US20060157386A1 - Hydrocracking catalysts for vacuum gas oil & de-metalized oil blend - Google Patents

Hydrocracking catalysts for vacuum gas oil & de-metalized oil blend Download PDF

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US20060157386A1
US20060157386A1 US11/320,928 US32092805A US2006157386A1 US 20060157386 A1 US20060157386 A1 US 20060157386A1 US 32092805 A US32092805 A US 32092805A US 2006157386 A1 US2006157386 A1 US 2006157386A1
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catalytic
catalyst
support material
dmo
metal
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Walid Al-Naeem
Shakeel Ahmed
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Saudi Arabian Oil Co
King Fahd University of Petroleum and Minerals
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Saudi Arabian Oil Co
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Assigned to KING, FAHD UNIVERSITY OF PETROLEUM AND MINERALS reassignment KING, FAHD UNIVERSITY OF PETROLEUM AND MINERALS ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: AHMED, SHAKEEL
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • 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
    • B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • 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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • 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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
    • B01J29/044—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 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
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    • 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
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    • 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
    • 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
    • C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten 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
    • 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
    • C10G45/12—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 containing crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • 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
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • 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
    • B01J35/30—
    • B01J35/615—
    • B01J35/633—
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B01J37/20—Sulfiding

Definitions

  • hydrocracking as a process for refining petroleum has resulted in its phenomenal growth during the past 15 years.
  • feedstocks can be converted to lower boiling or more desirable products.
  • Hydrocarbon feedstocks suitable for such treatment range from residue to naphtha. Products include such widely diverse materials such as gasoline, kerosene, middle distillates, lubricating oils, fuel oils, and various chemicals.
  • hydrocracking is typically carried out in a single stage reactor or in a two-stage reactor with the stages in series.
  • Numerous hydrocracking catalysts have been explored to treat various hydrocarbons, to reduce undesirable side effects of the catalytic treatment and/or to extend the life of the catalyst.
  • Development has also led to catalysts suitable for severe operating conditions. Efforts for cost effectiveness are ongoing. The choice of catalysts and of the particular process scheme will depend on many factors such as feed properties, desired products properties, size of the hydrocracking unit, and various other economic considerations.
  • VGO hydrocracking medium and heavy vacuum gas oil
  • DAO de-asphalted oil
  • DMO de-metallized oil
  • a catalyst would be advantageous that is capable of handling large hydrocarbon molecules and heavy poly-aromatic molecules, in particular, DMO.
  • a catalyst that can process VGO/DMO feed blend would be particularly advantageous.
  • a catalyst suitable for such heavy hydrocarbons would be advantageous.
  • the catalytic metal component includes molybdenum and the promoter metal includes nickel.
  • a particularly preferred catalytic support material includes MCM-41 mesoporous material.
  • ⁇ -alumina was used as binder for all catalyst prepared in this research. The amount of ⁇ -alumina used was around 70% of the total catalyst support for the test runs.
  • the USY zeolite is in an absence of ⁇ -zeolite.
  • the catalytic support material is ⁇ -zeolite.
  • the catalytic support material is USY zeolite.
  • the catalytic support material is amorphous silica alumina, also called ASA.
  • ASA has a non-uniform structure with low acidity and high surface area. The non-uniform structure tends to create acidic sites that are not available to large molecules, which leads to inferior performance of ASA alone as compared to MCM-41 or a combination of MCM-41 with ASA.
  • the USY and ⁇ -zeolite supports suffer from drawbacks related to the microporous nature of the supports which makes the catalyst less efficient for large molecules since it is diffusion limited.
  • the MCM-41 support material overcomes these flaws.
  • the catalytic support material is solely ultra stable Y zeolite, MCM41 mesoporous material, ⁇ -zeolite, amorphous silica alumina or combinations thereof.
