EP2046496A2 - Hydroprocessing catalyst and process of use - Google Patents

Hydroprocessing catalyst and process of use

Info

Publication number
EP2046496A2
EP2046496A2 EP07813564A EP07813564A EP2046496A2 EP 2046496 A2 EP2046496 A2 EP 2046496A2 EP 07813564 A EP07813564 A EP 07813564A EP 07813564 A EP07813564 A EP 07813564A EP 2046496 A2 EP2046496 A2 EP 2046496A2
Authority
EP
European Patent Office
Prior art keywords
catalyst composition
zeolite
acidic
component
range
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.)
Withdrawn
Application number
EP07813564A
Other languages
German (de)
French (fr)
Other versions
EP2046496A4 (en
Inventor
Theodorus Maesen
Darren Fong
Roger Vogel
Bowmann Lee
Dennis Dykstra
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.)
Chevron USA Inc
Original Assignee
Chevron USA Inc
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 Chevron USA Inc filed Critical Chevron USA Inc
Publication of EP2046496A2 publication Critical patent/EP2046496A2/en
Publication of EP2046496A4 publication Critical patent/EP2046496A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • C10G47/04—Oxides
    • 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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7815—Zeolite Beta
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil

Definitions

  • This invention is directed to a catalyst effective in hyd reprocessing and a process employing this catalyst.
  • the literature of the refining arts contains examples of two acidic components of a hydroprocessing catalyst exhibiting synergy. The two components together are more effective than either component alone in hydroprocessing hydrocarbon feeds.
  • U.S. Pat. No. 3,535,225 discloses a hydroprocessing catalyst comprising a zeolite such as Y, a faujasite, in combination with an amorphous aluminosilicate.
  • This application discloses a catalyst composition suitable for hydroprocessing a hydrocarbonaceous feedstock, said catalyst composition comprising three acidic components acting in synergy to provide enhanced catalytic activity when compared to any of the components alone or in combinations of two. It was discovered that addition of a zeolite having a cage window in the range from about 0.47 nm to about 0.85 nm in diameter (such as zeolite beta), to a combination of a zeolite in the range from about 0.47 nm to about 0.85 nm in diameter, (such as zeolite Y) and amorphous aluminosiltcate (ASA) or delaminated clay (such as saponite) significantly enhances the activity, the diesel yield, the heavy diesel cold flow properties, the hydrodenitrification effects, and the base oil yield of the combinations of Y and ASA alone.
  • a zeolite having a cage window in the range from about 0.47 nm to about 0.85 nm in diameter such as zeolite
  • Figure 1 illustrates the improved base oil yield that occurs when employing the catalyst of this invention.
  • Figure 2 illustrates the improved dewaxed oil viscosity index that occurs when employing the catalyst of this invention.
  • the feedstocks that may be hydroprocessed using the catalyst of this invention are selected from the group consisting of petroleum distillates, solvent-deasphalted petroleum residua, shale oils, Fischer-Tropsch derived feedstocks and coal tar distillates.
  • the feedstocks contain substantial amounts of materials boiling above 200 ° F, preferably substantial amounts of materials boiling in the range 350 ° to 1100 0 F, and more preferably in the range 400 ° to 1000 ° F.
  • Suitable feedstocks include those heavy distillates normally defined as heavy straight-run gas oils and heavy cracked cycle oils, as well as conventional FCC feed and portions thereof.
  • Cracked stocks mav be obtained from thermal or catalytic cracking of various stocks, including those obtained from petroleum, gilsonite, shale and coal tar
  • the feedstocks may have been subjected to a hydrofining and/or hydrogenation treatment, which may have been accompanied by some hydrocracking, before being supplied to the hydroprocessing zone organic nitrogen content be less than 100 Parts per million organic nitroen-
  • organic nitrogen content be less than 100 Parts per million organic nitroen-
  • a preferred range is 0.5 to 1000 parts per million; more preferably, 0.5 to 100 parts per million.
  • it is preferable to maintain the organic sulfur content of the feed to a range of from 0 to 3 weight percent, preferably from 0 to 1 weight percent.
  • oils and base oils are used interchangeably in this application and refer to products boiling at or above 700° F. “Fuels” boil in the range from C 5 + to below 700° F.
  • the hydroprocessing zone containing the catalyst of this invention is preferably operated at hydrocracking conditions including a temperature in the range 400 ° to 950 ° F preferably 500 ° to 850 ° F, a pressure in the range 800 to 3500psig, preferably 1000 to 3000 psig, a liquid hourly space velocity in the range 0.1 to 5.0, preferably 0.5 to 5.0, and more preferably 0.5 to 3.0.
  • the total hydrogen supply rate (makeup and recycle hydrogen) to the hydroprocessing zone is 200 to 20,000 s.c.f preferably 2000 to 20000 scf of hydrogen per barrel of said feedstock.
  • the operating conditions in the separate hydrotreating zone include a temperature of 400 ° to 900 ° F, preferably 500 ° to 800 ° F, a pressure of 800 to 3500 psig preferably 1000 to 2500 p.s.i.g and a liquid hourly space velocity of 0.1 to 5.0, preferably 0.5 to 3.0.
  • the total hydrogen supply rate (makeup and recycle hydrogen) is 200 to 20,000 s.c.f. of hydrogen per barrel of feedstock, preferably 2000 to 20,000 s.c.f. of hydrogen per barrel of feedstock.
  • the catalyst of this invention comprises three acidic components acting in synergy to provide enhanced catalytic activity.
  • One acidic component is a zeolite having a cage window in the range from about 0.47 nm to about 0.85 nm in diameter.
  • the cage window is the narrowest part of a nanopore system, and the cage is the widest part of the nanopore system.
