WO2006116914A1 - Catalyseur d'hydrocraquage, sa preparation et son utilisation - Google Patents

Catalyseur d'hydrocraquage, sa preparation et son utilisation Download PDF

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Publication number
WO2006116914A1
WO2006116914A1 PCT/CN2006/000799 CN2006000799W WO2006116914A1 WO 2006116914 A1 WO2006116914 A1 WO 2006116914A1 CN 2006000799 W CN2006000799 W CN 2006000799W WO 2006116914 A1 WO2006116914 A1 WO 2006116914A1
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Prior art keywords
molecular sieve
zeolite
weight
content
catalyst
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PCT/CN2006/000799
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English (en)
French (fr)
Inventor
Yichao Mao
Hong Nie
Jianwei Dong
Zhenlin Xiong
Zhihai Hu
Yahua Shi
Dadong Li
Original Assignee
China Petroleum & Chemical Corporation
Research Institute Of Petroleum Processing, Sinopec
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Application filed by China Petroleum & Chemical Corporation, Research Institute Of Petroleum Processing, Sinopec filed Critical China Petroleum & Chemical Corporation
Priority to US11/919,619 priority Critical patent/US8334231B2/en
Priority to EP06722404.8A priority patent/EP1900430B1/en
Priority to CA2606063A priority patent/CA2606063C/en
Publication of WO2006116914A1 publication Critical patent/WO2006116914A1/zh

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • 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
    • B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
    • B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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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
    • B01J29/78—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0202—Alcohols or phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0237—Amines
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    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • 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
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/50—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metal, 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
    • 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
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    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
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    • 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
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    • B01J2229/37—Acid treatment
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    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
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    • B01J2229/42—Addition of matrix or binder particles
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    • 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
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    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • 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
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    • C10G2300/1022—Fischer-Tropsch products
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    • 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
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    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
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    • 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
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    • C10G2300/1074—Vacuum distillates
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    • 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
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    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV

Definitions

  • Hydrocracking catalyst preparation method thereof and application thereof
  • the present invention relates to a hydrocracking catalyst, a process for its preparation and its use.
  • the hydrocracking catalyst is a bifunctional catalyst which has both catalytic cracking activity and hydrogenation activity, that is, contains both an acidic component and a hydrogenation active component;
  • the cracking component is generally selected from acidic silicoalumino, and the acidic silica alumina includes : Silica-alumina, zeolite molecular sieves and mixtures thereof,
  • the hydrogenation active component is generally selected from the group consisting of metals, metal oxides and/or metal sulfides of Groups VIB and VIII of the Periodic Table of the Elements.
  • CN1054150C discloses a diesel hydroconversion catalyst comprising a carrier composed of alumina, amorphous silica alumina and molecular sieves and a hydrogenation active metal supported on the carrier, wherein the content of W0 3 in the catalyst is 10 - 30 weight %, NiO content is 2-15% by weight, molecular sieve content is 5-45% by weight, alumina content is 30-70% by weight, amorphous silicon aluminum content is 5-25% by weight, and the molecular sieve is The Y type molecular sieve has a total infrared acid amount of 0.5-1 ⁇ mol/g and a unit cell constant of 2.436 - 2.444 nm.
  • the alumina is a pore-pore alumina having a pore volume of 0.8 to 1.1 liters per gram; and a surface area of 230 to 400 m 2 /g.
  • CN1184843 A discloses a diesel hydroconversion catalyst having a composition of 40-80% by weight of alumina, 0-20% by weight of amorphous silicon aluminum, and 5:30% by weight of molecular sieve, and the molecular sieve has a pore volume of 0.40. -0.52 liters/gram, specific surface 750-900 m 2 /g, unit cell constant 2.420-2.500, silicon-aluminum ratio 7-15 Y-type molecular sieve, VIB group metal content 10-30% by weight, V111 group metal oxide The content is 2-15% by weight.
  • No. 5,030,780 discloses a process for the saturation of aromatic hydrocarbon compounds which comprises a catalyst comprising a hydrogenation metal supported on a support comprising a zeolite and a porous heat-resistant inorganic An oxide, in particular a heat-resistant inorganic oxide containing silicon-aluminum dispersed in an alumina matrix, which comprises various natural or synthetically synthesized various crystalline silicalite zeolites, such as faujasite, mordenite, Erionite zeolite, Y-type zeolite, X-type zeolite, L-zeolite, omega zeolite, ZSM-4 zeolite, Beta zeolite, and the like.
  • a catalyst comprising a hydrogenation metal supported on a support comprising a zeolite and a porous heat-resistant inorganic An oxide, in particular a heat-resistant inorganic oxide containing silicon-aluminum dispersed in an alumina matrix, which comprises various natural or synthetic
  • CN1055961C discloses a hydrocracking which is particularly suitable for the production of middle distillates
  • the catalyst comprises an amorphous silicon aluminum component and a small pore alumina binder, the amorphous silicon aluminum content is 30-60 w%, at least one group VIB element and at least one race element, total hydrogenation metal oxide content 20-35w %, the balance is a small pore alumina binder characterized by a catalyst specific surface of 150-300 m 2 /g, a pore volume of 0.2 5 _0. 50 ml / g, a 4-15 nm pore distribution of 60-90 % , infrared acidity 0.30-0.50mmol / g.
  • a diesel hydrotreating catalyst comprising a support and molybdenum and/or tungsten and nickel and/or cobalt supported on the support, wherein the support consists of alumina and zeolite, alumina
  • the weight ratio to the zeolite is 90: 10-50: 50
  • the alumina is a composite of small pore alumina and macroporous alumina in a weight ratio of 75:25-50:50, wherein
  • the porous alumina is alumina having a pore volume of less than 80 angstroms in diameter and 95% or more of the total pore volume
  • the macroporous alumina is alumina having a pore volume of 60-600 angstroms in diameter and a total pore volume of 70% or more.
  • hydrocracking catalysts provided by the prior art can meet the requirements of some hydrocracking reactions, but the catalyst aromatics saturation and ring opening activity are still low. Detailed description of the invention
  • the object of the present invention is to overcome the disadvantages of the existing aromatic hydrocracking and low ring opening activity of the hydrocracking catalyst, and to provide a hydrocracking catalyst with high aromatic saturation and ring opening activity (hereinafter sometimes referred to as Inventive catalysts and methods for their preparation.
  • the invention further relates to the use of the hydrocracking catalyst in a hydrocarbon oil hydrocracking process.
  • the present invention first provides a hydrocracking catalyst comprising a composite shaped support of zeolite molecular sieve and alumina, at least one Group VIII metal component, at least one Group VIB metal component, and an organic additive
  • the organic additive is selected from one or more of an oxygen-containing or nitrogen-containing organic compound, and the content of the zeolite molecular sieve is from 3 to 60% by weight based on the weight of the catalyst, and the content of the alumina
  • the content of the organic additive is from 10 to 80% by weight, based on the oxide and based on the weight of the catalyst, and the content of the Group VIII metal component is from 1 to 15% by weight.
  • the Group VIB metal component is contained in an amount of 5 to 40% by weight.
  • the hydrocracking catalyst is other than a composite shaped support of zeolite molecules classified as alumina, at least one Group VIII metal component, at least one Group VIB metal component, and an organic additive, Contains other components. That is, the hydrocracking catalyst of one embodiment of the present invention is composed of the zeolite molecular sieve and the alumina The composite shaped support, the at least one Group VIII metal component, the at least one Group VIB metal component, and the organic additive, wherein the organic additive is selected from the group consisting of oxygen or nitrogen One or more of the organic compounds, the zeolite molecular sieve is contained in an amount of from 3 to 60% by weight, the alumina is contained in an amount of from 10 to 80% by weight, based on the weight of the catalyst, the organic additive
  • the content of the Group VIB metal component is from 0.1 to 40% by weight based on the oxide and based on the weight of the catalyst, the content of the Group VIII Group VIII metal component is from 1 to 15% by weight. It is 5-40% by weight.
  • the aromatic hydrogenation activity of the catalyst provided by the present invention is significantly improved as compared to the catalyst provided by the prior art process.
  • the catalyst C-1 provided by the present invention containing an organic additive is exemplified as the reference catalyst RC-1 except that the catalyst C1 contains 0.85 wt% of EDTA as an organic additive.
  • the aromatics hydroconversion activity of catalyst C1 was increased by 5% compared to the reference catalyst RC-1.
  • the invention also provides a preparation method of the hydrocracking catalyst, which comprises mixing together, molding and calcining a precursor of zeolite molecular sieve, alumina and/or alumina to prepare a composite shaped carrier, and then to the composite Introducing at least one Group VIII Group VIII metal component, at least one Group VIB metal component, and an organic additive to the shaped support, wherein the organic additive is selected from one or more of an oxygen-containing or nitrogen-containing organic compound And the components are used in an amount such that the content of each component in the obtained catalyst satisfies the following conditions: the content of the zeolite molecular sieve is from 3 to 60% by weight based on the weight of the catalyst, the oxidation The content of aluminum is 10 to 80% by weight, the content of the organic additive is 0.1 to 40% by weight, based on the weight of the catalyst, and the content of the Group VIII metal component is 1 -15% by weight, the Group VIB metal component is contained in an amount of 5 to 40% by weight.
  • the invention relates to the use of the hydrocracking catalyst in a hydrocarbon oil hydrocracking process.
  • the step of contacting the hydrocarbon oil feed with the hydrocracking catalyst under conditions of hydrogen presence and hydrocracking reaction is included.
  • the aromatic hydrocarbon hydroconversion efficiency of the hydrocarbon oil hydrocracking process can be greatly improved.
  • the present invention is to provide an additive containing an organic catalyst in the C-3 3 5 0 ⁇ , hydrogen partial pressure 6.4MPa, LHSV 0.75 hours under hydrogen to oil by volume as the method 800 Hydrocracking of the feedstock oil provided. It differs from the reference method in Comparative Example 3 only in that the hydrocracking process catalyst described below does not contain an organic additive.
  • the yield of the ⁇ 350 ⁇ produced oil in the above process was increased by 5.8 w%, and the BMCI value of the >350 ⁇ produced oil was 1.9 units lower than the comparative example, and the reaction temperature was increased to 380 ,, including The hydrocracking process of the addition of the organic catalyst ⁇ 35010 produced oil further increased by 16 w%, while the BMCI value of the >350*C produced oil was further reduced by 4.8 units.