  • a particularly preferred embodiment includes a single catalytic support material that is substantially all MCM-41. This material is mesoporous that is well-structured and has uniform morphology with high surface area. It also has low acidity as compared to beta and USY support materials.
  • the invention includes the use of proper support material and a balance between acidic and metallic function with the proper distribution of metals throughout the support material.
  • MCM-41 support material which contains both acidic and metallic site that are accessible to the large hydrocarbon molecules found in VGO and DMO. For this reason, high conversion is achieved.
  • the lower acidity of MCM-41 as compared to other support materials drives conversion toward selectivity towards mid distillates and limits the production of undesirable light gases.
  • the catalytic metal is in a sulfide form.
  • molybdenum in the form of molybdenum sulfide is preferred.
  • promoter metals include solely nickel.
  • the catalyst of the invention is particularly useful for VGO/DMO hydrocarbon blend contains at least 10% DMO by volume. Test runs have been made for VGO/DMO hydrocarbon blend contains at least 15% DMO by volume.
  • Impregnation of the catalytic metal and the promoter metal onto the catalytic support is accomplished through methods known in the art, such as co-impregnation method.
  • the process of catalytically converting a heavy hydrocarbon containing de-metallized oil includes the steps of introducing the heavy hydrocarbon containing de-metallized oil into a reactor stage and introducing the catalyst into the reactor stage.
  • the catalyst introduced into the reactor stage includes the catalytic support material, the catalytic metal impregnated upon the catalytic support material, and the promoter metal on the catalytic support material to enhance catalytic conversion.
  • the catalytic support material with catalytic metal and promoter metal operate to catalytically convert at least a portion of the de-metallized oil into hydrocarbon products having shorter carbon chains.
  • the process reaches and maintains a pre-defined temperature in the reactor operable to achieve conversion.
  • the pre-defined temperature is at least 390 degrees C. In a more particularly preferred embodiment, the pre-defined temperature is at least 400 degrees C.
  • a majority of the pores of the catalyst support are located within 20 to 50 Angstrom ( ⁇ ) and the catalyst support has a large surface area as measured through pore size distribution.
  • Table 1 shows examples of preferred embodiments. TABLE 1 Prepared Catalysts Textual Characteristics Average BET Surface Area Pore Volume Pore Diameter Sample (m 2 /g) (cm 3 /g) (A 0 ) NiMo-ASA 186 0.33 36 NiMo-MCM-41 324 0.40 25 NiMo- ⁇ 313 0.41 26 NiMo-USY 300 0.35 23
  • FIG. 1 depicts a schematic of a preferred embodiment of the process with the catalyst of the invention.
  • Table 2 shows the TPD of ammonia for all of the prepared hydrocracking catalysts.
  • the acidity of the prepared catalysts ranges from 0.33 mmol/g (NiMo-MCM-41) to 0.59 mmol/g (NiMo-USY).
  • the lower acidity of NiMo-MCM-41 catalyst is expected since MCM-41 is a silica based material and has low amount of alumina. Therefore, NiMo-MCM-41 catalyst has lower amount of ⁇ -alumina than the other prepared catalysts.
  • the catalytic metal such as molybdenum
  • the promoter metal such as nickel
  • Other group VIA and group VIIIA metals are useful as promoter metal and catalytic metal. These metals catalyze the hydrogenation of the feedstock, making it more reactive for cracking and heteroatom removal, as well as reducing the coking rate. They also initiate the cracking by forming a reactive olefin intermediate via dehydrogenation.
  • the metal site be in a metal sulfide form of the VIA group promoted by a nickel or cobalt sulfide.
  • the reactions that occur during the hydrocracking process take three major routes.
  • there are other reactions that take place during the hydrocracking process can include hydrodesulfurization, hydrodeintrofication, hydrodeoxigenation, olefin hydrogenation and partial aromatic hydrogenation.
  • NiMo-MCM-41 catalyst had the lowest acidity and the highest surface area. This is attributed to the fact that MCM-41 is a silica-based material and has low amounts of alumina. This is one of the advantages of MCM-41 being mesoporous and having low acidity. The mesoporous feature along with the lower acidity of NiMo-MCM41 catalyst promotes the highest conversion and the lowest gas make.

Abstract

This invention relates to a catalyst and a process for treating heavy hydrocarbons using the catalyst. The catalyst is useful for treating heavy hydrocarbons, de-metallize oil (DMO) and is particularly useful in VGO/DMO hydrocarbon blend. It is also useful for DAO. The catalyst acts to catalytically convert the VGO/DMO blend to shorter-chain valuable hydrocarbon products. The catalyst includes a catalytic support material, a catalytic metal impregnated upon the catalytic support material, and a promoter metal on the catalytic support material to enhance catalytic conversion. The combination of the catalytic support material with catalytic metal and promoter metal is operable to catalytically convert VGO/DMO into hydrocarbon products having shorter carbon chains.