  • Nanopores are defined as pores smaller than 0.2 nm in diameter.
  • BEA- (beta), ISV-, BEC-, IWR-, MTW-, SSZ-31-, OFF- (offretite), MAZ- (mazzite), MOR- (mordenite), MOZ-, AFI-, ZSM-48-, and SSY-type zeolites fit this description.
  • BEA possesses a Si/AI molar ratio in the range from about 100 to about 300, preferably in the range from about 100 to about 200.
  • the website defines pore diameters of the zeolites mentioned.
  • the 2 nd acidic component is a zeolite having a cage in the range from about 0.9 nm to about 2.0 in diameter.
  • This category includes large pore zeolites such as FAU-, EMT-, ITQ-21-, ERT-, and ITQ-33-type zeolites.
  • FAU, EMT and ERT are further described at the sources indicated above.
  • ITQ-21 is described in an article, "A large-cavity zeolite with wide pore windows, and potential as an oil refining catalyst.” Corma, Avelino; Diaz-Cabanas, Maria J.; Martinez-Triguero, Joaquin; Rey, Fermando; Rius, Jordi.
  • UPV-CSIC 1 Instit ⁇ to de Tecnologia Quimica, Universidad Politecnica de Valencia, Valencia, Spain. Nature (London, United Kingdom) (2002), 418(6897), 514-517.
  • iTQ-33 is described in the article, "High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings.” Corma, Avelino; Diaz- Cabanas, Maria J.; Jorda, Jose Luis; Martinez, Columbia; Moliner, Manuel. lnstituto de Tecnologia Quimica, UPV-CSIC, Universidad Politecnica de Valencia, Valencia, Spain. Nature (London, United Kingdom) (2006), 443(7113), 842-845.
  • the FAU-type zeolite has a Si/AI molar ratio in the range from about 10 to about 100, preferably in the range from about 10 to about 80.
  • the catalyst composition of the instant invention comprises active zeolite components ranging from about 1% to about 50% of the catalyst composition.
  • the 3 rd acidic component ranges from about 10% to about 90% of the catalyst composition, and is selected from the group comprising clays and amorphous silicayalumina. If an amorphous silica-alumina component is used, it is preferably selected from the group comprising silica, alumina, titania, zirconia, magnesia and their binary and tertiary compounds. Amorphous silica-alumina component is mesoporous, comprising pores in the range from 2.0 to 50 nm. If a clay is used as the third acidic component, it is preferably selected from a group comprising saponites, vermiculites, biotites, stevensites, hectorite, beidellite, montmorillonites, and nontronites.
  • the first acidic component is beta zeolite
  • the second acidic component is Y zeolite or USY zeolite
  • the third acidic component is amorphous silica/alumina.
  • the catalyst composition of this invention may further comprise a hydrogenation component from the Periodic Table which is selected from a Group VIB metal, a Group VIU metal, or mixtures thereof.
  • a hydrogenation component from the Periodic Table which is selected from a Group VIB metal, a Group VIU metal, or mixtures thereof.
  • the hydrogenation component is a combination of nickel and tungsten, nickel and molybdenum or cobalt and molybdenum.
  • a hydrocracking catalyst containing beta/Y/ASA/alumina was prepared per following procedure. 1.4 wt-% beta zeolite (CP81 1C-300 powder from S ⁇ d Chemie), 5.8 wt-% USY (CBV 760 zeolite powder from the PQ corporation), 71.3 wt-% ASA powder (Siral-40 obtained from Sasol), and 21.5 wt-% pseudo-boehmite alumina powder were mixed well.
  • nickel nitrate hexahydrate dissolved in diluted nitric acid were added, so that the total mix contained 0.64 wt-% HNO3, 12.5 wt-% Ni(NO3)2.6H2O, 43 % H2O.
  • an ammonium metatungstate solution (54.5 wt-% ammonium metatungstentate in water) was added, and enough water to yield an extrudable mix.
  • the paste was extruded in 1/20" asymmetrical quadrulobes, dried at 130 C for one hour and calcined at 510 C for one hour with purging excess dry air. After cooling down to room temperature the catalyst contained 5.1 wt-% NiO and 25.2 wt-% WO3 on a dry basis.
  • a hydrocracking catalyst containing beta/Y/alumina was prepared as above, but by starting with a powder mix consisting of 5.8 wt.% USY, 72.7 wt.% ASA powder and 21.5 wt.% pseudo-boehmite alumina powder.
  • Table 1 demonstrates that a catalyst comprising a combination of zeolite beta, zeolite Y and amorphous silica-alumina (ASA) has a higher activity in fuels hydroprocessing applications than a combination of zeolite Y and ASA alone. It results in a larger volume of heavier products.
  • a catalyst comprising a combination of zeolite beta, zeolite Y and amorphous silica-alumina (ASA) has a higher activity in fuels hydroprocessing applications than a combination of zeolite Y and ASA alone. It results in a larger volume of heavier products.
  • ASA amorphous silica-alumina
  • Table 2 illustrates improved cold flow improvement properties in fuels hydroprocessing for the catalyst comprising a combination of zeolite beta, zeolite Y and amorphous aluminosilicate(ASA) when compared against a catalyst combination of zeolite Y and ASA alone.
  • Table 3 illustrates that a catalyst comprising a combination of zeolite beta, zeolite Y and amorphous aluminosilicate (ASA) has a higher activity in tubes hydroprocessing applications than a combination of zeolite Y and ASA alone.
  • a catalyst comprising a combination of zeolite beta, zeolite Y and amorphous aluminosilicate (ASA) has a higher activity in tubes hydroprocessing applications than a combination of zeolite Y and ASA alone.
  • Table 4 illustrates improved viscosity index and pour point in lubes hydroprocessing for the catalyst comprising a combination of zeolite beta, zeolite Y and amorphous aluminosilicate (ASA) when compared against a catalyst combination of zeolite Y and ASA alone.
  • zeolite beta zeolite beta
  • zeolite Y zeolite Y
  • ASA amorphous aluminosilicate
  • Figure 1 illustrates the improved base oil yield that occurs when employing the catalyst of this invention.
  • Figure 2 illustrates the improved dewaxed oil viscosity index that occurs when employing the catalyst of this invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