  • the present invention relates to the invention of the following aspects:
  • a hydrocracking catalyst comprising a composite shaped support of zeolite molecular sieve and alumina, at least one Group VIII metal component, at least one Group VIB metal component, and an organic additive, said organic additive Or one or more selected from the group consisting of oxygen-containing or nitrogen-containing organic compounds, the zeolite molecular sieve is contained in an amount of from 3 to 60% by weight, and the alumina is contained in an amount of from 10 to 80% by weight based on the weight of the catalyst. %, the content of the organic additive is 0.1 to 40% by weight, based on the weight of the catalyst, and the content of the Group VIII metal component is 1 to 15% by weight, the first The content of the Group VIB metal component is from 5 to 40% by weight.
  • the hydrocracking catalyst according to aspect 1 characterized in that the catalyst is classified by the zeolite molecule into the composite shaped support of the alumina, the at least one Group VIII metal component, Said at least one Group VIB metal component and said organic additive composition.
  • the oxygen-containing organic compound is selected from one or more of an organic alcohol and an organic acid
  • the nitrogen-containing organic compound is selected from the group consisting of organic amines.
  • One or more of the zeolite molecular sieves having a content of 5 to 60% by weight, the alumina content being 15 to 80% by weight, and the organic additive content being 0.5-30% by weight, based on the oxide and based on the weight of the catalyst, the content of the Group VIII Group VIII metal component is 2-8 wt%, and the content of the Group VIB metal component is 10- 35 wt%.
  • zeolite molecule is selected from zeolite molecular sieves having a faujasite structure, zeolite molecular sieves having a Beta zeolite structure, and zeolite molecular sieves having a mordenite structure.
  • zeolite molecular sieves having a faujasite structure zeolite molecular sieves having a Beta zeolite structure
  • zeolite molecular sieves having a mordenite structure One or several.
  • the zeolite molecule having a faujasite structure is selected from the group consisting of a HY zeolite molecular sieve, a rare earth type Y zeolite REY molecular sieve, a rare earth type HY zeolite REHY molecular sieve, and an ultrastable Y.
  • the organic additive
  • the content of the alumina is 15 to 80% by weight
  • the content of the organic additive is 0.5 to 30% by weight, based on the oxide and based on the weight of the catalyst
  • the Group VIII The content of the metal component is 2 to 8% by weight
  • the content of the metal component of the Group VIB is 10 to 35% by weight.
  • zeolite molecule is selected from a zeolite molecular sieve having a faujasite structure, a zeolite molecular sieve having a Beta zeolite structure, and a zeolite molecular sieve having a mordenite structure. One or several of them. 11.
  • zeolite molecule having a faujasite structure is selected from the group consisting of a HY zeolite molecular sieve, a rare earth type Y zeolite REY molecular sieve, a rare earth type HY zeolite REHY molecular sieve, One or more of ultra-stable Y zeolite USY molecular sieves, rare earth type ultrastable Y zeolite REUSY molecular sieves and dealuminated Y zeolite molecular sieves.
  • a hydrocarbon oil hydrocracking process comprising contacting a hydrocarbon oil feed with the hydrocracking catalyst of any of the preceding aspects 1-7 under conditions of hydrogen presence and hydrocracking.
  • hydrocarbon oil hydrocracking process wherein the hydrocracking reaction conditions comprise: a reaction temperature of 200 to 650 Torr, a hydrogen partial pressure of 3 to 24 MPa, and a liquid hourly space velocity of 0.1 to 10 Hours — and the hydrogen oil volume ratio is 100 - 5000.
  • hydrocarbon oil hydrocracking process wherein the hydrocracking reaction conditions comprise: a reaction temperature of 220-510*C, a hydrogen partial pressure of 4-15 MPa, and a liquid hourly space velocity of 0.2. -5 hours - 1 , and the hydrogen oil volume ratio is 200-1000.
  • hydrocarbon oil hydrocracking process wherein the hydrocarbon oil is selected from the group consisting of heavy mineral oil, synthetic oil or a mixed distillate thereof.
  • Figure 1 is an infrared hydroxyl diagram of the zeolite molecular sieve prepared in Example 2.
  • Figure 2 is an infrared hydroxyl error diagram of the zeolite molecular sieve prepared in Example 3. The best way to implement the invention
  • the catalyst provided according to the present invention comprises a composite shaped support of zeolite molecules attributed to alumina, a Group VIII metal component, a Group VIB metal component, and an organic additive.
  • zeolite molecular sieves which are often used as cracking active components
  • a zeolite molecular sieve having a macroporous structure such as a zeolite molecular sieve having a faujasite structure, a beta zeolite structure or an omega zeolite structure
  • a zeolite molecular sieve having a mesoporous structure, such as a mordenite structure, ZSM-5 may be mentioned.
  • Zeolite structure ZSM-11 zeolite structure, ZSM-22 zeolite structure, ZSM-23 zeolite structure, ZSM-35 zeolite structure, ZSM-48 zeolite structure, ZSM-57 zeolite structure, etc.; or zeolite with small pore structure
  • Molecular sieves such as zeolite molecular sieves having an Erionite zeolite structure or a ZSM-34 zeolite structure.
  • the zeolite molecule is selected from one or more of a zeolite molecular sieve having an octagonal zeolite structure, a zeolite molecular sieve having a Beta zeolite structure, and a zeolite molecular sieve having a mordenite structure.
  • the zeolite molecular sieve having a faujasite structure is further preferably a Y-type zeolite molecular sieve, and the Y-type zeolite molecular sieve is further preferably selected from the group consisting of a HY zeolite molecular sieve, a rare earth type Y zeolite REY molecular sieve, a rare earth type HY zeolite REHY molecular sieve, and an ultrastable Y zeolite USY.
  • the zeolite molecular sieve has a ratio of B acid to L acid greater than 0.9, and when characterized by an infrared spectrum of the hydroxyl group, at least one characteristic peak characterizing the silanol group is present in the range of 3760 to 3685 cm- 1 . It is further preferred that the ratio of B acid to L acid is 1-10, and when characterized by the infrared spectrum of the hydroxyl group, two characteristic peaks characterizing the silyl group appear in the range of s so sess cm- 1 .
  • the ratio of citric acid to L acid of the zeolite molecular sieve was measured by a Bio-Rad IFS-3000 infrared spectrometer.
  • the specific method is as follows: the zeolite molecular sieve sample itself is finely ground and pressed into a self-supporting piece of about 10 mg/cm 2 , placed in an in-situ cell of an infrared spectrometer, and surface-purified for 2 hours under a vacuum of 350 ⁇ , 10" 3 Pa, After dropping to room temperature, the pyridine saturated vapor was introduced, and after adsorption and equilibration for 15 minutes, vacuum desorption was carried out for 30 minutes at 200 Torr, and the adsorption pyridine vibration spectrum was measured after dropping to room temperature.
  • the scanning range was MOOcm-i-OOcm- 1 , with 1540 soil.
  • the ratio of the infrared absorption of the 5 cm- 1 band to the weight and area of the sample defines the amount of B acid [unit The infrared absorption value of the area and unit mass sample is expressed as: AB ⁇ (cm 2 ⁇ g) - 1 ].
  • the ratio of the infrared absorption value of the 1450 ⁇ 5 cm 1 band to the weight and area of the sample piece defines the L acid amount [infrared absorption value per unit area, unit mass sample, expressed as: AL ⁇ (cm 2 ' g) 1 ] , the value of AB/AL is defined as the ratio of B acid to L acid of the zeolite molecular sieve.
  • the hydroxy infrared spectrum of the zeolite molecular sieve is determined by: grinding the zeolite molecular sieve sample into a self-supporting piece of about 10 mg/cm 2 and placing it in an in-situ pool of an infrared spectrometer. The measurement was carried out using a Bio-Rad IFS-3000 infrared spectrometer. Firstly, the surface was cleaned for 2 hours under vacuum of 350"C, 10 3 Pa, and the hydroxyl vibration spectrum was measured after falling to room temperature. The scanning range was
  • the zeolite molecular sieve used in the present invention may be commercially available or may be produced in accordance with a conventional method. This is well known to those skilled in the art.
  • alumina As the alumina, it can be selected from alumina which is commonly used as a catalyst substrate in the art, and it can be commercially available or can be produced by a conventional method.
  • the alumina is selected from the group consisting of gamma-alumina, eta-alumina,
  • cerium-alumina, ⁇ -alumina, and X-alumina or one selected from the group consisting of one or more selected from the group consisting of titanium, magnesium, boron, zirconium, hafnium, tantalum, and rare earth
  • ⁇ -alumina, ⁇ -alumina, ⁇ -alumina, and X-alumina of one or more added components preferably ⁇ -alumina and containing one or A plurality of cerium-alumina selected from one or more of titanium, magnesium, boron, zirconium, hafnium, cerium and rare earth.
  • the composite shaped support of the zeolite molecular sieve and the alumina may be commercially available or may be prepared according to a conventional molding method.
  • the shape of the composite molded carrier may, for example, be a microsphere, a sphere, a tablet or a strip.
  • a molding method for example, a method of molding and baking a mixture of alumina and/or its precursor and molecular sieve can be mentioned.
  • the precursor of the alumina may be selected from one or more of various hydrated alumina and aluminum sol, or may be selected from one selected from the group consisting of titanium, magnesium, boron, zirconium, hafnium, tantalum and rare earth.
  • One or more of hydrated alumina and aluminum sol of one or more added components are examples of alumina and aluminum sol of one or more added components.
  • the forming can be carried out by a conventional method such as tableting, rolling or extruding.
  • a conventional method such as tableting, rolling or extruding.
  • an appropriate amount of the extrusion aid and/or the adhesive may be added as needed, followed by extrusion molding.
  • the types and amounts of the extrusion aids and peptizers are well known to those skilled in the art and will not be described herein.
  • the calcination can be carried out in the field. Conventional methods and conditions, for example, a calcination temperature of from 350 to 950 Torr; preferably from 400 to 650, a calcination time of from 2 to 6 hours, preferably from 3 to 5 hours.
  • the content ratio of the zeolite molecular sieve to the alumina in the composite molded carrier is not particularly limited, and any appropriate value can be employed.
