TiO 2 wt % — 1.42 1.40 — SA m 2 /g 403 394 401 324 Cr.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
US11/991,378 2005-09-12 2006-09-06 Catalytic composition for hydrotreating of hydrocarbons and method for hydrotreating Abandoned US20090283443A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2005-264274 2005-09-12
JP2005264274 2005-09-12
PCT/JP2006/317612 WO2007032232A1 (ja) 2005-09-12 2006-09-06 炭化水素の水素化処理用触媒組成物および水素化処理方法

Publications (1)

Publication Number Publication Date
US20090283443A1 true US20090283443A1 (en) 2009-11-19

Family

ID=37864831

Family Applications (2)

Application Number Title Priority Date Filing Date
US11/991,378 Abandoned US20090283443A1 (en) 2005-09-12 2006-09-06 Catalytic composition for hydrotreating of hydrocarbons and method for hydrotreating
US13/067,687 Active US8148285B2 (en) 2005-09-12 2011-06-21 Method for manufacturing zeolite Y with aluminum and titanium inserted therein

Family Applications After (1)

Application Number Title Priority Date Filing Date
US13/067,687 Active US8148285B2 (en) 2005-09-12 2011-06-21 Method for manufacturing zeolite Y with aluminum and titanium inserted therein

Country Status (6)

Country Link
US (2) US20090283443A1 (ja)
EP (1) EP1938898B1 (ja)
JP (1) JP5100388B2 (ja)
KR (1) KR101378622B1 (ja)
CN (1) CN101262945B (ja)
WO (1) WO2007032232A1 (ja)

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100122935A1 (en) * 2007-05-01 2010-05-20 Nippon Oil Corporation Method of producing liquid fuel
US20110108459A1 (en) * 2009-11-10 2011-05-12 IFP Energies Nouvelles Hydrocracking process using a zeolite modified by basic treatment
US20110220549A1 (en) * 2010-03-11 2011-09-15 Exxonmobil Research And Engineering Company Low Small Mesoporous Peak Cracking Catalyst and Method of Using
US20120085681A1 (en) * 2009-08-21 2012-04-12 Cosmo Oil Co., Ltd. Support for hydrocracking catalyst of hydrocarbon oil, hydrocracking catalyst, and method for hydrocracking of hydrocarbon oil
US8932454B2 (en) 2008-09-18 2015-01-13 Exxonmobile Research And Engineering Co. Mesoporous Y hydrocracking catalyst and associated hydrocracking processes
FR3012125A1 (ja) * 2013-10-22 2015-04-24 China Petroleum & Chemical
US20150247095A1 (en) * 2014-01-30 2015-09-03 Kior, Inc. Method of biomass conversion using a multifunctional catalyst system
US9855552B2 (en) 2013-10-22 2018-01-02 China Petroleum & Chemical Corporation Metal modified y zeolite, its preparation and use
US9943836B2 (en) 2013-10-22 2018-04-17 China Petroleum & Chemical Corporation Metal modified Y zeolite, its preparation and use
US20180148651A1 (en) * 2015-08-04 2018-05-31 Saudi Arabian Oil Company Integrated process for producing anode grade coke
US10357761B2 (en) 2014-05-22 2019-07-23 Saudi Arabian Oil Company Catalyst for fluidized catalytic cracking and method for fluidized catalytic cracking
US11142703B1 (en) 2020-08-05 2021-10-12 Saudi Arabian Oil Company Fluid catalytic cracking with catalyst system containing modified beta zeolite additive
US11154845B1 (en) 2020-07-28 2021-10-26 Saudi Arabian Oil Company Hydrocracking catalysts containing USY and beta zeolites for hydrocarbon oil and method for hydrocracking hydrocarbon oil with hydrocracking catalysts
US11274068B2 (en) 2020-07-23 2022-03-15 Saudi Arabian Oil Company Process for interconversion of olefins with modified beta zeolite
US11332678B2 (en) 2020-07-23 2022-05-17 Saudi Arabian Oil Company Processing of paraffinic naphtha with modified USY zeolite dehydrogenation catalyst
US11420192B2 (en) 2020-07-28 2022-08-23 Saudi Arabian Oil Company Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts
US11446645B2 (en) 2020-07-02 2022-09-20 Saudi Arabian Oil Company FCC catalyst compositions for fluid catalytic cracking and methods of using the FCC catalyst compositions
US11484868B2 (en) 2020-09-30 2022-11-01 Saudi Arabian Oil Company Modified large crystallite USY zeolite for hydrocracking hydrocarbon oil
US11618858B1 (en) 2021-12-06 2023-04-04 Saudi Arabian Oil Company Hydrodearylation catalysts for aromatic bottoms oil, method for producing hydrodearylation catalysts, and method for hydrodearylating aromatic bottoms oil with hydrodearylation catalysts
US11725149B1 (en) 2022-06-13 2023-08-15 Saudi Arabian Oil Company Fluidized catalytic cracking processes and additives for improving gasoline yield and quality