This invention is directed to a catalyst composition effective in hydroprocessing and a process employing this catalyst. The catalyst composition comprises three acidic components acting in synergy to provide enhanced catalytic activity, when compared to any of the components alone or in combinations of two. Two of the components are large pore zeolites, and the third component is selected from the group comprising clays and amorphous silica/alumina.

Description

HYDROPROCESSING CATALYST AND PROCESS OF USE
This application claims priority from provisional application number US 60/820,907, filed July 31 , 2006.
Field of the Invention
This invention is directed to a catalyst effective in hyd reprocessing and a process employing this catalyst.
Background of the Invention
The literature of the refining arts contains examples of two acidic components of a hydroprocessing catalyst exhibiting synergy. The two components together are more effective than either component alone in hydroprocessing hydrocarbon feeds.
U.S. Pat. No. 3,535,225, discloses a hydroprocessing catalyst comprising a zeolite such as Y, a faujasite, in combination with an amorphous aluminosilicate.
Combinations of faujasites with clays are also disclosed in GB 1267416, U.S Pat. No. 3716475,and U.S. Pat. No. 3764519.
Summary of the Invention
This application discloses a catalyst composition suitable for hydroprocessing a hydrocarbonaceous feedstock, said catalyst composition comprising three acidic components acting in synergy to provide enhanced catalytic activity when compared to any of the components alone or in combinations of two. It was discovered that addition of a zeolite having a cage window in the range from about 0.47 nm to about 0.85 nm in diameter (such as zeolite beta), to a combination of a zeolite in the range from about 0.47 nm to about 0.85 nm in diameter, (such as zeolite Y) and amorphous aluminosiltcate (ASA) or delaminated clay (such as saponite) significantly enhances the activity, the diesel yield, the heavy diesel cold flow properties, the hydrodenitrification effects, and the base oil yield of the combinations of Y and ASA alone.
Brief Description of the Figures
Figure 1 illustrates the improved base oil yield that occurs when employing the catalyst of this invention.
Figure 2 illustrates the improved dewaxed oil viscosity index that occurs when employing the catalyst of this invention.
Detailed Description of the Invention
Feeds
The feedstocks that may be hydroprocessed using the catalyst of this invention are selected from the group consisting of petroleum distillates, solvent-deasphalted petroleum residua, shale oils, Fischer-Tropsch derived feedstocks and coal tar distillates. The feedstocks contain substantial amounts of materials boiling above 200 ° F, preferably substantial amounts of materials boiling in the range 350 ° to 11000 F, and more preferably in the range 400 ° to 1000 ° F. Suitable feedstocks include those heavy distillates normally defined as heavy straight-run gas oils and heavy cracked cycle oils, as well as conventional FCC feed and portions thereof. Cracked stocks mav be obtained from thermal or catalytic cracking of various stocks, including those obtained from petroleum, gilsonite, shale and coal tar The feedstocks may have been subjected to a hydrofining and/or hydrogenation treatment, which may have been accompanied by some hydrocracking, before being supplied to the hydroprocessing zone organic nitrogen content be less than 100 Parts per million organic nitroen- A preferred range is 0.5 to 1000 parts per million; more preferably, 0.5 to 100 parts per million. When contacting the catalyst of this invention, it is preferable to maintain the organic sulfur content of the feed to a range of from 0 to 3 weight percent, preferably from 0 to 1 weight percent.
Products
The terms "lubes" and "base oils" are used interchangeably in this application and refer to products boiling at or above 700° F. "Fuels" boil in the range from C5 + to below 700° F.
Operating Conditions