  • the zeolite molecular sieve is present in an amount of from 5 to 60% by weight, based on the weight of the catalyst ultimately obtained in the present invention, and the alumina is present in an amount of from 15 to 80% by weight.
  • the Group VIII metal component and the Group VIB metal component used as the metal component in the catalyst of the present invention can be selected from the corresponding types commonly used in the art.
  • the Group VIII metal component may be selected from the group consisting of cobalt and/or nickel
  • the Group VIB metal component may be selected from the group consisting of molybdenum and/or tungsten.
  • the specific content of these metal components in the catalyst of the present invention is not particularly limited as long as it is an amount effective for the action, which is easily understood by those skilled in the art.
  • the content of the Group VIII metal component is from 2 to 8% by weight, based on the weight of the catalyst of the present invention, based on the oxide, and the content of the Group VIB metal component. It is 10-35 wt%.
  • the catalyst of the present invention also uses an organic additive as an additive component.
  • the organic additive may be selected from one or more of an oxygen-containing or nitrogen-containing organic compound.
  • the oxygen-containing organic compound may be selected from one or more of an organic alcohol and an organic acid
  • the nitrogen-containing organic compound may be selected from one or more of organic amines.
  • the oxygen-containing organic compound is preferably selected from the group consisting of ethylene glycol, glycerol, polyethylene glycol (molecular weight 200-1500), acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-cyclohexanide diamine
  • tetraacetic acid and citric acid ethylenediamine or EDTA.
  • the content of the organic additive in the catalyst of the present invention is not particularly limited as long as it is a content effective for the action.
  • the organic additive is present in an amount of from 0.5 to 30% by weight, based on the weight of the catalyst of the invention.
  • the invention also provides a process for the preparation of the hydrocracking catalyst.
  • the catalyst preparation method of the present invention introduces these into a composite shaped support by using a prescribed additive component (including at least one Group VIII metal component, at least one Group VIB metal component, and an organic additive, etc.).
  • a prescribed additive component including at least one Group VIII metal component, at least one Group VIB metal component, and an organic additive, etc.
  • the way to add components is achieved.
  • the contacting process can be carried out by any method, and for example, a dipping method can be mentioned.
  • the impregnation method is not particularly limited, and a conventional method can be employed.
  • the catalyst which satisfies the content of the additive component specified in the present invention can be prepared by adjusting and controlling the concentration and amount of the additive component solution or the amount of the composite shaped carrier, which is easy for those skilled in the art. Understand.
  • the organic additive is introduced into the composite shaped support simultaneously with the Group VIII metal component and the Group VIB metal component, and as a preferred embodiment thereof, further A step of drying the obtained catalyst is included.
  • the organic additive and the Group VIII metal component and the Group VIB metal component are separately introduced into the composite shaped support to prepare the catalyst of the present invention.
  • a solution containing at least one Group VIII metal compound and at least one Group VIB metal compound is first contacted with the composite shaped support, and then dried, followed by baking or not, and then with The solution of the organic additive is contacted and dried.
  • the contacting process can be carried out by any method, and for example, a dipping method can be mentioned.
  • the impregnation method is not particularly limited, and a conventional method can be employed.
  • the drying and calcination conditions are conventionally used in the field for preparing a catalyst, and are not particularly limited, but may be, for example, a drying temperature of 80 to 350 ⁇ , preferably 100 to 300 ⁇ , and a drying time of 1 to 24 hours, preferably
  • the calcination temperature is from 350 to 550 Torr, preferably from 400 to 500 Torr, for 2 to 12 hours, and the calcination time is from 1 to 10 hours, preferably from 2 to 8 hours.
  • the amount of the organic additive added is 0.1 to 40% by weight, preferably 0.5 to 30, based on the weight of the catalyst, by selecting the amount of introduction of the organic additive. weight%.
  • the Group VIII metal compound and the Group VIB metal compound to be used are not particularly limited as long as they can provide the metal component required in the present invention, that is, the present invention can be used.
  • a type well known in the art the Group VIII metal compound may be selected from one or more of the soluble compounds of these metals, and examples thereof include nitrates, acetates, carbonates, and chlorines of these metals.
  • the Group VIB metal compound may be selected from one or more of the soluble compounds of these metals, and examples thereof include molybdate, secondary molybdate, tungstate, metatungstate, and ethyl tungsten.
  • One or more of the acid salts One or more of the acid salts.
  • the solvent used in the preparation of various solutions is conventionally selected by those skilled in the art, and is not particularly limited, and therefore no specific provisions are made herein.
  • the catalyst of the present invention may contain other components known in the art such as P, B or the like as needed.
  • the content of the metal component in the catalyst of the present invention can be measured by a conventional method in the art, and examples thereof include X-ray fluorescence spectrometry and the like. Other contents such as the carrier and the organic compound are calculated based on the actual amount of the feed.
  • the catalysts provided in accordance with the present invention after preparation, can be formed into a variety of readily operable shaped articles, such as microspheres, spheres, tablets or strips, depending on the purpose or requirement.
  • the molding can be carried out in a conventional manner, such as tableting, rolling, extruding, and the like.
  • the catalyst provided by the present invention can be presulfided with sulfur, hydrogen sulfide or a sulfur-containing raw material at a temperature of 140-370 Torr in the presence of hydrogen before use. It can also be vulcanized in situ in the vessel, thereby converting it to a sulfide type.
  • the invention also relates to the use of the hydrocracking catalyst in hydrocracking of hydrocarbon oils. That is, the present invention provides a hydrocarbon oil hydrocracking process comprising contacting a hydrocarbon oil feed with a hydrocracking catalyst of the present invention under conditions of hydrogen presence and hydrocracking.
  • the hydrocracking reaction conditions are not particularly limited, and usual reaction conditions can be employed.
  • the reaction temperature is 200-650"C, preferably 300-. 510 ⁇ , reaction pressure 3-24 MPa, preferably 4-15 MPa, liquid hourly space velocity 0.1-10 hr -1 , preferably 0.2-5 hr -1 , hydrogen oil volume ratio 100-5000, preferably 200-1000.
  • the hydrocracking process provided by the present invention can directly process various hydrocarbon oil feedstocks and hydrocrack them.
  • the hydrocracking process can be based on any of the hydrocracking, hydrotreating processes known to those skilled in the art, typically in the products obtained from the process.
  • the hydrocarbon oil feedstock may be selected from the group consisting of heavy mineral oils, synthetic oils, or mixed distillates thereof.
  • the heavy mineral oil is selected from the group consisting of straight-run gas oil, vacuum gas oil, demetallized oil, atmospheric residue, deasphalted vacuum residue, coker distillate, catalytic cracking Oil, shale oil, coal liquefied oil or tar sand oil, etc.
  • the synthetic oil is Fischer-Tropsch synthetic oil.
  • the catalyst provided by the invention is particularly suitable for the hydrocracking of heavy and inferior distillates to produce fractions having a distillation range of ⁇ 350 ⁇ and higher than 3501 C, and is particularly suitable for more hydrocracking processes for producing fractions below 350 TC. And more effective hydrocracking processes for reducing the aromatics and naphthenic content of the feed fraction, particularly as the distillate hydrocracking known to those skilled in the art increases the diesel cetane number, reduces the BMCI value of the tail oil, etc. .
  • the BMCI value referred to in the present invention refers to the US Bureau of Mining related index, which is well known to those skilled in the art, for example, in the literature (edited by Lin Shixiong, Petroleum Refining Engineering, Third Edition, Petroleum Industry Press, ISBN 7-5021-2886). -7) The specific calculation formula is given on page 74. Under comparable conditions, this value has a regular relationship with the aromatic and naphthenic content of the sample. Generally, the higher the value indicates the higher the content of aromatics and naphthenes in the sample.
  • each metal component in the examples was determined by X-ray fluorescence spectrometry.
  • This example describes the preparation of a low citrate/L acid ratio zeolite molecular sieve
  • An example illustrates the preparation of a zeolite molecular sieve having a high B acid and L acid ratio
  • This example illustrates the preparation of a high molecular weight B acid and L acid ratio with both silica gel molecular sieves.
  • This comparative example illustrates a reference catalyst and its preparation method.
  • CZ-1 zeolite 150 g (dry basis, the same below) CZ-1 zeolite is mixed with 850 g of dry-based pseudo-boehmite (produced by Shandong Aluminum Factory, trade name SD powder), 30 g of Tianjing powder, and extruded into a circumscribed circle diameter.
  • 850 g of dry-based pseudo-boehmite produced by Shandong Aluminum Factory, trade name SD powder
  • Tianjing powder 30 g
  • the composition of the catalyst carrier is shown in Table 2.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • the catalyst support was prepared in the same manner as in Comparative Example 1, except that CZ-2 was used instead of CZ-1 zeolite.
  • the obtained carrier was named CS-1, and 100g of CS-1 carrier was used with ammonium metatungstate (Sichuan Zigong Cemented Carbide Plant, tungsten oxide content was 82% by weight) 32.67g, nickel nitrate (Beijing Yili Fine Chemicals Co., Ltd.) product, the nickel oxide content is 25.4% by weight) 22.97 g, EDTA (Beijing chemical Plant) was immersed in 80 ml of an aqueous solution of 1.77 g, 1801C for 4 hours to obtain catalyst C-2, the composition shown in Table 3.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • the catalyst support was prepared in the same manner as in Comparative Example 1, except that CZ-3 was used instead of CZ-1 zeolite.
  • the obtained carrier was named CS-2, and 100 g of CS-2 carrier containing ammonium metatungstate (Sichuan Zigong Cemented Carbide Plant, tungsten oxide content of 82% by weight) 32.67 g, nickel nitrate (Beijing Yili Fine Chemicals Co., Ltd.) products, nickel oxide content was 25.4% by weight was impregnated 80ml) of 22.97 g, 120TC dried, calcined in 320 ⁇ 2 hours, and then with ethylene glycol (Beijing Yili fine Chemicals Co., Ltd.) 648, 4 0ml aqueous solution impregnation, 120 The crucible was treated for 10 hr to obtain a catalyst C-3, the composition of which is shown in Table 3. Comparative example 2
  • This comparative example illustrates the preparation of a proportional catalyst
  • Example 7 Comparative Catalyst RC-2 The catalyst was prepared exactly as in Example 6, except that the catalyst was loaded with MW and did not contain the treatment with ethylene glycol.