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5176151B2 (ja) * 2008-05-19 2013-04-03 コスモ石油株式会社 高オクタン価ガソリン基材の製造方法
US8361434B2 (en) * 2008-09-18 2013-01-29 Exxonmobil Research And Engineering Company Extra mesoporous Y zeolite
FR2940265B1 (fr) * 2008-12-22 2011-06-10 Total Raffinage Marketing Zeolithes y modifiees, leur procede de fabrication et leur utilisation
US9242234B2 (en) 2008-12-22 2016-01-26 Centre National De La Recherche Scientifique Modified Y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof
CN101519316B (zh) * 2009-04-15 2012-07-25 北京师范大学 一种泡沫沸石颗粒及其制备方法
CA2760181C (en) * 2009-04-29 2016-12-20 Pq Corporation Zeolite y
JP6022454B2 (ja) 2010-08-02 2016-11-09 サウジ アラビアン オイル カンパニー 炭化水素油用水素化分解触媒、水素化分解触媒の製造方法、及び水素化分解触媒を用いた炭化水素油の水素化分解方法
PH12013000353B1 (en) * 2012-12-05 2015-06-01 Cosmo Oil Co Ltd Hydrodesufurization catalyst for hydrocarbon oil
JP6013259B2 (ja) * 2013-04-03 2016-10-25 日揮触媒化成株式会社 水素化処理触媒用担体、その製造方法、水素化処理触媒、およびその製造方法
JP6660896B2 (ja) * 2016-02-01 2020-03-11 日揮触媒化成株式会社 炭化水素油の水素化処理触媒、その製造方法、および水素化処理方法
WO2017135193A1 (ja) * 2016-02-01 2017-08-10 日揮触媒化成株式会社 炭化水素油の水素化処理触媒、その製造方法、および水素化処理方法
US10941354B1 (en) 2019-10-01 2021-03-09 Saudi Arabian Oil Company Hydrocracking catalyst comprising a beta zeolite (*BEA) framework substituted with Ti and Zr and methods for its preparation and use
US11384300B2 (en) * 2019-12-19 2022-07-12 Saudi Arabian Oil Company Integrated process and system to upgrade crude oil

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4943545A (en) * 1987-06-08 1990-07-24 Mobil Oil Corporation Activation of zeolites
US5098687A (en) * 1984-04-26 1992-03-24 Uop Substituted aluminosilicate compositions and process for preparing same
US5601798A (en) * 1993-09-07 1997-02-11 Pq Corporation Process for preparing zeolite Y with increased mesopore volume
US5686374A (en) * 1994-09-01 1997-11-11 Japan Energy Corporation Catalyst for hydroprocessing

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2933708B2 (ja) * 1990-11-22 1999-08-16 触媒化成工業株式会社 改質ｙ型ゼオライト・その製法およびそれを使用した炭化水素接触分解用触媒組成物
JP3684265B2 (ja) * 1996-03-26 2005-08-17 触媒化成工業株式会社 均一なミクロポアと均一なメソポアの２種類の細孔を有するフォージャサイト型ゼオライトおよびその製造方法
CN1088092C (zh) * 1999-05-18 2002-07-24 中国石油化工集团公司 烃类加氢精制催化剂
JP3341011B2 (ja) * 1999-05-28 2002-11-05 独立行政法人産業技術総合研究所 触媒担体及び水素化用触媒
JP4394787B2 (ja) * 1999-12-16 2010-01-06 独立行政法人産業技術総合研究所 芳香族炭化水素の水素化触媒組成物
JP2002255537A (ja) * 2001-02-22 2002-09-11 National Institute Of Advanced Industrial & Technology 固体酸触媒
JP4138325B2 (ja) * 2002-02-06 2008-08-27 財団法人 国際石油交流センター 修飾ゼオライトおよびそれを用いた水素化処理触媒
JP2006150185A (ja) * 2004-11-26 2006-06-15 Petroleum Energy Center 水素化分解触媒組成物
JP4484677B2 (ja) * 2004-11-26 2010-06-16 日揮触媒化成株式会社 炭化水素接触分解用触媒組成物