The hydroprocessing zone containing the catalyst of this invention is preferably operated at hydrocracking conditions including a temperature in the range 400 ° to 950 ° F preferably 500 ° to 850 ° F, a pressure in the range 800 to 3500psig, preferably 1000 to 3000 psig, a liquid hourly space velocity in the range 0.1 to 5.0, preferably 0.5 to 5.0, and more preferably 0.5 to 3.0.
The total hydrogen supply rate (makeup and recycle hydrogen) to the hydroprocessing zone is 200 to 20,000 s.c.f preferably 2000 to 20000 scf of hydrogen per barrel of said feedstock.
Where a separate hydrotreating zone, is located ahead of the hydrocracking zone containing the catalyst of this invention, the operating conditions in the separate hydrotreating zone include a temperature of 400 ° to 900 ° F, preferably 500 ° to 800 ° F, a pressure of 800 to 3500 psig preferably 1000 to 2500 p.s.i.g and a liquid hourly space velocity of 0.1 to 5.0, preferably 0.5 to 3.0. The total hydrogen supply rate (makeup and recycle hydrogen) is 200 to 20,000 s.c.f. of hydrogen per barrel of feedstock, preferably 2000 to 20,000 s.c.f. of hydrogen per barrel of feedstock. Catalyst composition
The catalyst of this invention comprises three acidic components acting in synergy to provide enhanced catalytic activity. One acidic component is a zeolite having a cage window in the range from about 0.47 nm to about 0.85 nm in diameter. The cage window is the narrowest part of a nanopore system, and the cage is the widest part of the nanopore system. Nanopores are defined as pores smaller than 0.2 nm in diameter. Large pore zeolites such as BEA- (beta), ISV-, BEC-, IWR-, MTW-, SSZ-31-, OFF- (offretite), MAZ- (mazzite), MOR- (mordenite), MOZ-, AFI-, ZSM-48-, and SSY-type zeolites fit this description. These are documented at http://topaz.ethz.ch/IZA- SC/StdAtlas.htm. and in Baerlocher, Meier, and Olson's "Atlas of Zeolite Framework Types", Elsevier, 2001. BEA possesses a Si/AI molar ratio in the range from about 100 to about 300, preferably in the range from about 100 to about 200. The website defines pore diameters of the zeolites mentioned.
The 2nd acidic component is a zeolite having a cage in the range from about 0.9 nm to about 2.0 in diameter. This category includes large pore zeolites such as FAU-, EMT-, ITQ-21-, ERT-, and ITQ-33-type zeolites. FAU, EMT and ERT are further described at the sources indicated above. ITQ-21 is described in an article, "A large-cavity zeolite with wide pore windows, and potential as an oil refining catalyst." Corma, Avelino; Diaz-Cabanas, Maria J.; Martinez-Triguero, Joaquin; Rey, Fermando; Rius, Jordi. UPV-CSIC1 Institυto de Tecnologia Quimica, Universidad Politecnica de Valencia, Valencia, Spain. Nature (London, United Kingdom) (2002), 418(6897), 514-517. iTQ-33 is described in the article, "High-throughput synthesis and catalytic properties of a molecular sieve with 18- and 10-member rings." Corma, Avelino; Diaz- Cabanas, Maria J.; Jorda, Jose Luis; Martinez, Cristina; Moliner, Manuel. lnstituto de Tecnologia Quimica, UPV-CSIC, Universidad Politecnica de Valencia, Valencia, Spain. Nature (London, United Kingdom) (2006), 443(7113), 842-845. The FAU-type zeolite has a Si/AI molar ratio in the range from about 10 to about 100, preferably in the range from about 10 to about 80. The catalyst composition of the instant invention comprises active zeolite components ranging from about 1% to about 50% of the catalyst composition.
The 3rd acidic component ranges from about 10% to about 90% of the catalyst composition, and is selected from the group comprising clays and amorphous silicayalumina. If an amorphous silica-alumina component is used, it is preferably selected from the group comprising silica, alumina, titania, zirconia, magnesia and their binary and tertiary compounds. Amorphous silica-alumina component is mesoporous, comprising pores in the range from 2.0 to 50 nm. If a clay is used as the third acidic component, it is preferably selected from a group comprising saponites, vermiculites, biotites, stevensites, hectorite, beidellite, montmorillonites, and nontronites.
In one embodiment of this invention, the first acidic component is beta zeolite, the second acidic component is Y zeolite or USY zeolite and the third acidic component is amorphous silica/alumina.