  • Example 7 Comparative Catalyst RC-2 The catalyst was prepared exactly as in Example 6, except that the catalyst was loaded with MW and did not contain the treatment with ethylene glycol.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • the composition of the catalyst carrier is shown in Table 2. . After cooling to room temperature, take 100g of CS-4 carrier containing ammonium paramolybdate (Zhuzhou Cemented Carbide Factory, molybdenum oxide content is 80% by weight) 9.25g, ammonium metatungstate (Sichuan Zigong Cemented Carbide Factory, tungsten oxide content) 82 wt.%) 43.84 grams nickel nitrate (Beijing Yili fine Chemicals Co., Ltd, a nickel oxide content of 25.4% by weight was impregnated 80ml) of 18.05 g, 120TC dried, 450 ⁇ calcined 3hr.
  • This example illustrates the catalyst provided by the present invention and a process for the preparation thereof.
  • This example illustrates the performance of the catalyst provided by the present invention.
  • the hydrocracking activity of the catalysts C1-C5 was evaluated on a small fixed bed hydrocracking unit with a catalyst loading of 0.2 liters, a catalyst particle diameter of 0.3 - 0.45 mils, a reaction temperature of 390, a reaction pressure of 4.0 MPa, and hydrogen oil.
  • the ratio (molar ratio) is 25, the liquid hourly space velocity is 30 hours - 1 , and the micro-reverse evaluation is carried out with a solution of 5.41% tetrahydronaphthalene in n-octane.
  • the vulcanization was carried out before the reaction oil was introduced.
  • the vulcanization conditions were as follows: under a hydrogen pressure of 2.0 MPa, the temperature was raised to 60 C, a hexane solution containing 6% CS 2 was introduced, and the temperature was raised to 300 Torr, and the temperature was maintained for 4 hr.
  • Aromatic Hydroconversion Activity % 100 - [(Total tetralin in product + total amount of TCA in product) / Total amount of tetrahydronaphthalene in raw material] ⁇ 100.
  • This comparative example illustrates the performance of the reference catalyst.
  • This example illustrates the hydrocracking process provided by the present invention.
  • This example illustrates the hydrocracking process provided by the comparative invention.
  • the hydrocracking reaction was carried out on a 30-liter fixed-bed apparatus using RC-2 as a catalyst.
  • the catalyst loading was 20 liters.
  • the reaction conditions were: temperature 350 ⁇ , hydrogen partial pressure 6.4 MPa, liquid space-time
  • the hydrogen oil volume ratio of 800 was 0.75 hours, and the results are shown in Table 6.

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Description

一种加氢裂化催化剂、 其制备方法及其应用 发明领域
本发明涉及一种加氢裂化催化剂、 其制备方法及其应用。 技术背景
加氢裂化催化剂是一种双功能催化剂， 它同时具有催化裂解活性 和加氢活性， 即同时含有酸性组分和加氢活性组分； 裂化组分一般选 自酸性硅铝， 该酸性硅铝包括： 氧化硅-氧化铝、 沸石分子筛及其混合 物， 加氢活性组分一般选自元素周期表中 VIB族和 VIII族的金属、 金属氧化物和 /或金属硫化物。 为达到对加氢裂解产物的不同要求， 需 要对催化剂中的酸性组分和加氢活性组分进行适应性调变。
CN1054150C公开了一种柴油加氢转化催化剂， 该催化剂由氧化 铝、 无定形硅铝及分子筛组成的载体及负载在该载体上的加氢活性金 属组成，催化剂中 W03的含量为 10 - 30重％、 NiO的 含量为 2-15 重 %、 分子筛的含量为 5-45重％、 氧化铝的含量为 30-70重％、 无定形 硅铝的含量为 5-25 重％， 所述分子筛为 Y型分子筛， 其红外总酸量 为 0.5-1 亳摩尔 /克， 晶胞常数为 2.436 - 2.444纳米。 所述氧化铝为 孔容 0.8-1.1亳升 /克； 表面积 230-400米 2 /克的小孔氧化铝。
CN1184843 A公开了一种柴油加氢转化催化剂， 该催化剂的组成 为氧化铝 40-80重％、 无定形硅铝 0-20重％、 分子筛 5-：30重％， 所 述分子筛为孔容 0.40-0.52亳升 /克，比表面 750-900米 2 /克，晶胞 常 数 2.420-2.500， 硅铝比 7-15的 Y型分子筛， VIB族金属含量 10-30 重％， V111族金属氧化物的含量为 2-15重％。
US 5,030,780公开了一种芳烃化合物的饱和方法， 该方法使用了 一种催化剂， 所述催化剂含有负载在一种载体上的加氢金属， 所述催 化剂载体含有一种沸石与一种多孔耐热无机氧化物， 特别是含有分散 在氧化铝基质中的硅-铝的耐热无机氧化物， 所述沸石包括已知的自然 或人工合成的各种结晶硅铝沸石， 如八面沸石、 丝光沸石、 erionite 沸石、 Y型沸石、 X型沸石、 L沸石、 Ω沸石、 ZSM - 4沸石、 Beta 沸石等。
CN1055961C公开了一种特别适用于生产中间馏分油的加氢裂化 催化剂， 含有无定形硅铝组分和小孔氧化铝粘合剂， 无定形硅铝的含 量为 30-60w %， 至少一种 VIB族元素和至少一种種族元素， 加氢金 属氧化物总含量为 20-35w %， 余量为小孔氧化铝粘合剂， 其特征在于 催化剂比表面 150-300m2/g，孔容 0.25_0.50ml/g， 4-15nm孔分布在 60-90 % , 红外酸度 0.30-0.50mmol/g。
CN1400284A一种柴油加氢处理催化剂， 该催化剂含有一种载体 和负载在该载体上的钼和 /或钨及镍和 /或钴， 其特征在于， 所述载 体由氧化铝和沸石组成， 氧化铝与沸石的重量比为 90: 10-50： 50, 所述氧化铝是由小孔氧化铝和大孔氧化铝按照 75: 25-50： 50 的重量 比复合而成的氧化铝， 其中， 小孔氧化铝为直径小于 80埃孔的孔体 积占总孔体积 95 %以上的氧化铝， 大孔氧化铝为直径 60— 600埃孔的 孔体积占总孔体积 70 %以上的氧化铝。
现有技术提供的加氢裂化催化剂可满足一些加氢裂化反应的要 求， 但催化剂芳烃饱和及开环活性仍偏低。 发明详述
本发明的目的是克服现有的加氢裂化催化剂所存在的芳烃饱和及 开环活性较低的缺点， 提供一种芳烃饱和及开环活性均较高的加氢裂 化催化剂 （以下有时简称为本发明催化剂）及其制备方法。 本发明还 涉及所述加氢裂化催化剂在烃油加氢裂化方法中的应用。