Description

    RELATED APPLICATIONS
  • This patent application claims priority to U.S. Provisional Patent Application Ser. No. 60/639,909 filed on Dec. 29, 2004, which is incorporated by reference in its entirety.
    • BACKGROUND OF THE INVENTION
  • 1. Technical Field of the Invention
  • This invention relates generally to the field of catalytic treatment of heavy hydrocarbons to produce desirable hydrocarbon products, in particular, a novel catalyst operable to catalytically treat de-metallized oil (DMO) and Vacuum Gas Oil (VGO) Blend.
  • 2. Description of the Prior Art
  • The flexibility of hydrocracking as a process for refining petroleum has resulted in its phenomenal growth during the past 15 years. Through catalytic treatment, feedstocks can be converted to lower boiling or more desirable products. Hydrocarbon feedstocks suitable for such treatment range from residue to naphtha. Products include such widely diverse materials such as gasoline, kerosene, middle distillates, lubricating oils, fuel oils, and various chemicals.
  • Commercial hydrocracking is typically carried out in a single stage reactor or in a two-stage reactor with the stages in series. Numerous hydrocracking catalysts have been explored to treat various hydrocarbons, to reduce undesirable side effects of the catalytic treatment and/or to extend the life of the catalyst. Development has also led to catalysts suitable for severe operating conditions. Efforts for cost effectiveness are ongoing. The choice of catalysts and of the particular process scheme will depend on many factors such as feed properties, desired products properties, size of the hydrocracking unit, and various other economic considerations.
  • While hydrocracking has been investigated in the past for the purpose of hydrocracking medium and heavy vacuum gas oil (VGO), there is a need to address heavier and different hydrocarbons such as de-asphalted oil (DAO) or de-metallized oil (DMO) to convert this into suitable product for gasoline lines, jet fuels and diesel oils according to geographical and seasonal variations in demand. LPG and lubricating bases would also be desirable products. A catalyst would be advantageous that is capable of handling large hydrocarbon molecules and heavy poly-aromatic molecules, in particular, DMO. A catalyst that can process VGO/DMO feed blend would be particularly advantageous. As it is notable that the world market is tending toward heavier hydrocarbons, a catalyst suitable for such heavy hydrocarbons would be advantageous.
    • SUMMARY OF THE INVENTION
  • The current invention includes a catalyst for and a process for hydrotreating/hydrocracking heavy hydrocarbons. The catalyst is particularly useful for treating de-metallized oil (DMO) and is particularly useful in VGO/DMO hydrocarbon blend. The catalyst acts to catalytically convert the VGO/DMO blend to shorter-chain valuable hydrocarbon products. The catalyst includes a catalytic support material, a catalytic metal impregnated upon the catalytic support material, and a promoter metal on the catalytic support material to enhance catalytic conversion. The combination of the catalytic support material with catalytic metal and promoter metal is operable to catalytically convert VGO/DMO into hydrocarbon products having shorter carbon chains.
  • In a preferred embodiment, the catalytic metal component includes molybdenum and the promoter metal includes nickel.
  • Regarding the catalytic support materials, a particularly preferred catalytic support material includes MCM-41 mesoporous material. γ-alumina was used as binder for all catalyst prepared in this research. The amount of γ-alumina used was around 70% of the total catalyst support for the test runs. In a particularly preferred embodiment, the USY zeolite is in an absence of γ-zeolite.
  • In another preferred embodiment, the catalytic support material is β-zeolite. In another preferred embodiment, the catalytic support material is USY zeolite. In yet another preferred embodiment, the catalytic support material is amorphous silica alumina, also called ASA. ASA has a non-uniform structure with low acidity and high surface area. The non-uniform structure tends to create acidic sites that are not available to large molecules, which leads to inferior performance of ASA alone as compared to MCM-41 or a combination of MCM-41 with ASA. Similarly, the USY and β-zeolite supports suffer from drawbacks related to the microporous nature of the supports which makes the catalyst less efficient for large molecules since it is diffusion limited. These supports used alone tend to plug rapidly, thereby deactivating the catalyst. However, the MCM-41 support material overcomes these flaws. In a preferred embodiment, the catalytic support material is solely ultra stable Y zeolite, MCM41 mesoporous material, β-zeolite, amorphous