The catalyst composition of this invention may further comprise a hydrogenation component from the Periodic Table which is selected from a Group VIB metal, a Group VIU metal, or mixtures thereof. Preferably the hydrogenation component is a combination of nickel and tungsten, nickel and molybdenum or cobalt and molybdenum.
Catalyst Preparation
Examples - Catalyst Preparation
Preparation of Co-mul beta/Y/ASA catalyst A hydrocracking catalyst containing beta/Y/ASA/alumina was prepared per following procedure. 1.4 wt-% beta zeolite (CP81 1C-300 powder from Sϋd Chemie), 5.8 wt-% USY (CBV 760 zeolite powder from the PQ corporation), 71.3 wt-% ASA powder (Siral-40 obtained from Sasol), and 21.5 wt-% pseudo-boehmite alumina powder were mixed well. To this mix, nickel nitrate hexahydrate dissolved in diluted nitric acid were added, so that the total mix contained 0.64 wt-% HNO3, 12.5 wt-% Ni(NO3)2.6H2O, 43 % H2O. To this mix an ammonium metatungstate solution (54.5 wt-% ammonium metatungstentate in water) was added, and enough water to yield an extrudable mix. The paste was extruded in 1/20" asymmetrical quadrulobes, dried at 130 C for one hour and calcined at 510 C for one hour with purging excess dry air. After cooling down to room temperature the catalyst contained 5.1 wt-% NiO and 25.2 wt-% WO3 on a dry basis.
Preparation of Co-mul Y/A SA catalyst
A hydrocracking catalyst containing beta/Y/alumina was prepared as above, but by starting with a powder mix consisting of 5.8 wt.% USY, 72.7 wt.% ASA powder and 21.5 wt.% pseudo-boehmite alumina powder.
Table 1 demonstrates that a catalyst comprising a combination of zeolite beta, zeolite Y and amorphous silica-alumina (ASA) has a higher activity in fuels hydroprocessing applications than a combination of zeolite Y and ASA alone. It results in a larger volume of heavier products.
β/Y/ASA for Fuels Applications: Higher Activity and Heavier Products than Y/ASA
Y/ASA β/Y/ASA
Conversion, LV % <700°F -74 -72
CAT, DF Base Base - 27
C4-, Wt % 3.4 3,3
C5-180° F, LV % 7.4 6.4
180-2500F, LV % 11.0 9.9
250-5500F, LV % 51.0 48.0
550-7000F, LV % 16.9 20.0
700-EP, LV% 26.4 28.0
N/S, ppm 0.2/12 0.1/8
TABLE 1 Table 2 illustrates improved cold flow improvement properties in fuels hydroprocessing for the catalyst comprising a combination of zeolite beta, zeolite Y and amorphous aluminosilicate(ASA) when compared against a catalyst combination of zeolite Y and ASA alone.
β/Y/ASA for Fuels Applications Key Product Properties
Y/ASA β/Y/ASA
Conversion, LV % <700°F -74 -72
CAT, 0F Base Base - 27
Jet Cut / Smoke Point, mm 27 25
Freeze, 0C -62 -63
Heavy Diesel / Pour, 0C -22 -31
Cloud, 0C -10 -8
Cetane Index 63.6 63.0
UCO: N/S. ppm 0.2/10 0.2/<6
Pour, C 34 30
TABLE 2
Table 3 illustrates that a catalyst comprising a combination of zeolite beta, zeolite Y and amorphous aluminosilicate (ASA) has a higher activity in tubes hydroprocessing applications than a combination of zeolite Y and ASA alone.
β/Y/ASA for Lube Applications: Similar Yields But Higher Activity Than Y/ASA
Y/ASA β/Y/ASA
Conversion, LV % <700°F -40 -40
CAT, 0F Base Base -- 16
C4-, Wt % 1.3 1.5
C5-I8O F, LV % 2.1 2.2
180-250 F, LV % 3,6 3.7
250-550 F, LV % 23.4 24.3
550-700 F, LV % 18.4 17.8
700-EP, LV % 59.3 59.6
N/S, ppm 1.2/28 0.1/11
TABLE 3 Table 4 illustrates improved viscosity index and pour point in lubes hydroprocessing for the catalyst comprising a combination of zeolite beta, zeolite Y and amorphous aluminosilicate (ASA) when compared against a catalyst combination of zeolite Y and ASA alone.
β/Y/ASA for Lube Applications Key Product Properties
Y/ASA BMASA
Conversion, LV % <700°F -40 -40
CAT, °F Base Base -16
Jet Cut / Smoke Point, mm 19 20
Freeze, 0C -62 -61
Heavy Diesel / Pour, °C -12 -13
Cloud, 0C -9 -5
Cetane Index 47.7 51.7
UCO / N/S, ppm 0.2/29 0.2/12
V L 126 127
Viscosity ® 1000C 6.18 6.25
Pour, 0C 43 30
TABLE 4
Table 5; Arab Gulf vacuum gas oil (VGO) Feedstock Properties
TABLE 5 Conditions: 5000 scf/b, LHSV=0.75, 2300 psi, temperature range 700 ° - 800 ° F. This feedstock was used to generate data of Tables 1-4 and Figures 1 and 2.
Figure 1 illustrates the improved base oil yield that occurs when employing the catalyst of this invention.
Figure 2 illustrates the improved dewaxed oil viscosity index that occurs when employing the catalyst of this invention.