因此， 本发明首先提供了一种加氢裂化催化剂， 其包含沸石分子 筛与氧化铝的复合成型载体、 至少一种第 VIII族金属组分、 至少一 种第 VIB族金属组分以及有机添加物， 所述有机添加物选自含氧或含 氮有机化合物中的一种或几种， 以所述催化剂的重量为基准， 所述沸 石分子筛的含量为 3-60重量％， 所述氧化铝的含量为 10-80重量％， 所述有机添加物的含量为 0.1-40重量％， 以氧化物计并以所述催化剂 的重量为基准， 所述第 VIII族金属组分的含量为 1-15重量％, 所述 第 VIB族金属组分的含量为 5-40重量％。
在一个实施方案中， 所述加氢裂化催化剂除了沸石分子歸与氧化 铝的复合成型载体、 至少一种第 VIII族金属组分、 至少一种第 VIB 族金属组分以及有机添加物以外， 不含有其他组分。 也就是说， 本发 明一个实施方案的加氢裂化催化剂由所述沸石分子筛与所述氧化铝的 所述复合成型载体、 所述至少一种第 VIII族金属组分、 所述至少一 种第 VIB族金属组分以及所述有机添加物组成， 其中所述有机添加物 选自含氧或含氮有机化合物中的一种或几种， 以所述催化剂的重量为 基准， 所述沸石分子筛的含量为 3-60 重量％， 所述氧化铝的含量为 10-80 重量％， 所述有机添加物的含量为 0.1-40 重量％， 以氧化物计 并以所述催化剂的重量为基准， 所述笫 VIII族金属组分的含量为 1-15 重量％， 所述第 VIB族金属组分的含量为 5-40重量％。
与现有技术方法提供的催化剂相比， 本发明提供的催化剂的芳烃 加氢转化活性得到显著提高。
例如， 以含有有机添加物的本发明提供的催化剂 C-1 为例， 它与 参比催化剂 RC-1 的区别仅在于所述催化剂 C1 含有 0.85 重量％的 EDTA作为有机添加物。 在采用含四氢萘 5.61 %的正辛烷溶液进行评 价时， 催化剂 C1 的芳烃加氢转化活性与参比催化剂 RC-1 相比可提 高 5 %。
本发明还提供了所述加氢裂化催化剂的制备方法， 其包括将沸石 分子筛、 氧化铝和 /或氧化铝的前身物混合在一起， 成型和焙烧， 以制 备复合成型载体， 之后向所述复合成型载体中引入至少一种笫 VIII 族金属组分、 至少一种第 VIB族金属组分以及有机添加物， 其中所述 有机添加物选自含氧或含氮有机化合物中的一种或几种， 并且所述各 组分的用量要使得所获得的催化剂中各组分的含量满足以下条件： 以 所述催化剂的重量为基准， 所述沸石分子筛的含量为 3-60重量％, 所 述氧化铝的含量为 10-80重量％， 所述有机添加物的含量为 0.1-40重 量％, 以氧化物计并以所述催化剂的重量为基准， 所述第 VIII族金属 组分的含量为 1-15重量％， 所述第 VIB族金属组分的含量为 5-40重 量％。
另外， 本发明还涉及所述加氢裂化催化剂在烃油加氢裂化方法中 的应用。 在本发明所涉及的烃油加氢裂化方法中， 包括在氢气存在和 加氢裂化反应条件下， 使烃油进料与所述加氢裂化催化剂接触的步 骤。 通过采用本发明所述的加氢裂化催化剂， 可以大大提高烃油加氢 裂化方法的芳烃加氢转化效率。
例如， 以含有有机添加物的本发明提供的催化剂 C-3在 350Ό、 氢分压 6.4MPa、 液时空速 0.75小时 氢油体积比 800的方法下进行 所提供原料油的加氢裂化。 它与参比方法对比例 3 的区别仅在于后述 加氢裂化方法催化剂中不含有机添加物。 两种方法进行对比， 在相同 的条件下， 前述过程 < 350Ό生成油的收率提高 5.8w%, 同时 >350Ό 生成油的 BMCI值较对比例低 1.9单位， 将反应温度提高到 380Ό后， 含添加有机物催化剂的加氢裂化过程< 35010生成油的收率进一步提 高 16w%， 同时 >350*C生成油的 BMCI值进一步降低 4.8单位。
也就是说， 本发明涉及以下几个方面的发明：
1、 一种加氢裂化催化剂， 其包含沸石分子筛与氧化铝的复合成 型载体、 至少一种第 VIII族金属组分、 至少一种第 VIB族金属组分 以及有机添加物， 所述有机添加物选自含氧或含氮有机化合物中的一 种或几种， 以所述催化剂的重量为基准， 所述沸石分子筛的含量为 3- 60重量％， 所述氧化铝的含量为 10-80重量％， 所述有机添加物的含 量为 0.1-40重量％， 以氧化物计并以所述催化剂的重量为基准， 所述 第 VIII族金属组分的含量为 1-15重量％， 所述第 VIB族金属组分的 含量为 5-40重量％。
2、 按照方面 1 所述的加氢裂化催化剂， 其特征在于， 该催化剂 由所述沸石分子歸与所述氧化铝的所述复合成型载体、 所述至少一种 第 VIII族金属组分、 所述至少一种笫 VIB族金属组分以及所述有机 添加物组成。
3、 按照方面 1 或 2 所述的加氢裂化催化剂， 其特征在于， 所述 含氧有机化合物选自有机醇和有机酸中的一种或几种， 所述含氮有机 化合物选自有机胺中的一种或几种， 以所述催化剂的重量为基准， 所 述沸石分子筛的含量为 5-60重量％， 所述氧化铝的含量为 15-80重量 %， 所述有机添加物的含量为 0.5-30重量％， 以氧化物计并以所述催 化剂的重量为基准， 所述笫 VIII族金属组分的含量为 2-8重量％， 所 述第 VIB族金属组分的含量为 10-35重量％。
4、 按照方面 1 或 2 所述的加氢裂化催化剂， 其特征在于， 所述 沸石分子筛选自具有八面沸石结构的沸石分子筛、 具有 Beta 沸石结 构的沸石分子筛和具有丝光沸石结构的沸石分子筛中的一种或几种。
5、 按照方面 4 所述的加氢裂化催化剂， 其特征在于， 所述具有 八面沸石结构的沸石分子筛选自 HY沸石分子筛、稀土型 Y沸石 REY 分子筛、 稀土型 HY沸石 REHY分子筛、 超稳 Y沸石 USY分子筛、 稀土型超稳 Y沸石 REUSY分子筛和脱铝 Y型沸石分子筛中的一种或 几种。
6、 按照方面 1、 2、 4或 5所述的加氢裂化催化剂， 其特征在于， 所述沸石分子筛的 B酸与 L酸的比值大于 0.9， 以羟基红外谱图表征 时， 所述沸石分子筛在 3760 ~ 3685cm-1的范围内出现至少一个表征硅 羟基的特征峰。
7、 按照方面 6 所述的加氢裂化催化剂， 其特征在于， 所述沸石 分子筛的 B酸与 L酸的比值为 1-10， 以羟基红外谱图表征时， 所述 沸石分子筛在 S eO^GSScm-1的范围内出现两个表征硅羟基的特征峰。
8、 按照方面 1 所述的加氢裂化催化剂的制备方法， 该方法包括 将沸石分子歸、氧化铝和 /或氧化铝的前身物混合在一起，成型和焙烧， 以制备复合成型载体， 之后向所述复合成型载体中引入至少一种笫 VIII族金属组分、 至少一种第 VIB 族金属组分以及有机添加物， 其 中所述有机添加物选自含氧或含氮有机化合物中的一种或几种， 并且 所述各组分的用量要使得所获得的催化剂中各组分的含量满足以下条 件： 以所述催化剂的重量为基准， 所述沸石分子筛的含量为 3-60重量 %，所述氧化铝的含量为 10-80重量％，所述有机添加物的含量为 0.1-40 重量％， 以氧化物计并以所述催化剂的重量为基准， 所述第 VIII族金 属组分的含量为 1-15重量％， 所述第 VIB族金属组分的含量为 5-40 重量％。
9、 按照方面 8 所述的加氢裂化催化剂的制备方法， 其特征在于， 所述含氧有机化合物选自有机醇和有机酸中的一种或几种， 所述含氮 有机化合物选自有机胺中的一种或几种， 并且所述各组分的用量要使 得所获得的催化剂中各组分的含量满足以下条件： 以所述催化剂的重 量为基准， 所述沸石分子筛的含量为 5-60重量％， 所述氧化铝的含量 为 15-80重量％， 所述有机添加物的含量为 0.5-30重量％， 以氧化物 计并以所述催化剂的重量为基准，所述第 VIII族金属组分的含量为 2-8 重量％， 所述第 VIB族金属组分的含量为 10-35重量％。
10、 按照方面 8所述的加氢裂化催化剂的制备方法， 其特征在于， 所述沸石分子筛选自具有八面沸石结构的沸石分子筛、 具有 Beta 沸 石结构的沸石分子筛和具有丝光沸石结构的沸石分子筛中的一种或几 种。 11、 按照方面 10 所述的加氢裂化催化剂的制备方法， 其特征在 于， 所述具有八面沸石结构的沸石分子筛选自 HY沸石分子筛、 稀土 型 Y沸石 REY分子筛、 稀土型 HY沸石 REHY分子筛、 超稳 Y沸石 USY分子筛、 稀土型超稳 Y沸石 REUSY分子筛和脱铝 Y型沸石分 子筛中的一种或几种。
12、 按照方面 8、 10 或 11 所述的加氢裂化催化剂的制备方法， 其特征在于， 所述沸石分子筛的 B酸与 L酸的比值大于 0.9， 以羟基 红外谱图表征时， 所述沸石分子筛在 3760 ~ 3685cm-1的范围内出现至 少一个表征硅羟基的特征峰。
13、 按照方面 11 所述的加氢裂化催化剂的制备方法， 其特征在 于， 所述沸石分子筛的 B酸与 L酸的比值为 1.0-10.0， 以羟基红外谱 图表征时， 所述沸石分子筛在 3760 ~ 3685cm-1的范围内出现两个表征 硅羟基的特征峰。
14、 一种烃油加氢裂化方法， 该方法包括在氢气存在和加氢裂化 反应条件下， 使烃油进料与前述方面 1-7任一项所述的加氢裂化催化 剂接触。
15、 按照方面 14 所述的烃油加氢裂化方法， 其特征在于， 所述 的加氢裂化反应条件包括： 反应温度 200 - 650Ό , 氢分压 3-24兆帕， 液时空速 0.1-10小时— 并且氢油体积比 100 - 5000。
16、 按照方面 15 所述的烃油加氢裂化方法， 其特征在于， 所述 的加氢裂化反应条件包括： 反应温度 220-510*C、 氢分压 4-15 兆帕、 液时空速 0.2-5小时 - 1, 并且氢油体积比 200-1000。
17、 按照方面 14 所述的烃油加氢裂化方法， 其特征在于， 所述 烃油选自重质矿物油、 合成油或其混合馏分油。
18、 按照方面 17 所述的烃油加氢裂化方法， 其特征在于， 所述 重质矿物油选自直馏瓦斯油、 减压瓦斯油、 脱金属油、 常压渣油、 脱 沥青减压渣油、 焦化馏出油、 催化裂化馏出油、 页岩油、 煤液化油或 沥青砂油， 所述合成油为费托合成油。 附图的筒单说明