silica alumina or combinations thereof. A particularly preferred embodiment includes a single catalytic support material that is substantially all MCM-41. This material is mesoporous that is well-structured and has uniform morphology with high surface area. It also has low acidity as compared to beta and USY support materials. The invention includes the use of proper support material and a balance between acidic and metallic function with the proper distribution of metals throughout the support material. This is accomplished through the very well-structured morphology features of MCM-41 support material, which contains both acidic and metallic site that are accessible to the large hydrocarbon molecules found in VGO and DMO. For this reason, high conversion is achieved. Advantageously the lower acidity of MCM-41 as compared to other support materials drives conversion toward selectivity towards mid distillates and limits the production of undesirable light gases.
  • In a preferred embodiment of the invention, the catalytic metal is in a sulfide form. For example, molybdenum in the form of molybdenum sulfide is preferred.
  • In a preferred embodiment, promoter metals include solely nickel.
  • The catalyst of the invention is particularly useful for VGO/DMO hydrocarbon blend contains at least 10% DMO by volume. Test runs have been made for VGO/DMO hydrocarbon blend contains at least 15% DMO by volume.
  • Impregnation of the catalytic metal and the promoter metal onto the catalytic support is accomplished through methods known in the art, such as co-impregnation method. The process of catalytically converting a heavy hydrocarbon containing de-metallized oil includes the steps of introducing the heavy hydrocarbon containing de-metallized oil into a reactor stage and introducing the catalyst into the reactor stage. The catalyst introduced into the reactor stage includes the catalytic support material, the catalytic metal impregnated upon the catalytic support material, and the promoter metal on the catalytic support material to enhance catalytic conversion. The catalytic support material with catalytic metal and promoter metal operate to catalytically convert at least a portion of the de-metallized oil into hydrocarbon products having shorter carbon chains.
  • The process reaches and maintains a pre-defined temperature in the reactor operable to achieve conversion. In a preferred embodiment, the pre-defined temperature is at least 390 degrees C. In a more particularly preferred embodiment, the pre-defined temperature is at least 400 degrees C.
  • In a preferred embodiment, a majority of the pores of the catalyst support are located within 20 to 50 Angstrom (Å) and the catalyst support has a large surface area as measured through pore size distribution. Table 1 shows examples of preferred embodiments.
    TABLE 1
    Prepared Catalysts Textual Characteristics
    Average
    BET Surface Area Pore Volume Pore Diameter
    Sample (m2/g) (cm3/g) (A0)
    NiMo-ASA 186 0.33 36
    NiMo-MCM-41 324 0.40 25
    NiMo-β 313 0.41 26
    NiMo-USY 300 0.35 23
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • So that the manner in which the features, advantages and objects of the invention, as well as others that will become apparent, may be understood in more detail, more particular description of the invention briefly summarized above may be had by reference to the embodiment thereof which is illustrated in the appended drawings, which form a part of this specification. It is to be noted, however, that the drawings illustrate only a preferred embodiment of the invention and is therefore not to be considered limiting of the invention's scope as it may admit to other equally effective embodiments.
  • FIG. 1 depicts a schematic of a preferred embodiment of the process with the catalyst of the invention.
    • DETAILED DESCRIPTION OF THE INVENTION
  • Several catalysts were prepared using nickel (Ni)/molybdenum (Mo) metals loadings along with the four different support materials identified above. The four catalyst formulations created in this manner were characterized using gas sorption analyzer, temperature programmed reduction (TPR) and temperature programmed de-sorption (TPD). Moreover, the catalyst formulations were tested in a batch reactor and compared against a commercial catalyst. The outcome of this work showed that the formulation including MCM-41 catalyst support, resulting in NiMo-MCM-41, has performed better than the commercial catalyst on heavy hydrocarbons, in particular, VGO/DMO blends. NiMo-MCM-41 showed higher hydrodesulfurization (HDS) and hydrogenation activities. In addition, it had higher conversion and higher diesel yield than commercial catalyst.