Claims

WHAT IS CLAIMED IS:
1) A catalyst composition suitable for hydroprocessing a hydrocarbonaceous feedstock, said catalyst composition comprising three acidic components acting in synergy to provide enhanced catalytic activity when compared to any of the components alone or in combinations of two.
2) The catalyst composition of claim 1 , wherein the first acidic component is a zeolite having a cage window in the range from about 0.47 nm to about 0.85 nm in diameter, the 2nd acidic component is a zeolite having a cage in the range from about 0.9 nm to about 2.0 nm in diameter, and the 3rd acidic component is selected from the group comprising clays and amorphous silica/alumina.
3) The catalyst composition of claim 2 wherein the 1st acidic zeolite, and the 2nd acidic zeolite are large pore zeolites.
4) The catalyst composition of claim 3 wherein the 1st acidic zeolite is selected from the group consisting of BEA-, ISV-, BEC-, IWR-, MTW-,
SSZ-31-, OFF-, MAZ-, MOR-, MOZ-, AFI-, ZSM-48-, and SSY-type zeolites.
5) The catalyst composition of claim 4 wherein the 1st acidic zeolite is a BEA-type zeolite.
6) The catalyst composition of claim 5 wherein the BEA-type zeolite has a Si/AI ratio in the range from about 100 to about 300, preferably in the range from about 100 to about 200.
7) The catalyst composition of claim 1 wherein the 2nd acidic zeolite is selected from the group comprising FAU-, EMT-, ITQ-21-, ERT-, and ITQ-33-type zeolites. 8) The catalyst composition of claim 7 wherein the 2nd acidic zeolite is a FAU-type zeolite.
9) The catalyst composition of claim 8 wherein the FAU-type zeolite has a Si/AI molar ratio in the range from about 10 to about 100, preferably in the range from about 10 to about 60.
10) The catalyst composition of claim 1 wherein said catalyst composition comprises active zeolite components ranging from about 1 % to about
50% of the catalyst composition.
11) The catalyst composition of claim 1 wherein the 3rd acidic component ranges from about 10% to about 90% of the catalyst composition.
12) The catalyst composition of claim 1 wherein the 3rd acidic material comprises at least one amorphous silica-alumina component selected from the group comprising silica, alumina, titania, zirconia, magnesia and their binary and tertiary compounds.
13) The catalyst composition of claim 12 wherein said amorphous silica- alumina component is mesoporous.
14) The catalyst of claim 13, wherein the amorphous silica-alumina component comprises pores in the range from 2.0 to 50 nm.
15) The catalyst composition of claim 1 wherein the 3rd acidic material is a phyllosilicate.
16) The catalyst composition of claim 15 wherein the phyllosilicate is a clay selected from a group comprising saponites, vermiculit.es, biotites, stevensites, hectorite, beidellite, montmorillonites, and nontronites. 17) The catalyst composition of claim 1 wherein said catalyst composition further comprises a hydrogenation component from the Periodic Table which is selected from a Group VIB metal , a Group VIIl metal , or mixtures thereof.
18) The catalyst composition of claim 17 wherein the hydrogenation component is a combination of nickel and tungsten.
19) The catalyst composition of claim 2, wherein the first acidic component is beta zeolite, the second acidic component is Y zeolite or USY zeolite and the third acidic component is amorphous silica/alumina.
20) The process of hydrocracking a hydrocarbonaceous feedstock with a catalyst composition, said catalyst composition comprising three acidic components acting in synergy to provide enhanced catalytic activity when compared to any of the components alone or in combinations of two.
EP07813564.7A 2006-07-31 2007-07-31 Hydroprocessing catalyst and process of use Withdrawn EP2046496A4 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US82090706P 2006-07-31 2006-07-31
US82898307A 2007-07-26 2007-07-26
PCT/US2007/074782 WO2008016888A2 (en) 2006-07-31 2007-07-31 Hydroprocessing catalyst and process of use

Publications (2)

Publication Number Publication Date
EP2046496A2 true EP2046496A2 (en) 2009-04-15
EP2046496A4 EP2046496A4 (en) 2014-08-06

Family

ID=38997794

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07813564.7A Withdrawn EP2046496A4 (en) 2006-07-31 2007-07-31 Hydroprocessing catalyst and process of use

Country Status (3)

Country Link
EP (1) EP2046496A4 (en)
JP (1) JP2009545441A (en)
WO (1) WO2008016888A2 (en)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102451744B (en) * 2010-10-15 2014-03-05 中国石油化工股份有限公司 Preparation method of hydrocracking catalyst
CN104588121B (en) * 2013-11-03 2017-04-12 中国石油化工股份有限公司 Hydrocracking catalyst carrier and preparation method thereof
US10046317B2 (en) 2015-08-11 2018-08-14 Chevron U.S.A. Inc. Middle distillate hydrocracking catalyst containing zeolite beta with low OD acidity and large domain size
US10040058B2 (en) * 2015-08-11 2018-08-07 Chevron U.S.A. Inc. Middle distillate hydrocracking catalyst containing zeolite USY, and zeolite beta with low acidity and large domain size
US10183286B2 (en) * 2015-08-11 2019-01-22 Chevron U.S.A. Inc. Noble metal zeolite catalyst for second-stage hydrocracking to make middle distillate
CN109304226B (en) * 2017-07-28 2021-06-01 中国石油天然气股份有限公司 Hydrocracking catalyst for increasing production of heavy naphtha and aviation kerosene, and preparation method and application thereof
CN109423336B (en) * 2017-08-31 2020-09-11 中国石油化工股份有限公司 Hydrocracking method
US11779909B2 (en) 2018-12-13 2023-10-10 China Petroleum & Chemical Corporation Hydrocracking catalyst, preparation method therefor and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6133186A (en) * 1997-03-06 2000-10-17 Shell Oil Company Process for the preparation of a catalyst composition
US6190538B1 (en) * 1998-08-03 2001-02-20 Shell Oil Company Process for the preparation of a catalyst composition
US20020094931A1 (en) * 2000-10-26 2002-07-18 Fenglai Wang Highly active midbarrel hydrocracking catalyst and the preparation thereof
WO2008011291A2 (en) * 2006-07-17 2008-01-24 Uop Llc Hydrocracking catalyst containing beta and y zeolites, and process for its use to make distillate
WO2008011289A2 (en) * 2006-07-17 2008-01-24 Uop Llc Hydrocracking catalyst containing beta and y zeolites, and process for its use to make distillate

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4837396A (en) * 1987-12-11 1989-06-06 Mobil Oil Corporation Zeolite beta containing hydrocarbon conversion catalyst of stability
US5160033A (en) * 1988-03-30 1992-11-03 Uop Octane gasoline catalyst and process using same in a hydrocracking process
US5350501A (en) * 1990-05-22 1994-09-27 Union Oil Company Of California Hydrocracking catalyst and process
US5194412A (en) * 1991-01-22 1993-03-16 W. R. Grace & Co.-Conn. Catalytic compositions
AU4823600A (en) * 1999-05-05 2000-11-17 Exxon Chemical Patents Inc. Zeolite bound catalyst containing at least three different zeolites; use for hydrocarbon conversion
CA2579445A1 (en) * 2004-09-08 2006-03-16 Shell Internationale Research Maatschappij B.V. Hydrocracking catalyst composition