图 1是实例 2制得的沸石分子筛的红外羟基语图。
图 2是实例 3制得的沸石分子筛的红外羟基错图。 实施发明的最佳方式
按照本发明提供的催化剂包含沸石分子歸与氧化铝的复合成型载 体、 第 VIII族金属组分、 第 VIB族金属组分和有机添加物等作为催
Figure imgf000009_0001
定， 可以举出选自常作为裂化活性组分的沸石分子筛中的一种或几 种。 具体而言， 可以举出具有大孔结构的沸石分子筛， 比如具有八面 沸石结构、 Beta 沸石结构或 Ω沸石结构的沸石分子筛； 具有中孔结构 的沸石分子筛， 比如具有丝光沸石结构、 ZSM-5 沸石结构、 ZSM-11 沸石结构、 ZSM-22沸石结构、 ZSM-23沸石结构、 ZSM-35沸石结构、 ZSM-48 沸石结构、 ZSM-57 沸石结构等的沸石分子筛； 或者具有小 孔结构的沸石分子筛， 比如具有 Erionite沸石结构或 ZSM-34沸石结 构的沸石分子筛。 在优选的实施方案中， 所述沸石分子筛选自具有八 面沸石结构的沸石分子筛、 具有 Beta 沸石结构的沸石分子筛和具有 丝光沸石结构的沸石分子筛中的一种或几种。 所述具有八面沸石结构 的沸石分子筛进一步优选 Y型沸石分子筛， 所述 Y型沸石分子筛进 一步优选选自 HY沸石分子筛、 稀土型 Y沸石 REY分子筛、 稀土型 HY沸石 REHY分子筛、 超稳 Y沸石 USY分子筛、 稀土型超稳 Y沸 石 REUSY分子筛、含磷 Y型沸石分子筛、含磷 Y型超稳沸石分子筛、 含磷 HY型沸石分子筛和脱铝 Y型沸石分子筛中的一种或几种。
在优选的实施方案中， 所述沸石分子筛的 B酸与 L酸的比值大于 0.9, 在以羟基红外谱图表征时， 在 3760 ~ 3685cm-1的范围内出现至 少一个表征硅羟基的特征峰， 进一步优选 B酸与 L酸的比值为 1-10， 在以羟基红外谱图表征时， 在 s so sesscm-1的范围内出现两个表征 硅羟基的特征峰。
所述沸石分子筛的 Β酸与 L酸的比值采用 Bio-Rad IFS-3000型 红外光谱仪测定。 具体方法为： 将沸石分子筛样品自身研细后压成约 10mg/cm2的自撑片， 置于红外光谱仪的原位池中， 于 350Ό、 10"3Pa 真空度下表面净化处理 2 小时， 降至室温后引入吡啶饱和蒸气， 吸附 平衡 15分钟之后， 在 200Ό下抽真空脱附 30分钟， 降至室温后测吸 附定吡啶振动光谱。 扫描范围为 MOOcm-i- OOcm-1, 以 1540土 5 cm-1 谱带的红外光吸收值与样品片重量和面积的比值定义其 B 酸量 [单位 面积、 单位质量样品的红外光吸收值， 表示为： AB · (cm2 · g)-1]。 以 1450 ± 5 cm 1谱带的红外光吸收值与样品片重量和面积的比值定义其 L 酸量 [单位面积、 单位质量样品的红外光吸收值， 表示为： AL · (cm2 ' g) 1] , 将 AB/AL的值定义为所述沸石分子筛的 B酸与 L 酸的比值。
所述沸石分子筛的羟基红外谱图的测定方法为： 将沸石分子筛样 品研细后压成约 10mg/cm2的自撑片， 置于红外光谱仪的原位池中。 采用 Bio-Rad IFS-3000型红外光谱仪进行测定。 首先于 350"C、 103Pa 真空度下表面净化处理 2 小时， 降至室温后测其羟基振动光谱， 扫描 范围为
Figure imgf000010_0001
本发明所采用的沸石分子筛可以是市售的， 也可以按照常规方法 进行制备。 这是本领域技术人员所公知的。
作为所述氧化铝， 可以从本领域常用作为催化剂基质的氧化铝中 选择， 可以是市售的， 也可以按照常规的方法进行制备。
在优选的实施方案中， 所述氧化铝选自 γ -氧化铝、 η -氧化铝、
Θ -氧化铝、 δ -氧化铝和 X -氧化铝中的一种或几种， 或者选自含 有一种或几种选自钛、 镁、 硼、 锆、 钍、 铌和稀土之中的一种或几种 添加组分的 Υ -氧化铝、 η -氧化铝、 Θ -氧化铝、 δ -氧化铝和 X -氧化铝中的一种或几种， 优选 γ -氧化铝和含有一种或几种选自 钛、 镁、 硼、 锆、 钍、 铌和稀土之中的一种或几种添加组分的 Υ -氧 化铝。
所述沸石分子筛与所述氧化铝的所述复合成型载体可以是市售 的， 也可以按照常规的成型方法进行制备。 作为所述复合成型载体的 形状， 例如可以举出微球、 球形、 片剂或条形等。 作为所述成型方法， 例如可以举出将氧化铝和 /或其前身物与分子筛的混合物经成型并焙烧 的方法。 所述氧化铝的前身物可以选自各种水合氧化铝和铝溶胶中的 一种或几种， 也可以选自含有选自钛、 镁、 硼、 锆、 钍、 铌和稀土之 中的一种或几种添加组分的水合氧化铝和铝溶胶中的一种或几种。 所 述成型可以采用常规的方法进行， 比如压片、 滚球或挤条等方法。 在 复合成型载体的挤出成型时， 可以根据需要先加入适量的助挤剂和 /或 胶粘剂， 然后再挤出成型。 所述助挤剂和胶溶剂的种类及用量为本领 域技术人员所公知， 在此不赘述。 另外， 所述的焙烧可以采用本领域 惯用的方法和条件， 比如， 焙烧温度为 350 - 950Ό ; 优选为 400 - 650 焙烧时间为 2— 6小时， 优选为 3 - 5小时。
对所述复合成型载体中所述沸石分子筛与所述氧化铝的含量比例 并没有特别的限定， 可以采用任何适宜的数值。 在一个优选的实施方 案中， 以本发明最终所获得的催化剂的重量为基准， 所述沸石分子筛 的含量为 5-60重量％， 所述氧化铝的含量为 15-80重量％。
本发明所迷催化剂中作为金属组分使用的第 VIII族金属组分和第 VIB 族金属组分可以从本领域常用的相应类型中选择。 比如所述第 VIII族金属组分可以选自钴和 /或镍等， 所述第 VIB族金属组分可以 选自钼和 /或钨等。 对这些金属组分在本发明所述催化剂中的具体含量 并没有特别的限定， 只要是能有效起到活性作用的含量即可， 这一点 是本领域技术人员所容易理解的。
在优选的实施方案中， 以氧化物计并以本发明所述催化剂的重量 为基准， 所述第 VIII族金属组分的含量为 2-8 重量％， 所述第 VIB 族金属组分的含量为 10-35重量％。
如前所述， 本发明所述催化剂还使用有机添加物作为添加组分。 所述有机添加物可以选自含氧或含氮有机化合物中的一种或几种。 举 例而言， 所述含氧有机化合物可以选自有机醇和有机酸中的一种或几 种， 所述含氮有机化合物可以选自有机胺中的一种或几种。 所述含氧 有机化合物优选选自乙二醇、 丙三醇、 聚乙二醇 （分子量为 200 - 1500 )、 乙酸、 马来酸、 草酸、 氨基三乙酸、 1，2 -环己垸二胺四乙酸 和柠檬酸中的一种或几种， 所述含氮有机化合物可以举出乙二胺或 EDTA。
对所述有机添加物在本发明所述催化剂中的含量并没有特别的限 定， 只要是能有效起到活性作用的含量即可。 在优选的实施方案中， 以本发明所述催化剂的重量为基准， 所述有机添加物的含量为 0.5-30 重量％。
在一个实施方案中， 本发明还提供所述加氢裂化催化剂的制备方 法。
本发明所述的催化剂制备方法通过以规定的添加组分（包括至少 一种第 VIII族金属组分、 至少一种第 VIB族金属组分以及有机添加 物等） 用量向复合成型载体中引入这些添加组分的方式来实现。 比如 可以举出将有机添加物与至少一种第 VIII族金属化合物和至少一种 第 VIB族金属化合物一起配制成混合溶液后， 与所述复合成型载体接 触的方法； 或者将至少一种笫 VIII族金属化合物和至少一种笫 VIB 族金属化合物与有机添加物分别单独配制成溶液后， 再与所述复合成 型载体接触的方法等。 所述的接触过程可以通过任何方法实现， 例如 可以举出浸渍法。 所述的浸渍方法并没有特别的限定， 可以采用常规 的方法。
根据本发明， 通过对添加组分溶液的浓度、 用量或复合成型载体 用量的调节和控制， 可以制备出满足本发明所规定的添加组分含量的 所述催化剂， 这是本领域技术人 所容易理解的。
在一个实施方案中， 将有机添加物与第 VIII族金属组分和第 VIB 族金属组分同时引入所述复合成型载体中来制备本发明所述的催化 剂， 作为其优选的实施形式， 还进一步包括干燥所获得的催化剂的步 骤。在另一个实施方案中，将有机添加物与第 VIII族金属组分和第 VIB 族金属组分分别引入所述复合成型载体中来制备本发明所述的催化 剂。 作为其优选的实施形式， 首先使含有至少一种第 VIII族金属化 合物和至少一种第 VIB族金属化合物的溶液与所述复合成型载体接 触， 然后干燥， 接着焙烧或不焙烧， 之后再与含有有机添加物的溶液 接触并干燥。 所述的接触过程可以通过任何方法实现， 例如可以举出 浸渍法。 所述的浸渍方法并没有特别的限定， 可以采用常规的方法。 所述干燥和焙烧的条件为本领域制备催化剂时惯用的条件， 并没有特 别的限定， 但可以举出干燥温度为 80-350Ό , 优选为 100-300Ό， 干 燥时间为 1-24小时， 优选为 2-12小时， 焙烧温度为 350-550Ό优选为 400-500 Ό , 焙烧时间为 1-10小时， 优选为 2-8小时。
按照本发明， 规定通过选择所述有机添加物的引入量， 而使得最 终获得的催化剂中， 以催化剂的重量为基准， 所述有机添加物的含量 为 0.1-40重量％， 优选为 0.5-30重量％。
在制备本发明所述的催化剂时， 对所采用的第 VIII族金属化合物 和第 VIB族金属化合物并没有特别的限定， 只要它们能够提供本发明 所需要的金属组分即可， 即可以采用本领域公知的类型。 具体而言， 所述第 VIII族金属化合物可以选自这些金属的可溶性化合物中的一 种或几种， 例如， 可以举出这些金属的硝酸盐、 醋酸盐、 碳酸盐、 氯 化物和可溶性络合物中的一种或几种。 所述第 VIB族金属化合物可以 选自这些金属的可溶性化合物中的一种或几种， 例如， 可以举出钼酸 盐、 仲钼酸盐、 钨酸盐、 偏钨酸盐和乙基偏钨酸盐中的一种或几种。