  • Most of the hydrocracking catalysts of commercial interest are dual functional in nature, consisting of both a hydrogenation-dehydrogenation component and an acidic support. The reactions catalyzed by the individual components are quite different. In specific catalysts, the relative strengths of the two components can be varied. The reactions occurring and the products formed are influenced by the balance between these two components.
    TABLE 2
    Acidity for all prepared catalysts
    Catalyst Acidity (mmol/g) Peak Temperature (° C.)
    NiMo-MCM-41 0.33 264
    NiMo-ASA 0.50 252
    NiMo-β 0.56 233
    NiMo-USY 0.59 238
  • Table 2 shows the TPD of ammonia for all of the prepared hydrocracking catalysts. The acidity of the prepared catalysts ranges from 0.33 mmol/g (NiMo-MCM-41) to 0.59 mmol/g (NiMo-USY). The lower acidity of NiMo-MCM-41 catalyst is expected since MCM-41 is a silica based material and has low amount of alumina. Therefore, NiMo-MCM-41 catalyst has lower amount of γ-alumina than the other prepared catalysts.
  • The catalytic metal, such as molybdenum, and the promoter metal, such as nickel, provide the hydrogenation-dehydrogenation functions. As noted, this is preferably in the sulfide form. Other group VIA and group VIIIA metals are useful as promoter metal and catalytic metal. These metals catalyze the hydrogenation of the feedstock, making it more reactive for cracking and heteroatom removal, as well as reducing the coking rate. They also initiate the cracking by forming a reactive olefin intermediate via dehydrogenation.
  • Since hydrocracking of industrial feedstocks is to be carried in presence of hydrogen sulfide and organic sulfur compounds, it is preferred that the metal site be in a metal sulfide form of the VIA group promoted by a nickel or cobalt sulfide.
  • The reactions that occur during the hydrocracking process take three major routes. First, non-catalytic thermal cleavage of C-C bonds via hydrocarbon radicals, with hydrogen addition (hydropyrolysis). Second, monofunctional C-C bond cleavage with hydrogen addition over hydrogenation components consisting of metals, oxides or sulfides (hydrogenolysis). Third, bifunctional C-C bond cleavage with hydrogen addition over bifunctional catalysts consisting of a hydrogenation component dispersed on a porous, acidic support. In addition to the above reactions, there are other reactions that take place during the hydrocracking process. These can include hydrodesulfurization, hydrodeintrofication, hydrodeoxigenation, olefin hydrogenation and partial aromatic hydrogenation.
    TABLE 3
    Experimental Design
    Catalyst Systems
    Com- NiMo- NiMo- NiMo- NiMo-
    mercial MCM-41 USY β ASA
    Catalyst
    Preparation
    γ-alumina binder, 70 70 70 70
    wt %
    Support, wt % 30 30 30 30
    NiO, wt % 2.5 2.5 2.5 2.5
    MoO3, wt % 12 12 12 12
    Ni, wt % 2 2 2 2
    Mo, wt % 8 8 8 8
    Atomic Ratio 0.2 0.2 0.2 0.2
    Catalyst
    Characterization
    Surface Area, 324 300 313 186
    m2/g
    Pore Vol., cm3/g 0.4 0.35 0.41 0.33
    Pore Size, 25 23 26 36
    Angstrom
    Acidity, 0.33 0.59 0.56 0.5
    mmol/gm
    Catalyst
    Evaluation
    Batch Reactor — —
    No. of Runs 5 1 1 1 1
    Temperatures, 410 410 410 410 410
    deg. C.
    Pressures, kg/cm2 150 150 150 150 150
    Feed weight, g 100 100 100 100 100
    Catalyst weight, g 3 3 3 3 3
  • The commercial catalyst that was used for comparison is DHC-8 from Universal Oil Products (UOP) Company. γ-alumina was used as binder for all catalyst prepared in this test shown above. The amount of γ-alumina used was 70% of the total catalyst support.
    TABLE 4
    Feedstock Definition
    VGO/DMO
    Feedstock Properties VGO DMO 85%/15%
    Specific Gravity 0.92-0.93 0.96-0.97 0.93-0.94
    Total Nitrogen, wt ppm 700-900 1300-2100 1100-1200
    Total Sulfur, wt % 2-3   3-3.5 2.6-2.8
    ASTM Distillation, D2887
    5%, ° C. 279 402
    50%, max ° C. 472 596 495
    90%, max ° C. 543 678 615
    Ni + V wt. ppm <1  8.0-13.5 2-3
  • TABLE 5
    Tested catalysts conversion for 800-900° F. cut and 900-1050° F. cut
    1Conversion %
    NiMo- NiMo- NiMo- NiMo-
    Cut Range, ° F. Commercial MCM-41 β ASA USY
    800-900 13.37 19.23 17.57 15.78 15.04
    900-1050 35.29 36.33 32.74 34.56 35.69
    Overall 27.01 29.97 27.01 27.47 27.89
  • Among the four catalyst formulations described above that are encompassed within the invention, NiMo-MCM-41 catalyst had the lowest acidity and the highest surface area. This is attributed to the fact that MCM-41 is a silica-based material and has low amounts of alumina. This is one of the advantages of MCM-41 being mesoporous and having low acidity. The mesoporous feature along with the lower acidity of NiMo-MCM41 catalyst promotes the highest conversion and the lowest gas make.
  • While the invention has been shown or described in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes without departing from the scope of the invention.