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6133186A (en) * 1997-03-06 2000-10-17 Shell Oil Company Process for the preparation of a catalyst composition
US6190538B1 (en) * 1998-08-03 2001-02-20 Shell Oil Company Process for the preparation of a catalyst composition
US20020094931A1 (en) * 2000-10-26 2002-07-18 Fenglai Wang Highly active midbarrel hydrocracking catalyst and the preparation thereof
WO2008011291A2 (en) * 2006-07-17 2008-01-24 Uop Llc Hydrocracking catalyst containing beta and y zeolites, and process for its use to make distillate
WO2008011289A2 (en) * 2006-07-17 2008-01-24 Uop Llc Hydrocracking catalyst containing beta and y zeolites, and process for its use to make distillate

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2008016888A2 *

Also Published As

Publication number Publication date
EP2046496A4 (en) 2014-08-06
WO2008016888A3 (en) 2008-08-07
JP2009545441A (en) 2009-12-24
WO2008016888A2 (en) 2008-02-07

Similar Documents

Publication Publication Date Title
US10030202B2 (en) Mesoporous composite of molecular sieves for hydrocracking of heavy crude oils and residues
EP2046496A2 (en) Hydroprocessing catalyst and process of use
EP0044965B1 (en) Catalyst and process for simultaneous hydrotreating and hydrodewaxing of hydrocarbons
AU680503B2 (en) Process for preparing an alumina bound zeolite catalyst
EP1137740B1 (en) Catalytic dewaxing process
AU724363B2 (en) Layered catalyst system for lube oil hydroconversion
US9944863B2 (en) Middle distillate hydrocracking catalyst
CA2931187C (en) Hydrocracking of gas oils with increased distillate yield
AU2022202785A1 (en) Middle distillate hydrocracking catalyst with a base extrudate having a high nanopore volume
RU2140966C1 (en) Method of preparing main component of lubricating oil using catalyst with high selectivity of viscosity index
US4816538A (en) Nickel-containing hydrocracking catalyst
US4600498A (en) Mild hydrocracking with a zeolite catalyst containing silica-alumina
US20150306582A1 (en) Middle distillate hydrocracking catalyst with a base extrudate having a low particle density
US4923592A (en) Nickel-containing hydrocracking catalyst and process
US5332490A (en) Catalytic process for dewaxing hydrocarbon feedstocks
KR102293750B1 (en) Hydrotreating and dewaxing process
RU2768876C2 (en) Dewaxing catalyst system
US4790927A (en) Process for simultaneous hydrotreating and hydrodewaxing of hydrocarbons
US20150306581A1 (en) Middle distillate hydrocracking catalyst with a base extrudate having a high total nanopore volume
US20150306584A1 (en) Middle distillate hydrocracking catalyst manufactured using a high nanopore volume amorphous silica-alumina support
RU2798341C2 (en) Catalytic system for dewaxing
CN116023992A (en) Hydrocracking method for producing low-aromatic high-paraffin content diesel oil from heavy distillate oil
JPS58219294A (en) Hydrogenation of heavy oil
SA96170517B1 (en) Catalyst compositions containing beta-zeolite and their use in hydrocarbon conversion processes for the production of low-boiling materials

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090223

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA HR MK RS

RIC1 Information provided on ipc code assigned before grant

Ipc: C10G 47/20 20060101ALI20090610BHEP

Ipc: C10G 47/10 20060101ALI20090610BHEP

Ipc: B01J 29/80 20060101ALI20090610BHEP

Ipc: B01J 29/18 20060101ALI20090610BHEP

Ipc: B01J 29/08 20060101ALI20090610BHEP

Ipc: B01J 29/06 20060101AFI20090610BHEP

DAX Request for extension of the european patent (deleted)
RBV Designated contracting states (corrected)

Designated state(s): BE DE FR IT NL

A4 Supplementary search report drawn up and despatched

Effective date: 20140703

RIC1 Information provided on ipc code assigned before grant

Ipc: B01J 29/80 20060101ALI20140629BHEP

Ipc: B01J 29/08 20060101ALI20140629BHEP

Ipc: B01J 29/06 20060101AFI20140629BHEP

Ipc: C10G 47/20 20060101ALI20140629BHEP

Ipc: C10G 47/10 20060101ALI20140629BHEP

Ipc: B01J 29/18 20060101ALI20140629BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CHEVRON U.S.A. INC.

18D Application deemed to be withdrawn

Effective date: 20150203

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230522