另外， 在本发明催化剂的制备过程中， 配制各种溶液时所用的溶 剂是本领域技术人员可常规选择的， 并没有特别的限定， 因此在本文 中不做具体的规定。
本发明催化剂在制备过程中所采用的设备等也是本领域公知的， 在此就不做赘述。
再者， 除了上述指出的几种添加组分以外， 本发明所述的催化剂 中还可以根据需要含有本领域所公知的其他组分， 如 、 P或 B等。
进一步需要指出的是， 本发明催化剂中金属组分的含量可采用本 领域常规的方法测定， 比如可举出 X射线荧光光谱法等。 其它如载体 和有机化合物的含量， 则依据实际的投料量进行计算。
按照本发明所提供的催化剂在制备后， 视不同目的或要求可制成 各种易于操作的成型物， 例如微球、 球形、 片剂或条形等。 该成型可 按常规的方法进行， 比如压片、 滚球、 挤条等。
按照本领域的常规方法， 本发明提供的催化剂在使用之前， 通常 可在氢气存在下， 于 140-370 Ό的温度下用硫、 硫化氢或含硫原料进 行预硫化， 这种预硫化可在器外进行， 也可在器内原位硫化， 由此将 其转化为硫化物型。
在还一个实施方案中， 本发明还涉及所述加氢裂化催化剂在烃油 加氢裂化中的应用。 即， 本发明提供了一种烃油加氢裂化方法， 该方 法包括在氢气存在和加氢裂化反应条件下， 使烃油进料与本发明所述 的加氢裂化催化剂接触。
在本发明提供的烃油加氢裂化方法中， 对所述的加氢裂化反应条 件没有任何特别的限定， 可以采用通常的反应条件， 例如可举出反应 温度 200-650"C， 优选 300-510Ό , 反应压力 3-24兆帕， 优选 4-15兆 帕， 液时空速 0.1-10小时 -1， 优选 0.2-5小时 -1， 氢油体积比 100-5000， 优选 200-1000。
采用本发明提供的加氢裂化方法可直接加工各类烃油原料， 对其 进行加氢裂化。 该加氢裂化过程可以基于本领域技术人员所公知的任 何一种加氢裂化、 加氢处理过程， 通常的该过程所得到的产品中一般 含有沸点和或分子量低于进料烃类的产品。 所述烃油原料可以选自重 质矿物油、 合成油或其混合馏分油。 在优选的实施方案中， 所述重质 矿物油选自直馏瓦斯油、 减压瓦斯油、 脱金属油、 常压渣油、 脱沥青 减压渣油、 焦化馏出油、 催化裂化镏出油、 页岩油、 煤液化油或沥青 砂油等， 所述合成油为费托合成油。
本发明提供的催化剂特别适用于重质和劣质馏分油的加氢裂化以 生产馏程为 <350Ό和高于 3501C的馏分， 特别的适用于更多的生产低 于 350TC馏分的加氢裂化过程， 和或更有效的降低进料馏分中芳烃和 环烷烃含量的加氢裂化过程， 特别的如本领域技术人员所公知的馏分 油加氢裂化提高柴油十六烷值， 降低尾油的 BMCI值等。
本发明中所述的 BMCI值是指美国矿务局相关指数， 为本领域技 术人员所公知， 例如在文献（林世雄主编， 石油炼制工程第三版， 石 油工业出版社， ISBN7-5021-2886-7 ) 74 页给出其具体计算公式。 在 可比条件下， 该值同样品中芳烃和环烷烃含量成一定规律的对应关 系， 一般的该值越高表明样品中芳烃和环烷烃含量越高。
下面将通过实例来说明本发明， 但这些实例并不用来限制本发 明。
实例中各金属组分的含量用 X射线荧光光谱法测定。
实例中所用试剂， 除特别说明的以外， 均为化学纯试剂。 实施例
实例 1
本实例描述低 Β酸/ L酸比值沸石分子筛的制备
取 200g 干基 NaY 沸石分子筛 （长岭催化剂长生产， 晶胞常数 24.68, 相对结晶度 100， 比表面 720m2/g，氧化钠含量 13.1w% )，加入 200g硫酸铵（北京益利精细化学品有限公司产品） ， 2000ml 水， 搅 拌， 升温至 90TC后恒温 2hr。 过滤， 水洗三次， 得沸石分子筛 NY-1。
取 100克 NY-1 , 置于一管式炉中， 边升温边 入水蒸气至 600Ό , 恒温 2hr, 降温取出后， 加入 1000ml含硫酸 0.5 %的水溶液， 搅拌， 升温至 90Ό后恒温 2hr， 水洗三次， 得滤饼沸石分子筛 NY-2
重复上述水热处理和酸洗过程三次，得沸石分子筛 CZ-1,取 CZ-1 进行红外羟基和 B酸 L酸分析， 结果见表 1。 实例 2
实例说明具有高 B酸和 L酸比值沸石分子筛的制备
取 100克 NY-1 , 120Ό干燥， 置于马弗炉中， 升温至 600TC , 恒 温 2hr, 降温取出后， 加入 1000ml含硫酸 0.1 %、 硫酸铵（北京益利 精细化学品有限公司产品） 100克的水溶液中， 搅拌升温至 90Ό后恒 温 2hr， 过滤得滤饼， 将该滤饼重复上述交换过程三次， 120TC干燥得 沸石分子筛 CZ-2, 取 CZ-2进行红外羟基（其红外羟基谱图参见附图 1 )和 B酸 L酸分析， 结果见表 1。 实例 3
本实例说明具有高 B酸和 L酸比值、 同时具有两种硅羟基沸石分 子筛的制备
取 100克 NY-1, 置于马弗炉中， 边升温边通入水蒸气升温至 550 Ό， 恒温 2hr， 降温取出后， 加入 1000ml含硫酸 0.1 %、 硫酸铵（北 京益利精细化学品有限公司产品） 100克的水溶液中， 搅拌升温至 90 Ό后恒温 2hr， 过滤得滤饼， 将该滤饼重复上述交换过程二次， 将所 得滤饼加入含氟硅酸铵 2克、 硫酸铵（北京益利精细化学品有限公司 产品） 100克的 500ml水溶液， 搅拌升温至 90Ό后恒温 2hr， 过滤， 干燥得沸石分子筛 CZ-3, 取 CZ-3进行红外羟基（其红外羟基谱图参 见附图 2 )和 B酸 L酸分析， 结果见表 1。
Figure imgf000015_0001
Figure imgf000015_0002
对比例 1
本对比例说明参比催化剂及其制备方法。
将 150克（干基， 下同） CZ-1沸石同 850克干基拟薄水铝石 （山 东铝厂生产， 商品名 SD粉） ， 30克田菁粉混合， 挤成外接圆直径为 1.6 亳米的三叶形条， 120Ό烘干， 5501C温度下焙烧 3 小时， 得载体 RS-1, 催化剂载体组成见表 2。 降温至室温后， 取 100g RS-1载体用 含偏钨酸铵（四川自贡硬质合金厂， 氧化钨含量为 82 重量％ ) 32.67 克、 硝酸镍（北京益利精细化学品有限公司产品， 氧化镍含量为 25.4 重量％ ) 22.97克的 80ml水溶液浸渍， 120TC烘干， 在 480Ό焙烧 4小 时， 得到催化剂 R-1 , 其组成见表 3。 实例 4
本实例说明本发明提供的催化剂及其制备方法。
取 100g RS-1 载体用含偏钨酸铵（四川自贡硬盾合金厂， 氧化钨 含量为 82重量％ ) 32.67克、 硝酸镍（北京益利精细化学品有限公司 产品， 氧化镍含量为 25.4 重量％ ) 22.97 克、 EDTA (北京化工厂产 品 ) 1.77克的 80ml水溶液浸渍， 180Ό处理 4小时， 得到催化剂 其组成见表 3。 实例 5
本实例说明本发明提供的催化剂及其制备方法。
催化剂载体制备同对比例 1， 所不同的是采用 CZ-2代替 CZ-1沸 石。 所得载体命名为 CS-1 , 取 100g CS-1载体用含偏钨酸铵（四川自 贡硬质合金厂， 氧化钨含量为 82重量％ ) 32.67克、 硝酸镍（北京益 利精细化学品有限公司产品， 氧化镍含量为 25.4重量％ ) 22.97克、 EDTA (北京化工厂产品） 1.77克的 80ml水溶液浸渍， 1801C处理 4 小时， 得到催化剂 C-2， 其组成见表 3。 实例 6
本实例说明本发明提供的催化剂及其制备方法。
催化剂载体制备同对比例 1， 所不同的是采用 CZ-3代替 CZ-1沸 石。 所得载体命名为 CS-2, 取 100g CS-2载体用含偏钨酸铵（四川自 贡硬质合金厂， 氧化钨含量为 82重量％ ) 32.67克、 硝酸镍（北京益 利精细化学品有限公司产品， 氧化镍含量为 25.4重量％ ) 22.97克的 80ml水溶液浸渍， 120TC烘干， 在 320Ό焙烧 2 小时， 再用含乙二醇 (北京益利精细化学品有限公司产品）48,4 的 60ml水溶液浸渍， 120 Ό处理 10hr， 得到催化剂 C-3， 其组成见表 3。 对比例 2
本对比例说明参比例催化剂的制备
对比催化剂 RC-2完全按照实例 6进行催化剂的制备， 所不同的 是催化剂附载 MW后不包含用乙二醇处理的过程。 实例 7
本实例说明本发明提供的催化剂及其制备方法。
将 450克干基氢氧化铝粉（长岭催化剂厂生产， 商品名 CL干胶 粉） ， 350克干基拟薄水铝石 （山东铝厂生产， 商品名 SD粉） ， 100 克干基 ZSM-5 沸石分子筛 （长呤建长催化剂厂生产， 硅铝比 50， B 酸同 L酸的比值为 4.3 ) ， 100克干基 Beta沸石分子筛 （长岭建长催 化剂厂生产， 硅铝比 27， B酸同 L酸的比值为 3.2 ) ， 挤成外接圆直 径为 3.6 亳米的蝶型条， 1201C烘干， 550Ό温度下焙烧 3 小时， 得载 体 CS-3, 催化剂载体组成见表 2。 降温至室温后， 取 100g CS-4载体 用含仲钼酸铵（株洲硬质合金厂， 氧化钼含量为 80重量％ ) 9.25克， 偏钨酸铵（四川自贡硬质合金厂， 氧化钨含量为 82重量％ ) 43.84克、 硝酸镍（北京益利精细化学品有限公司产品， 氧化镍含量为 25.4重量 % ) 18.05克的 80ml水溶液浸渍， 120TC干燥， 450Ό焙烧 3hr。 降温 至室温后， 用含柠檬酸 26.41克的 50ml水溶液浸渍， 120 Ό干燥 4hr 得到催化剂 C-4, 其组成见表 3。 实例 8
本实例说明本发明提供的催化剂及其制备方法。