Claims (27)

1. A catalyst for treating VGO/DMO hydrocarbon blend to catalytically convert the VGO/DMO blend to shorter-chain valuable hydrocarbon products, the catalyst comprising:
a catalytic support material comprising MCM-41 mesoporous material,
a catalytic metal impregnated upon the catalytic support material, and,
a promoter metal on the catalytic support material to enhance catalytic conversion,
the catalytic support material with catalytic metal and promoter metal operable to catalytically convert VGO/DMO into hydrocarbon products having shorter carbon chains.
2. The catalyst of claim 1 wherein the catalytic metal component is molybdenum and the promoter metal is nickel.
3. The catalyst of claim 2 wherein the catalytic support material is solely MCM-41 mesoporous material.
4. The catalyst of claim 2 wherein substantially all of the nickel is in the form of nickel sulfide.
5. The catalyst of claim 1 wherein the catalytic metal component is selected from the group consisting of molybdenum, tungsten and combinations thereof, and wherein the promoter metal is selected from a group consisting of nickel, cobalt and combinations thereof.
6. The catalyst of claim 1 wherein the VGO/DMO hydrocarbon blend contains at least 10% DMO by volume.
7. The catalyst of claim 1 wherein the VGO/DMO hydrocarbon blend contains at least 15% DMO by volume.
8. The catalyst of claim 1 wherein the catalytic metal and the promoter metal are impregnated upon the catalytic support through co-impregnation.
9. The catalyst of claim 1 wherein the catalytic metal and the promoter metal are impregnated upon the catalytic support through successive impregnation.
10. The process of catalytically converting a heavy hydrocarbon containing de-metallized oil comprising the steps of:
introducing the heavy hydrocarbon containing de-metallized oil into a reactor stage,
introducing the catalyst into the reactor stage, the catalyst comprising:
a catalytic support material comprising MCM-41 mesoporous material,
a catalytic metal impregnated upon the catalytic support material, and,
a promoter metal on the catalytic support material to enhance catalytic conversion,
the catalytic support material with catalytic metal and promoter metal operable to catalytically convert at least a portion of the de-metallized oil into hydrocarbon products having shorter carbon chains.
11. The process of claim 10 wherein the catalytic metal component is molybdenum and the promoter metal is nickel.
12. The catalyst of claim 11 wherein the catalytic support material includes ultra stable Y zeolite.
13. The process of claim 11 wherein the catalytic support material is solely MCM-41 mesoporous material.
14. The process of claim 11 wherein the catalytic support material includes β-zeolite.
15. The process of claim 11 wherein the catalytic support material includes amorphous silica alumina.
16. The process of claim 11 wherein the catalytic support material is selected from the group consisting of ultra stable Y zeolite, MCM-41 mesoporous material, β-zeolite, amorphous silica alumina, and combinations thereof.
17. The process of claim 11 wherein at least a portion of the nickel is in the form of nickel sulfide.
18. The process of claim 11 wherein the catalytic metal component is selected from the group consisting of nickel, cobalt and combinations thereof, and wherein the promoter metal is selected from a group consisting of molybdenum, tungsten and combinations thereof.
19. The process of claim 11 wherein the VGO/DMO hydrocarbon blend contains at least 10% DMO by volume.
20. The process of claim 11 wherein the VGO/DMO hydrocarbon blend contains at least 15% DMO by volume.
21. The process of claim 18 wherein at least a portion of the nickel is in the form of nickel sulfide.
22. The process of claim 18 wherein at least a portion of the cobalt is in the form of cobalt sulfide.
23. The process of claim 10 wherein the catalytic metal and the promoter metal are impregnated upon the catalytic support through co-impregnation.
24. The process of claim 10 wherein the catalytic metal and the promoter metal are impregnated upon the catalytic support through successive impregnation.
25. The process of claim 10 further comprising the step of maintaining a pre-defined temperature in the reactor.
26. The process of claim 25 wherein the pre-defined temperature is at least 390 degrees C.
27. The process of claim 25 wherein the pre-defined temperature is at least 400 degrees C.
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EP1835993A1 (en) 2007-09-26
JP5260059B2 (en) 2013-08-14
CN101094720B (en) 2013-04-24
RU2416462C2 (en) 2011-04-20
WO2006071963A1 (en) 2006-07-06

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