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5098687A (en) * 1984-04-26 1992-03-24 Uop Substituted aluminosilicate compositions and process for preparing same
US4943545A (en) * 1987-06-08 1990-07-24 Mobil Oil Corporation Activation of zeolites
US5601798A (en) * 1993-09-07 1997-02-11 Pq Corporation Process for preparing zeolite Y with increased mesopore volume
US5686374A (en) * 1994-09-01 1997-11-11 Japan Energy Corporation Catalyst for hydroprocessing

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8366911B2 (en) * 2007-05-01 2013-02-05 Nippon Oil Corporation Method of producing liquid fuel
US20100122935A1 (en) * 2007-05-01 2010-05-20 Nippon Oil Corporation Method of producing liquid fuel
US8932454B2 (en) 2008-09-18 2015-01-13 Exxonmobile Research And Engineering Co. Mesoporous Y hydrocracking catalyst and associated hydrocracking processes
US9512371B2 (en) * 2009-08-21 2016-12-06 Cosmo Oil Co., Ltd. Support for hydrocracking catalyst of hydrocarbon oil, hydrocracking catalyst, and method for hydrocracking of hydrocarbon oil
US20120085681A1 (en) * 2009-08-21 2012-04-12 Cosmo Oil Co., Ltd. Support for hydrocracking catalyst of hydrocarbon oil, hydrocracking catalyst, and method for hydrocracking of hydrocarbon oil
US20110108459A1 (en) * 2009-11-10 2011-05-12 IFP Energies Nouvelles Hydrocracking process using a zeolite modified by basic treatment
US8641889B2 (en) * 2009-11-10 2014-02-04 IFP Energies Nouvelles Hydrocracking process using a zeolite modified by basic treatment
US20110220549A1 (en) * 2010-03-11 2011-09-15 Exxonmobil Research And Engineering Company Low Small Mesoporous Peak Cracking Catalyst and Method of Using
WO2011112644A1 (en) * 2010-03-11 2011-09-15 Exxonmobil Research And Engineering Company Low small mesoporous peak cracking catalyst and method of using
US8715487B2 (en) 2010-03-11 2014-05-06 Exxonmobil Research And Engineering Company Low small mesoporous peak cracking catalyst and method of using
GB2521515B (en) * 2013-10-22 2021-04-28 China Petroleum & Chem Corp A metal modified Y zeolite, its preparation and use
FR3012125A1 (ja) * 2013-10-22 2015-04-24 China Petroleum & Chemical
US9855552B2 (en) 2013-10-22 2018-01-02 China Petroleum & Chemical Corporation Metal modified y zeolite, its preparation and use
US9943836B2 (en) 2013-10-22 2018-04-17 China Petroleum & Chemical Corporation Metal modified Y zeolite, its preparation and use
GB2521516B (en) * 2013-10-22 2021-04-21 China Petroleum & Chem Corp A metal modified Y zeolite, its preparation and use
RU2670744C2 (ru) * 2013-10-22 2018-10-25 Чайна Петролеум & Кемикал Корпорейшн Модифицированный металлом цеолит типа y и способ его получения
RU2670744C9 (ru) * 2013-10-22 2018-12-13 Чайна Петролеум & Кемикал Корпорейшн Модифицированный металлом цеолит типа y и способ его получения
US20150247095A1 (en) * 2014-01-30 2015-09-03 Kior, Inc. Method of biomass conversion using a multifunctional catalyst system
US10357761B2 (en) 2014-05-22 2019-07-23 Saudi Arabian Oil Company Catalyst for fluidized catalytic cracking and method for fluidized catalytic cracking
US10669485B2 (en) * 2015-08-04 2020-06-02 Saudi Arabian Oil Company Integrated process for producing anode grade coke
US10954447B2 (en) 2015-08-04 2021-03-23 Saudi Arabian Oil Company Integrated process for producing anode grade coke
US20180148651A1 (en) * 2015-08-04 2018-05-31 Saudi Arabian Oil Company Integrated process for producing anode grade coke
US11446645B2 (en) 2020-07-02 2022-09-20 Saudi Arabian Oil Company FCC catalyst compositions for fluid catalytic cracking and methods of using the FCC catalyst compositions
US11332678B2 (en) 2020-07-23 2022-05-17 Saudi Arabian Oil Company Processing of paraffinic naphtha with modified USY zeolite dehydrogenation catalyst
US11274068B2 (en) 2020-07-23 2022-03-15 Saudi Arabian Oil Company Process for interconversion of olefins with modified beta zeolite
US11154845B1 (en) 2020-07-28 2021-10-26 Saudi Arabian Oil Company Hydrocracking catalysts containing USY and beta zeolites for hydrocarbon oil and method for hydrocracking hydrocarbon oil with hydrocracking catalysts
US11420192B2 (en) 2020-07-28 2022-08-23 Saudi Arabian Oil Company Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts
US11142703B1 (en) 2020-08-05 2021-10-12 Saudi Arabian Oil Company Fluid catalytic cracking with catalyst system containing modified beta zeolite additive
US11484868B2 (en) 2020-09-30 2022-11-01 Saudi Arabian Oil Company Modified large crystallite USY zeolite for hydrocracking hydrocarbon oil
US11618858B1 (en) 2021-12-06 2023-04-04 Saudi Arabian Oil Company Hydrodearylation catalysts for aromatic bottoms oil, method for producing hydrodearylation catalysts, and method for hydrodearylating aromatic bottoms oil with hydrodearylation catalysts
US11725149B1 (en) 2022-06-13 2023-08-15 Saudi Arabian Oil Company Fluidized catalytic cracking processes and additives for improving gasoline yield and quality