将 400克干基拟薄水铝石 （山东铝厂生产， 商品名 SD粉） ， 600 克干基 REHY 沸石分子筛 （长岭催化剂厂生产， 商品名 REHY, 晶 胞常数 24.55， B酸同 L酸比值 1.8 ) ， 挤成外接圆直径为 3.6亳米的 蝶型条， 120Ό烘干， 500Ό温度下焙烧 3小时， 得载体 CS-4, 催化剂 载体组成见表 2。 降温至室温后， 取 100g CS-4载体用含乙二胺 56·31 克的 80ml水溶液浸渍， 105Ό处理 2 小时,再用含偏钨酸铵（四川自贡 硬质合金厂， 氧化钨含量为 82重量％ ) 22.64克、 硝酸镍（北京益利 精细化学品有限公司产品，氧化镍含量为 25.4重量％ )36.58克的 60ml 水溶液浸渍， ΙΙΟΌ处理 8hr， 得到催化剂 C-5， 其组成见表 3。 表 2
Figure imgf000018_0001
表 3
Figure imgf000018_0002
实例 9〜13
本实例说明本发明提供催化剂的性能。
在小型固定床加氢裂化装置上评价催化剂 C1-C5 的加氢裂化活 性， 催化剂装量为 0.2亳升， 催化剂颗粒直径为 0.3 - 0.45亳米， 反应 温度 390 , 反应压力 4.0兆帕， 氢油比（摩尔比） 为 25, 液时空速 为 30小时 -1， 用含四氢萘 5.61 %的正辛烷溶液进行微反评价， 催化剂 进反应油前进行硫化， 硫化条件为： 在氢气压力 2.0MPa 的条件下， 升温至 60 C， 通入含 6%CS2的正己烷溶液， 升温至 300Ό， 恒温 4hr。
以下式定义催化剂的芳烃加氢转化活性：
芳烃加氢转化活性％ = 100 - [ (产物中四氢萘总量 +产物中蔡总 量） /原料中四氢萘总量 ] χ 100。
评价结果见表 4。 对比例 2
本对比例说明参比催化剂的性能。
采用实例 9的方法进行 RC-1催化剂的评价。 结果见表 4。 表 4
Figure imgf000019_0001
由表 4可知， 采用含有机添加物的催化剂 C-l， 芳烃转化活性能 明显提高， 相对于未采用添加物的催化剂 RC-1 , 其活性提高 5.0 %。 采用含高 B酸同 L酸比值沸石及有机添加物制备催化剂 C-2, 其活性 提高 11.0 %， 而采用同时具有两个硅羟基峰沸石制备的 C-3催化剂， 其活性进一步提高至 19.0 %。 实例 14〜： 15
本实例说明本发明提供的加氢裂化方法。
采用表 5的原料油， 以 C-3为催化剂在 30亳升固定床装置上进 行加氢裂化反应， 催化剂装量为 20亳升， 反应条件为： 温度 350Ό和 380Ό、 氢分压 6.4MPa、 液时空速 0.75 小时 氢油体积比 800， 结 果列于表 6中。 对比例 3
本实例说明对比发明提供的加氢裂化方法。
采用表 5的原料油， 以 RC-2为催化剂在 30亳升固定床装置上进 行加氢裂化反应， 催化剂装量为 20亳升， 反应条件为： 温度 350Ό、 氢分压 6.4MPa、 液时空速 0.75小时 氢油体积比 800， 结果列于表 6中。
Figure imgf000020_0001
表 6给出的结果可以表明， 采用含有机物添加物催化剂 C-3的加 氢裂化过程相对于未含有机添加物催化剂 RC-2 对比加氢裂化过程， 在完全相同的条件下， 前述过程< 35010生成油的收率提高 5.8w%， 同时 >350Ό生成油的 BMCI值较对比例低 1.9单位， 将反应温度提高 到 380Ό后， 含添加有机物催化剂的加氢裂化过程< 350"€生成油的收 率进一步提高 16w%， 同时 >350Ό生成油的 BMCI值进一步降低 4.8 单位。

Claims

权 利 要 求
1. 一种加氢裂化催化剂， 其包含沸石分子筛与氧化铝的复合成 型载体、 至少一种笫 VIII族金属组分、 至少一种笫 VIB族金属组分 以及有机添加物， 所述有机添加物选自含氧或含氮有机化合物中的一 种或几种， 以所述催化剂的重量为基准， 所述沸石分子筛的含量为 3- 60重量％， 所述氧化铝的含量为 10-80重量％, 所述有机添加物的含 量为 0.1-40重量％， 以氧化物计并以所述催化剂的重量为基准， 所述 第 VIII族金属组分的含量为 1-15重量％， 所述第 VIB族金属组分的 含量为 5-40重量％。
2. 按照权利要求 1 所述的加氢裂化催化剂， 其特征在于， 该催 化剂由所述沸石分子筛与所述氧化铝的所述复合成型载体、 所述至少 一种第 VIII族金属组分、 所述至少一种第 VIB族金属组分以及所述 有机添加物组成。
3. 按照权利要求 1 或 2 所述的加氢裂化催化剂， 其特征在于， 所述含氧有机化合物选自有机醇和有机酸中的一种或几种， 所述含氮 有机化合物选自有机胺中的一种或几种， 以所述催化剂的重量为基 准， 所述沸石分子筛的含量为 5-60重量％, 所述氧化铝的含量为 I5- 80重量％, 所述有机添加物的含量为 0.5-30重量％， 以氧化物计并以 所述催化剂的重量为基准， 所述第 VIII族金属组分的含量为 2-8重量 %, 所述第 VIB族金属组分的含量为 10-35重量％。
4. 按照权利要求 1 或 2 所述的加氢裂化催化剂， 其特征在于， 所述沸石分子筛选自具有八面沸石结构的沸石分子筛、 具有 Beta 沸 石结构的沸石分子筛和具有丝光沸石结构的沸石分子筛中的一种或几 种。
5. 按照权利要求 4 所述的加氢裂化催化剂， 其特征在于， 所述 具有八面沸石结构的沸石分子筛选自 HY沸石分子筛、 稀土型 Y沸石 REY分子筛、 稀土型 HY沸石 REHY分子筛、 超稳 Y沸石 USY分子 筛、 稀土型超稳 Y沸石 REUSY分子筛和脱铝 Y型沸石分子筛中的一 种或几种。
6. 按照权利要求 1、 2、 4 或 5 所述的加氢裂化催化剂， 其特征 在于， 所述沸石分子筛的 B酸与 L酸的比值大于 0.9， 以羟基红外谱 图表征时， 所述沸石分子筛在 S GO SeSScm-1的范围内出现至少一个 表征硅羟基的特征峰。
7. 按照权利要求 6 所述的加氢裂化催化剂， 其特征在于， 所述 沸石分子筛的 B酸与 L酸的比值为 1-10， 以羟基红外谱图表征时， 所述沸石分子筛在 S GO-SSSScm-1的范围内出现两个表征硅羟基的特 征峰。
8. 按照权利要求 1 所述的加氢裂化催化剂的制备方法， 该方法 包括将沸石分子歸、 氧化铝和 /或氧化铝的前身物混合在一起， 成型和 焙烧， 以制备复合成型载体， 之后向所述复合成型载体中引入至少一 种第 VIII族金属组分、 至少一种第 VIB族金属组分以及有机添加物， 其中所述有机添加物选自含氧或含氮有机化合物中的一种或几种， 并 且所述各组分的用量要使得所获得的催化剂中各组分的含量满足以下 条件： 以所述催化剂的重量为基准， 所述沸石分子筛的含量为 3-60重 量％， 所述氧化铝的含量为 10-80 重量％, 所述有机添加物的含量为 0.1-40重量％，以氧化物计并以所述催化剂的重量为基准，所述笫 VIII 族金属组分的含量为 1-15重量％， 所述第 VIB族金属组分的含量为 5-40重量％。
9. 按照权利要求 8 所述的加氢裂化催化剂的制备方法， 其特征 在于， 所述含氧有机化合物选自有机醇和有机酸中的一种或几种， 所 述含氮有机化合物选自有机胺中的一种或几种， 并且所述各组分的用 量要使得所获得的催化剂中各组分的含量满足以下条件： 以所述催化 剂的重量为基准， 所述沸石分子筛的含量为 5-60重量％， 所述氧化铝 的含量为 15-80重量％， 所述有机添加物的含量为 0.5-30重量％, 以 氧化物计并以所述催化剂的重量为基准， 所述第 VIII族金属组分的 含量为 2-8重量％， 所述第 VIB族金属组分的含量为 10-35重量％。
10. 按照权利要求 8 所述的加氢裂化催化剂的制备方法， 其特征 在于，所述沸石分子筛选自具有八面沸石结构的沸石分子筛、具有 Beta 沸石结构的沸石分子筛和具有丝光沸石结构的沸石分子筛中的一种或 几种。
11. 按照权利要求 10 所述的加氢裂化催化剂的制备方法， 其特 征在于， 所述具有八面沸石结构的沸石分子筛选自 HY沸石分子筛、 稀土型 Y沸石 REY分子筛、 稀土型 HY沸石 REHY分子筛、 超稳 Y 沸石 USY分子筛、 稀土型超稳 Y沸石 REUSY分子筛和脱铝 Y型沸 石分子筛中的一种或几种。
12. 按照权利要求 8、 10或 11 所述的加氢裂化催化剂的制备方 法， 其特征在于， 所述沸石分子筛的 B酸与 L酸的比值大于 0.9, 以 羟基红外 图表征时， 所述沸石分子筛在 S GO ^^eSScm-1的范围内出 现至少一个表征硅羟基的特征峰。
13. 按照权利要求 11 所述的加氢裂化催化剂的制备方法， 其特 征在于， 所述沸石分子筛的 B酸与 L酸的比值为 1.0-10.0， 以羟基红 外谱图表征时， 所述沸石分子筛在 3760 ~ 3685cm-1的范围内出现两个 表征硅羟基的特征峰。
14. 一种烃油加氢裂化方法， 该方法包括在氢气存在和加氢裂化 反应条件下， 使烃油进料与前述权利要求 1-7任一项所述的加氢裂化 催化剂接触。
15. 按照权利要求 14 所述的烃油加氢裂化方法， 其特征在于， 所述的加氢裂化反应条件包括： 反应温度 200 - 650Ό , 氢分压 3-24 兆帕， 液时空速 0.1-10小时— 并且氢油体积比 100 - 5000。
16. 按照权利要求 15 所述的烃油加氢裂化方法， 其特征在于， 所述的加氢裂化反应条件包括： 反应温度 220_5101C、 氢分压 4-15兆 帕、 液时空速 0.2-5小时— 并且氢油体积比 200-1000。
17. 按照权利要求 14 所述的烃油加氢裂化方法， 其特征在于， 所述烃油选自重质矿物油、 合成油或其混合馏分油。
18. 按照权利要求 17所述的烃油加氢裂化方法， 其特征在于， 所 述重质矿物油选自直馏瓦斯油、 减压瓦斯油、 脱金属油、 常压渣油、 脱沥青减压渣油、 焦化馏出油、 催化裂化馏出油、 页岩油、 煤液化油 或沥青砂油， 所述合成油为费托合成油。
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