Also Published As

Publication number Publication date
EP1938898A4 (en) 2012-08-01
US20110251049A1 (en) 2011-10-13
EP1938898B1 (en) 2019-06-12
KR101378622B1 (ko) 2014-03-26
CN101262945B (zh) 2010-05-19
JP5100388B2 (ja) 2012-12-19
EP1938898A1 (en) 2008-07-02
KR20080048060A (ko) 2008-05-30
CN101262945A (zh) 2008-09-10
US8148285B2 (en) 2012-04-03
WO2007032232A1 (ja) 2007-03-22
JPWO2007032232A1 (ja) 2009-03-19

Similar Documents

Publication Publication Date Title
US8148285B2 (en) Method for manufacturing zeolite Y with aluminum and titanium inserted therein
US10293332B2 (en) Hydrocracking catalyst for hydrocarbon oil, method for producing hydrocracking catalyst, and method for hydrocracking hydrocarbon oil with hydrocracking catalyst
EP1875963B1 (en) Process for the preparation of a cracking catalyst
KR101205602B1 (ko) 베타 제올라이트 및 ｙ 제올라이트를 포함하는 수소화분해촉매 및 나프타 제조를 위한 이의 사용 방법
US7300900B2 (en) Catalyst comprising at least one zeolite chosen from ZBM-30, SM-48 EU-2 and EU-11 and at least one Y zeolite and process of hydroconversion of hydrocarbon charges using such a catalyst
US8795513B2 (en) Hydrocracking catalyst for heavy oil and method for hydrotreating heavy oil using same
US11420192B2 (en) Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts
US20220008908A1 (en) Methods of producing hydrocracking catalyst
JP3341011B2 (ja) 触媒担体及び水素化用触媒
US6682650B2 (en) Zeolite catalyst carrier and hydrogenation catalyst using same
JP6382275B2 (ja) 高沸点留分含有炭化水素油用水素化分解触媒、高沸点留分含有炭化水素油用水素化分解触媒の製造方法、及び水素化分解触媒を用いた炭化水素油の水素化分解方法
JP2006150185A (ja) 水素化分解触媒組成物
CN111672534A (zh) 加氢裂化催化剂及其制备方法与应用
US11618858B1 (en) Hydrodearylation catalysts for aromatic bottoms oil, method for producing hydrodearylation catalysts, and method for hydrodearylating aromatic bottoms oil with hydrodearylation catalysts
US11484868B2 (en) Modified large crystallite USY zeolite for hydrocracking hydrocarbon oil

Legal Events

Date Code Title Description
AS Assignment

Owner name: PETROLEUM ENERGY CENTER, JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KURODA, RYUZO;USHIO, MASARU;REEL/FRAME:020631/0062

Effective date: 20080204

Owner name: CATALYSTS & CHEMICALS INDUSTRIES CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KURODA, RYUZO;USHIO, MASARU;REEL/FRAME:020631/0062

Effective date: 20080204

AS Assignment

Owner name: JGC CATALYSTS AND CHEMICALS LTD., JAPAN

Free format text: CHANGE OF NAME;ASSIGNOR:CATALYSTS & CHEMICALS INDUSTRIES CO., LTD.;REEL/FRAME:021798/0890

Effective date: 20080701

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION