WO2018192520A1 - Optimized diesel hydrocracking catalyst and method for preparing same - Google Patents

Optimized diesel hydrocracking catalyst and method for preparing same Download PDF

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WO2018192520A1
WO2018192520A1 PCT/CN2018/083510 CN2018083510W WO2018192520A1 WO 2018192520 A1 WO2018192520 A1 WO 2018192520A1 CN 2018083510 W CN2018083510 W CN 2018083510W WO 2018192520 A1 WO2018192520 A1 WO 2018192520A1
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molecular sieve
modified
hydrocracking catalyst
aluminum
preparing
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PCT/CN2018/083510
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French (fr)
Chinese (zh)
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明卫星
石友良
许莉
杨伟光
赖波
王春锋
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武汉凯迪工程技术研究总院有限公司
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Publication of WO2018192520A1 publication Critical patent/WO2018192520A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
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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
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
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    • 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
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    • 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
    • B01J29/42—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 iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
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    • 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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    • B01J29/04—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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/7284—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7684—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
    • 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
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7692—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
    • 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
    • B01J29/78—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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7884—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7892—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects

Definitions

  • the invention relates to a catalyst, in particular to an optimized diesel hydrocracking catalyst and a preparation method thereof.
  • Hydrocracking is a very important technology for the efficient conversion of heavy oil and clean oil production in the refining industry. It can process heavy crude oil with high sulfur and high metal. It has wide source of raw materials, great production flexibility, good product quality and middle distillate. High oil yield. Hydrocracking technology can directly produce low aromatics, low sulfur and low nitrogen high quality middle distillate products from reduced pressure diesel (VGO), which can meet increasingly stringent environmental requirements, and catalysts play a central role in hydrocracking reactions. The key to hydrocracking technology is the development and improvement of catalysts.
  • the conventional preparation methods of the hydrocracking catalyst mainly include a dipping method, a coprecipitation method and a kneading method.
  • the preparation process of the kneading method is the simplest, and the requirements for the process and the catalyst dosing are not high, but the preparation process is relatively extensive, the catalyst The dispersibility of each component is not good, and some metal hydrogenation active centers are covered, which can not exert its activity better. It is usually used for catalysts with less hydrogenation performance; the preparation process of coprecipitation method is the most complicated.
  • the impregnation method is the most widely used method for preparing hydrocracking catalysts. Firstly, the carrier which meets the performance requirements of the catalyst, such as the shape, mechanical strength, specific surface and acidity of the carrier, is prepared, and then the metal group is supported by a saturated or supersaturated impregnation method. The metal component is enriched in the catalyst to make the catalyst have higher mechanical strength and fully exert its Hydrogen performance.
  • the hydrocracking catalyst prepared by the prior method has simple mechanical mixing between the components, and the components in the catalyst are easily agglomerated into secondary particles, so that the dispersibility of the active component is poor, and the prepared catalyst is difficult to prepare.
  • the best performance is achieved, and there are also problems with complicated preparation processes and high costs.
  • CN98114489.6 discloses a hydrocracking catalyst, amorphous silico-alumina and Y-type molecular sieves as cracking components, and Group VIB and Group VIII metal oxides as hydrogenation components, using a series of hydrocracking.
  • the middle distillate oil is produced, and the catalyst has good nitrogen resistance, but the preparation method is complicated and the preparation cost is high.
  • CN1393521A discloses a medium oil type hydrocracking catalyst and a preparation method thereof, wherein the carrier used for the catalyst is amorphous silicon aluminum, aluminum oxide and Y and ⁇ composite molecular sieve, wherein the composite molecular sieve is after the ⁇ molecular sieve raw powder is burned to the template.
  • the carrier used for the catalyst is amorphous silicon aluminum, aluminum oxide and Y and ⁇ composite molecular sieve, wherein the composite molecular sieve is after the ⁇ molecular sieve raw powder is burned to the template.
  • CN1351121A discloses a hydrocracking catalyst containing modified ⁇ molecular sieve and amorphous silicon aluminum and a preparation method thereof, wherein the modified ⁇ molecular sieve directly exchanges the synthesized molecular sieve slurry with ammonium, and then roasts deammonium, acid
  • the modified ⁇ molecular sieve is obtained by treatment and hydrothermal treatment. Since a large amount of non-skeletal aluminum is retained in the pores of the molecular sieve, the acidity and diffusion property of the modified molecular sieve are affected, which ultimately affects the yield and properties of the diesel product.
  • the object of the present invention is to provide an optimized diesel hydrocracking catalyst and a preparation method thereof, which can significantly reduce the freezing point of the diesel fraction and increase the cetane number of the diesel fuel under the premise of ensuring the diesel oil yield.
  • the technical scheme adopted by the present invention is: an optimized diesel hydrocracking catalyst comprising the following components and their weight percentages: 1 to 25% of modified molecular sieves, 10 to 65% ⁇ -Al 2 O 3 , 15 to 70% amorphous silicon aluminum, 9 to 40% binder and 10 to 35% active metal oxide; the catalyst has a specific surface area of 200 to 400 m 2 /g, The total pore volume is from 0.30 to 0.65 cm 3 /g.
  • the catalyst raw material comprises the following components and their weight percentages: 3.3 to 5.4% modified molecular sieve, 21.6 to 27% ⁇ -Al 2 O 3 , 29.7 to 35% amorphous silicon aluminum, 15 to 25 % binder and 20-28% active metal oxide; the catalyst has a specific surface area of 341-375 m 2 /g, and a total pore volume of 0.49-0.57 cm 3 /g; the catalyst is columnar and the length is 3 to 8 mm.
  • the modified molecular sieve is one of a modified ⁇ molecular sieve, a modified Y molecular sieve, a modified MOR molecular sieve, a modified ZSM-5 molecular sieve, a modified ZSM-22 molecular sieve, and a modified ZSM-23 molecular sieve or Several.
  • the active metal in the active metal oxide is one or more of W, Mo, Ni, and Co.
  • the modified ⁇ molecular sieve has a specific surface area of 450 to 750 m 2 /g and a total pore volume of 0.3 to 0.5 cm 3 /g.
  • the modified Y-type molecular sieve has a specific surface area of 750 to 860 m 2 /g and a total pore volume of 0.35 to 0.55 cm 3 /g.
  • the modified MOR molecular sieve has a specific surface area of 300 to 560 m 2 /g and a total pore volume of 0.3 to 0.45 cm 3 /g.
  • a method for preparing the above optimized diesel hydrocracking catalyst comprises the following steps:
  • step 2) preparing modified molecular sieve and ⁇ -Al 2 O 3 composite material: adding the modified molecular sieve obtained in step 1) to a mixed solution of aluminum salt and alkali for precipitation, fully precipitating, and then taking the slurry to be sequentially dried and calcined, and then changed.
  • Molecular sieve and ⁇ -Al 2 O 3 composite
  • the ammonium exchange condition is: the temperature is 60 to 90 ° C, and the ammonium salt used is 0.4 to 0.6 mol/L of ammonium chloride or ammonium nitrate.
  • the hydrothermal treatment conditions are: a temperature of 630 to 750 ° C, a treatment time of 1 to 4 hours, and a gauge pressure of 0.05 to 0.4 MPa.
  • the aluminum salt treatment condition is: the aluminum salt solution used has an Al 3+ concentration of 0.5 to 1.5 mol/L, and the mass ratio of the aluminum salt to the modified molecular sieve is 4 to 30:1.
  • the temperature is 70 to 100 ° C, and the treatment time is 1 to 5 hours.
  • the modified molecular sieve is a modified ⁇ molecular sieve
  • the crystallization temperature is 135 to 145 ° C
  • the calcination de-template treatment conditions are: after the temperature rise rate is 2 ° C / min, the temperature is raised to 540-560 ° C, Roasted for 7 to 9 hours.
  • the aluminum source is one or more of pseudoboehmite, aluminum sulfate and sodium metaaluminate
  • the silicon source is one of white carbon black, silica sol and water glass. Or several.
  • the aluminum salt is one or more of aluminum sulfate, aluminum nitrate and aluminum chloride;
  • the base is one or more of ammonium oxalate, ammonia water, sodium hydroxide and potassium hydroxide.
  • the control temperature is 50-70 ° C
  • the pH is 3-7
  • the drying temperature is 110-130 ° C
  • the baking temperature is 300-600 ° C
  • the baking time is 2 ⁇ . 4 hours.
  • the drying temperature is 100 to 120 ° C
  • the time is 18 to 22 hours
  • the activation temperature is 450 to 600 ° C
  • the activation time is 4 to 6 hours.
  • the present invention has the following advantages:
  • a modified molecular sieve is added to the aluminum salt solution for preparing ⁇ -Al 2 O 3 , and after adding a precipitating agent, the precipitate of aluminum hydroxide is deposited and the modified molecular sieve is wrapped, and the precipitate is dried, After calcination, the cracking active component can be uniformly dispersed into the alumina.
  • the catalyst of the invention has a more uniform acidity center, suitable acidity, large specific surface area and pore volume, and alumina in the catalyst. Molecular sieves are more closely contacted, which facilitates the rapid transfer of reactants and product molecules between the acid center and the cracking center, so that there is better synergy between the cracking and hydrogenation active components.
  • the hydrocracking catalyst of the invention has suitable cracking action and good isomerization effect on long-chain alkyl groups of long-chain alkanes, aromatic hydrocarbons and naphthenes, good middle distillate selectivity and high catalytic activity. Under the premise of ensuring diesel oil yield, the freezing point of diesel fraction is obviously reduced, and the cetane number of diesel is improved.
  • the invention optimizes the matching between the hydrogenation function and the acidic function, forms a combination of strong hydrogenation function and medium acid or weak acid function, and the positive carbon ion can be more hydrogenated and saturated at the hydrogenation active center.
  • the direction of the formation proceeds, reducing the secondary cracking of the cracked product.
  • the specific surface area and pore volume are measured by low temperature liquid nitrogen physical adsorption, the molar ratio of silicon to aluminum is determined by chemical method, and the framework silica aluminum is determined by NMR; the amount of infrared acid, B acid and L acid are adsorbed by pyridine.
  • the spectroscopy method, the sodium content is determined by plasma emission spectroscopy, and the relative crystallinity of the molecular sieve is determined by the XRD method.
  • modified ⁇ molecular sieve by hydrothermal synthesis method (specific surface area: 450-750 m 2 /g, total pore volume: 0.3-0.5 cm 3 /g), modified Y-type molecular sieve (specific surface area of 750-860 m 2 / g, total pore volume is 0.35-0.55 cm 3 /g), modified MOR molecular sieve (specific surface area is 300-560 m 2 /g, total pore volume is 0.3-0.45 cm 3 /g), modified ZSM-5 molecular sieve, One or more of the modified ZSM-22 molecular sieve and the modified ZSM-23 molecular sieve, according to the molecular sieve compounding molar ratio, the template or the guiding agent, the aluminum salt, and the water are mixed and stirred to a clear solution (where the modified Y The molecular sieve needs to adjust the alkalinity of the mixed solution with hydrochloric acid, and then the silicon source is added to the obtained clear solution under stirring,
  • the catalyst material the modified molecular sieve and the alumina composite material, the amorphous silicon aluminum, the active metal oxide and the binder are mixed, compacted, formed, dried and activated to obtain a catalyst, and the rolling time is obtained.
  • the strip is extruded into a column shape, the length is 3 to 8 mm, dried at 120 ° C for 20 hours, and calcined at 450 to 600 ° C for 5 to 6 hours to obtain a catalyst.
  • the ammonium exchange was carried out twice at a concentration of 0.5 mol/L ammonium chloride solution at 80 ° C, and the liquid-solid ratio was 10:1. Further, hydrothermal treatment is carried out at a water vapor pressure of 0.15 MPa, a treatment temperature of 600 ° C, and a treatment time of 2.5 hours, followed by treatment with an aluminum salt, and the hydrothermally treated molecular sieve is placed in a flask with a reflux device and can be sealed, and added.
  • the composite material of molecular sieve and ⁇ -Al 2 O 3 was 195.5 g (dry basis 93%), amorphous silicon aluminum 238.6 g (dry basis 88%), MoO 3 90.5 g (99.1 wt%), Ni(NO 3 ) 2 ⁇ 6H 2 O (NiO, 26.6wt%) 116.7g, binder 360g (dry basis 25%) were mixed, crushed in a wheel mill for 40 minutes, crushed into a squeezeable paste, extruded into strips, The shape is columnar, the length is 3-8 mm, and dried at 120 ° C for 20 hours, and calcined at 500 ° C for 5-6 hours to obtain a hydrocracking catalyst, numbered C-1, and the properties are shown in Table 2.
  • the modified molecular sieve was the same as the ⁇ modified molecular sieve in Example 1; the molecular sieve and the ⁇ -Al 2 O 3 composite were the same as in Example 1; the composite material was 195.5 g (dry basis 93%), amorphous silicon aluminum 204.5 g (dry basis) 88%), MoO 3 is 108.5 g (99.1 wt%), Ni(NO 3 ) 2 ⁇ 6H 2 O (NiO, 26.6 wt%) is 163.4 g, and binder 360 g (dry basis 25%) is mixed.
  • the roller mill is rolled for 40 minutes, crushed into a squeezing paste, extruded into strips, and shaped into a column shape, having a length of 3 to 8 mm, dried at 120 ° C for 20 hours, and calcined at 500 ° C for 5 to 6 hours to obtain Hydrocracking catalyst, numbered C-2, properties are shown in Table 2.
  • the modified molecular sieve was the same as the ⁇ -modified molecular sieve in Example 1; 140 g of ammonium oxalate and 3000 ml of aluminum chloride solution (concentration: 1.5 mol/L) were weighed and mixed in a 5000 ml beaker to modify 52.6 g (dry basis 98%). Molecular sieves were added to the mixture, kept at a constant temperature of 70 ° C, and continuously added with 2 mol/L of ammonia water until the pH was 4, and evaporated at 85 ° C. The aspirated white solid was dried at 100 ° C for 3 hours and calcined at 500 ° C for 4 hours to obtain a molecular sieve.
  • the ⁇ -Al 2 O 3 composite material was 272.8 g (dry basis 93%), and the conversion rate was 72.3%.
  • the composite material of molecular sieve and ⁇ -Al 2 O 3 was 173.2 g (dry basis 93%), amorphous silicon aluminum 238.6 g (dry basis 88%), MoO 3 was 108.5 g (99.1 wt%), Ni(NO 3 ) 2 ⁇ 6H 2 O (NiO, 26.6wt%) was 116.7g, binder 360g (dry basis 25%) was mixed, crushed in a wheel mill for 40 minutes, crushed into a squeezing paste, extruded
  • the molding has a columnar shape and a length of 3 to 8 mm, and is dried at 120 ° C for 20 hours and calcined at 500 ° C for 5 to 6 hours to obtain a hydrocracking catalyst, which is numbered C-3, and the properties are shown in Table 2.
  • the modified molecular sieve was the same as the ⁇ modified molecular sieve in Example 1; the composite material of molecular sieve and ⁇ -Al 2 O 3 was the same as in Example 3, and the composite material was 173.2 g (dry basis 93%) and amorphous silicon aluminum 204.5 g (dry). 88%), MoO 3 is 108.5 g (99.1 wt%), Ni(NO 3 ) 2 ⁇ 6H 2 O (NiO, 26.6 wt%) is 233.4 g, and binder 360 g (dry basis 25%) is mixed.
  • the modified molecular sieve was the same as the ⁇ -modified molecular sieve of Example 1; 20.5 g of modified molecular sieve (dry basis 98%), alumina 169.8 g (dry basis 96%), amorphous silica aluminum 238.6 g ( Dry base 88%), MoO 3 is 90.5 g (99.1 wt%), Ni(NO 3 ) 2 ⁇ 6H 2 O (NiO, 26.6 wt%) is 116.7 g, and binder 360 g (dry basis 25%) is mixed.
  • the modified molecular sieve was the same as the ⁇ -modified molecular sieve of Example 1; 33.4 g of modified molecular sieve (dry basis 98%), alumina 135.3 g (dry basis 96%), amorphous silica aluminum 238.6 g ( Dry base 88%), MoO 3 is 108.5 g (99.1 wt%), Ni(NO 3 ) 2 ⁇ 6H 2 O (NiO, 26.6 wt%) is 116.7 g, and binder 360 g (dry basis 25%) is mixed.
  • Example 1 The catalysts of Example 1 and Comparative Example 1 were evaluated on a fixed bed hydrogenation experimental apparatus under the following conditions: a total reaction pressure of 10 MPa, a hydrogen oil volume ratio of 1000, a volumetric space velocity of 1.0 h -1 , and a reduced pressure.
  • Distillate oil (VGO) is a feedstock oil, and the properties of the feedstock oil are shown in Table 3.
  • Catalysts C-1 and C-5 were evaluated under the same process conditions, and the evaluation results are shown in Table 4.
  • the catalyst of Example 1 had better middle distillate oil under the same process conditions.
  • Raw material oil Vacuum distillate Density (20 ° C), kg / m 3 912.3 Distillation range, °C IBP/10% 315/403 30%/50% 442/461 70%/90% 495/526 95%/EBP 532/544 Freezing point, °C 32 Nitrogen, ⁇ g/g 1568 Carbon, wt% 84.53 Hydrogen, wt% 11.72 Carbon residue, wt% 0.32 BMCI value 43

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Abstract

An optimized diesel hydrocracking catalyst and a method for preparing same. Raw materials comprise the following components in percentage by weight: 1-25% of modified molecular sieve, 10-65% of γ-Al2O3, 15-70% of amorphous silica-alumina, 9-40% of binder, and 10-35% of active metal oxide. The specific surface area of the catalyst is 200-450 m2/g, and the total pore volume is 0.30-0.65 cm3/g. To obtain a carrier, a modified molecular sieve is added to an inorganic aluminum salt solution used for preparing γ-Al2O3, and precipitation, drying, and roasting are performed to obtain a composite of molecular sieve and γ-Al2O3; then the remaining materials are mixed with the composite according to the material proportion of the catalyst, and rolling, forming, drying, and activation are performed to obtain the catalyst. The molecular sieve in the catalyst carrier has a high silica/alumina ratio and high specific surface area, and is highly dispersed in the carrier; thus, the carrier has more uniform acid sites, and alumina is in closer contact with the molecular sieve; and therefore, the catalyst can remarkably reduce the pour point of a diesel fraction and improve the cetane number of diesel while guaranteeing a high diesel yield.

Description

优化型柴油加氢裂化催化剂及其制备方法Optimized diesel hydrocracking catalyst and preparation method thereof 技术领域Technical field
本发明涉及催化剂，具体地指一种优化型柴油加氢裂化催化剂及其制备方法。The invention relates to a catalyst, in particular to an optimized diesel hydrocracking catalyst and a preparation method thereof.
背景技术Background technique
加氢裂化作为炼油工业非常重要的重质油高效转化和清洁油品生产的技术，可加工高硫、高金属的重质原油，具有原料来源广，生产灵活性大，产品质量好及中间馏分油收率高等特点。加氢裂化技术可以从减压柴油(VGO)直接生产低芳烃，低硫及低氮的高品质中间馏分油产品，可以满足日益严格的环保要求，而催化剂在加氢裂化反应中起核心作用，加氢裂化技术的关键在于催化剂的研制和改进。Hydrocracking is a very important technology for the efficient conversion of heavy oil and clean oil production in the refining industry. It can process heavy crude oil with high sulfur and high metal. It has wide source of raw materials, great production flexibility, good product quality and middle distillate. High oil yield. Hydrocracking technology can directly produce low aromatics, low sulfur and low nitrogen high quality middle distillate products from reduced pressure diesel (VGO), which can meet increasingly stringent environmental requirements, and catalysts play a central role in hydrocracking reactions. The key to hydrocracking technology is the development and improvement of catalysts.
加氢裂化催化剂常规的制备方法主要有浸渍法，共沉淀法及混捏法等，其中混捏法的制备工艺最简单，对工艺及催化剂配料的要求都不高，但由于其制备过程较粗放，催化剂中各组分的分散性不好，部分金属加氢活性中心被覆盖，不能更好的发挥其活性，通常为加氢性能要求不是很高的催化剂所采用；共沉淀法制备技术制备过程最为复杂，但催化剂中各组分的分散度很好，各组分之间的匹配关系好，加氢和裂化活性中心在催化剂中均匀分布，使催化剂加氢与裂化活性中心具有更高的协同作用；浸渍法是制备加氢裂化催化剂最广泛的使用方法，首先制备出符合催化剂性能要求的载体，如载体的形状、机械强度、比表面和酸性等，然后通过饱和或过饱和浸渍方法进行负载金属组分，金属组分富集于催化剂中，使催化剂具有更高的机械强度，充分发挥其加氢性能。The conventional preparation methods of the hydrocracking catalyst mainly include a dipping method, a coprecipitation method and a kneading method. Among them, the preparation process of the kneading method is the simplest, and the requirements for the process and the catalyst dosing are not high, but the preparation process is relatively extensive, the catalyst The dispersibility of each component is not good, and some metal hydrogenation active centers are covered, which can not exert its activity better. It is usually used for catalysts with less hydrogenation performance; the preparation process of coprecipitation method is the most complicated. However, the dispersion of each component in the catalyst is very good, the matching relationship between the components is good, and the hydrogenation and cracking active centers are evenly distributed in the catalyst, so that the catalyst hydrogenation and cracking active center have higher synergistic effect; The impregnation method is the most widely used method for preparing hydrocracking catalysts. Firstly, the carrier which meets the performance requirements of the catalyst, such as the shape, mechanical strength, specific surface and acidity of the carrier, is prepared, and then the metal group is supported by a saturated or supersaturated impregnation method. The metal component is enriched in the catalyst to make the catalyst have higher mechanical strength and fully exert its Hydrogen performance.
然而，现有方法制得的加氢裂化催化剂，其组分之间都是简单的机械混合，催化剂中各组分容易团聚为二次粒子，使得活性组分分散性较差，制备的催化剂难以发挥最佳性能，而且还存在制备流程复杂，成本高的问题。如：CN98114489.6公开了一种加氢裂化催化剂，无定形硅铝及Y型分子筛作为裂化组分，第VIB族及第VIII族族金属氧化物为加氢组分，采用一段串联加氢裂化生产中间馏分油，该催化剂具有很好的抗氮性，但其制备方法较为复杂，制备成本较高。CN1393521A公开了一种中油型加氢裂化催化剂及其制备方法，催化剂所用载体为无定形硅铝、氧化铝和Y和β的复合型分子筛，其中复合分子筛是将β分子筛原粉烧去模板剂后与改性Y型分子筛混合后，再进行铵交换处理而得，该催化剂的催化活性不高，航煤和柴油的中间馏分油的产品质量一般，需进 一步提高。CN1351121A公布了一种含改性β分子筛和无定型硅铝的加氢裂化催化剂及其制备方法，该方法中改性β分子筛是将合成后的分子筛浆液直接进行铵交换，然后焙烧脱铵，酸处理和水热处理得到改性β分子筛，由于大量非骨架铝滞留在分子筛孔道中，影响了改性分子筛的酸性及其扩散性能，最终影响了柴油产品的产率和性质。However, the hydrocracking catalyst prepared by the prior method has simple mechanical mixing between the components, and the components in the catalyst are easily agglomerated into secondary particles, so that the dispersibility of the active component is poor, and the prepared catalyst is difficult to prepare. The best performance is achieved, and there are also problems with complicated preparation processes and high costs. For example, CN98114489.6 discloses a hydrocracking catalyst, amorphous silico-alumina and Y-type molecular sieves as cracking components, and Group VIB and Group VIII metal oxides as hydrogenation components, using a series of hydrocracking. The middle distillate oil is produced, and the catalyst has good nitrogen resistance, but the preparation method is complicated and the preparation cost is high. CN1393521A discloses a medium oil type hydrocracking catalyst and a preparation method thereof, wherein the carrier used for the catalyst is amorphous silicon aluminum, aluminum oxide and Y and β composite molecular sieve, wherein the composite molecular sieve is after the β molecular sieve raw powder is burned to the template. After mixing with the modified Y-type molecular sieve and then performing ammonium exchange treatment, the catalytic activity of the catalyst is not high, and the product quality of the middle distillate of jet fuel and diesel oil is generally required to be further improved. CN1351121A discloses a hydrocracking catalyst containing modified β molecular sieve and amorphous silicon aluminum and a preparation method thereof, wherein the modified β molecular sieve directly exchanges the synthesized molecular sieve slurry with ammonium, and then roasts deammonium, acid The modified β molecular sieve is obtained by treatment and hydrothermal treatment. Since a large amount of non-skeletal aluminum is retained in the pores of the molecular sieve, the acidity and diffusion property of the modified molecular sieve are affected, which ultimately affects the yield and properties of the diesel product.
发明内容Summary of the invention
本发明的目的就是要提供一种优化型柴油加氢裂化催化剂及其制备方法，该催化剂能在保证柴油收率的前提下，明显降低柴油馏分的凝点，并提高柴油的十六烷值。The object of the present invention is to provide an optimized diesel hydrocracking catalyst and a preparation method thereof, which can significantly reduce the freezing point of the diesel fraction and increase the cetane number of the diesel fuel under the premise of ensuring the diesel oil yield.
为实现上述目的，本发明采用的技术方案是：一种优化型柴油加氢裂化催化剂，所述催化剂原料包括以下组分及其重量百分比：1～25％的改性分子筛，10～65％的γ-Al 2O 3，15～70％的无定形硅铝，9～40％的粘结剂及10～35％的活性金属氧化物；所述催化剂的比表面积为200～400m 2/g，总孔容为0.30～0.65cm 3/g。 In order to achieve the above object, the technical scheme adopted by the present invention is: an optimized diesel hydrocracking catalyst comprising the following components and their weight percentages: 1 to 25% of modified molecular sieves, 10 to 65% γ-Al 2 O 3 , 15 to 70% amorphous silicon aluminum, 9 to 40% binder and 10 to 35% active metal oxide; the catalyst has a specific surface area of 200 to 400 m 2 /g, The total pore volume is from 0.30 to 0.65 cm 3 /g.
进一步地，所述催化剂原料包括以下组分及其重量百分比：3.3～5.4％的改性分子筛，21.6～27％的γ-Al 2O 3，29.7～35％的无定形硅铝，15～25％的粘结剂及20～28％的活性金属氧化物；所述催化剂的比表面积为341～375m 2/g，总孔容为0.49～0.57cm 3/g；所述催化剂呈柱状，长度为3～8mm。 Further, the catalyst raw material comprises the following components and their weight percentages: 3.3 to 5.4% modified molecular sieve, 21.6 to 27% γ-Al 2 O 3 , 29.7 to 35% amorphous silicon aluminum, 15 to 25 % binder and 20-28% active metal oxide; the catalyst has a specific surface area of 341-375 m 2 /g, and a total pore volume of 0.49-0.57 cm 3 /g; the catalyst is columnar and the length is 3 to 8 mm.
进一步地，所述改性分子筛为改性β分子筛、改性Y型分子筛、改性MOR分子筛、改性ZSM-5分子筛、改性ZSM-22分子筛及改性ZSM-23分子筛中的一种或几种。Further, the modified molecular sieve is one of a modified β molecular sieve, a modified Y molecular sieve, a modified MOR molecular sieve, a modified ZSM-5 molecular sieve, a modified ZSM-22 molecular sieve, and a modified ZSM-23 molecular sieve or Several.
进一步地，所述活性金属氧化物中的活性金属为W、Mo、Ni和Co的一种或几种。Further, the active metal in the active metal oxide is one or more of W, Mo, Ni, and Co.
进一步地，所述改性β分子筛比表面积为450～750m 2/g，总孔容为0.3～0.5cm 3/g。 Further, the modified β molecular sieve has a specific surface area of 450 to 750 m 2 /g and a total pore volume of 0.3 to 0.5 cm 3 /g.
进一步地，所述改性Y型分子筛比表面积为750～860m 2/g，总孔容为0.35～0.55cm 3/g。 Further, the modified Y-type molecular sieve has a specific surface area of 750 to 860 m 2 /g and a total pore volume of 0.35 to 0.55 cm 3 /g.
更进一步地，所述改性MOR分子筛比表面积为300～560m 2/g，总孔容为0.3～0.45cm 3/g。 Further, the modified MOR molecular sieve has a specific surface area of 300 to 560 m 2 /g and a total pore volume of 0.3 to 0.45 cm 3 /g.
一种上述优化型柴油加氢裂化催化剂的制备方法，包括以下步骤：A method for preparing the above optimized diesel hydrocracking catalyst comprises the following steps:
1)水热合成法制备改性分子筛：将四乙基溴化铵溶液、氢氧化钠、铝源和水混合并搅拌至澄清溶液，然后加入硅源，继续搅拌得到硅铝凝胶；所述硅源、铝源、氢氧化钠、四乙基溴化铵溶液及水按配料摩尔比SiO 2∶Al 2O 3∶Na 2O∶四乙基溴化铵∶H 2O为50～70∶1∶5～8∶15～20∶1000～1200的比例加入；接着，将硅铝凝胶进行晶化和提纯，再进行焙烧脱模板处理，得分子筛；然后，将脱完模板后的分子筛依次进行铵交换、水 热处理和铝盐处理，得到改性分子筛； 1) preparing a modified molecular sieve by hydrothermal synthesis: mixing tetraethylammonium bromide solution, sodium hydroxide, aluminum source and water and stirring to a clear solution, then adding a silicon source, and continuing to stir to obtain a silica-alumina gel; The silicon source, the aluminum source, the sodium hydroxide, the tetraethylammonium bromide solution and the water have a molar ratio of SiO 2 :Al 2 O 3 :Na 2 O:tetraethylammonium bromide:H 2 O of 50 to 70: Adding in a ratio of 1:5 to 8:15 to 20:1000 to 1200; then, crystallization and purification of the silica-alumina gel, followed by calcination and de-template treatment to obtain a molecular sieve; then, the molecular sieve after the template is removed Performing ammonium exchange, hydrothermal treatment and aluminum salt treatment to obtain a modified molecular sieve;
2)制备改性分子筛与γ-Al 2O 3复合材料：将步骤1)所得改性分子筛加入铝盐和碱的混合溶液中进行沉淀，充分沉淀后取浆液依次进行干燥和焙烧处理，得改性分子筛与γ-Al 2O 3复合材料； 2) preparing modified molecular sieve and γ-Al 2 O 3 composite material: adding the modified molecular sieve obtained in step 1) to a mixed solution of aluminum salt and alkali for precipitation, fully precipitating, and then taking the slurry to be sequentially dried and calcined, and then changed. Molecular sieve and γ-Al 2 O 3 composite;
3)制备催化剂：将改性分子筛与γ-Al 2O 3复合材料、无定形硅铝、粘结剂及活性金属氧化物按所述原料比例进行混合，依次碾压、成型、干燥及活化，即可得所述加氢裂化催化剂。 3) preparing a catalyst: mixing the modified molecular sieve with the γ-Al 2 O 3 composite material, the amorphous silicon aluminum, the binder and the active metal oxide according to the ratio of the raw materials, sequentially rolling, forming, drying and activating, The hydrocracking catalyst can be obtained.
进一步地，所述步骤1)中，铵交换条件为：温度为60～90℃，所用铵盐为0.4～0.6mol/L的氯化铵或硝酸铵。Further, in the step 1), the ammonium exchange condition is: the temperature is 60 to 90 ° C, and the ammonium salt used is 0.4 to 0.6 mol/L of ammonium chloride or ammonium nitrate.
进一步地，所述步骤1)中，水热处理条件为：温度为630～750℃，处理时间为1～4小时，表压为0.05～0.4MPa。Further, in the step 1), the hydrothermal treatment conditions are: a temperature of 630 to 750 ° C, a treatment time of 1 to 4 hours, and a gauge pressure of 0.05 to 0.4 MPa.
进一步地，所述步骤1)中，铝盐处理条件为：所用铝盐溶液中，Al 3+浓度为0.5～1.5mol/L，铝盐与改性分子筛质量比为4～30∶1，处理温度为70～100℃，处理时间为1～5小时。 Further, in the step 1), the aluminum salt treatment condition is: the aluminum salt solution used has an Al 3+ concentration of 0.5 to 1.5 mol/L, and the mass ratio of the aluminum salt to the modified molecular sieve is 4 to 30:1. The temperature is 70 to 100 ° C, and the treatment time is 1 to 5 hours.
进一步地，所述步骤1)中，改性分子筛为改性β分子筛，晶化温度为135～145℃，焙烧脱模板处理条件为：以升温速率2℃/min升温至540～560℃后，焙烧7～9h。Further, in the step 1), the modified molecular sieve is a modified β molecular sieve, the crystallization temperature is 135 to 145 ° C, and the calcination de-template treatment conditions are: after the temperature rise rate is 2 ° C / min, the temperature is raised to 540-560 ° C, Roasted for 7 to 9 hours.
进一步地，所述步骤1)中，铝源为拟薄水铝石、硫酸铝和偏铝酸钠中的一种或几种；硅源为白炭黑、硅溶胶和水玻璃中的一种或几种。Further, in the step 1), the aluminum source is one or more of pseudoboehmite, aluminum sulfate and sodium metaaluminate; the silicon source is one of white carbon black, silica sol and water glass. Or several.
进一步地，所述步骤2)中，铝盐为硫酸铝、硝酸铝和氯化铝中的一种或多种；碱为草酸铵、氨水、氢氧化钠和氢氧化钾中的一种或多种。Further, in the step 2), the aluminum salt is one or more of aluminum sulfate, aluminum nitrate and aluminum chloride; the base is one or more of ammonium oxalate, ammonia water, sodium hydroxide and potassium hydroxide. Kind.
进一步地，所述步骤2)中，沉淀过程中，控制温度为50～70℃，pH值为3～7；干燥温度为110～130℃；焙烧温度为300～600℃，焙烧时间为2～4小时。Further, in the step 2), during the precipitation, the control temperature is 50-70 ° C, the pH is 3-7, the drying temperature is 110-130 ° C, the baking temperature is 300-600 ° C, and the baking time is 2 ～. 4 hours.
更进一步地，所述步骤3)中，干燥温度为100～120℃，时间为18～22小时；活化温度为450～600℃，活化时间为4～6小时。Further, in the step 3), the drying temperature is 100 to 120 ° C, the time is 18 to 22 hours, the activation temperature is 450 to 600 ° C, and the activation time is 4 to 6 hours.
与现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
其一，本发明加氢裂化催化剂，在制备γ-Al 2O 3的铝盐溶液中加入改性分子筛，加入沉淀剂后，使得氢氧化铝沉淀沉积并将改性分子筛包裹起来，沉淀干燥、焙烧后，能够使裂化活性组分均匀的分散到氧化铝中，与现有技术相比，本发明催化剂具有更加均 匀酸性中心、适宜的酸度、大的比表面积和孔容，催化剂中氧化铝与分子筛接触的更加紧密，有利于反应物及产物分子在酸性中心与裂化中心之间的快速转移，使裂化和加氢两种活性组分之间具有更好的协同作用。 First, in the hydrocracking catalyst of the present invention, a modified molecular sieve is added to the aluminum salt solution for preparing γ-Al 2 O 3 , and after adding a precipitating agent, the precipitate of aluminum hydroxide is deposited and the modified molecular sieve is wrapped, and the precipitate is dried, After calcination, the cracking active component can be uniformly dispersed into the alumina. Compared with the prior art, the catalyst of the invention has a more uniform acidity center, suitable acidity, large specific surface area and pore volume, and alumina in the catalyst. Molecular sieves are more closely contacted, which facilitates the rapid transfer of reactants and product molecules between the acid center and the cracking center, so that there is better synergy between the cracking and hydrogenation active components.
其二，本发明加氢裂化催化剂对长链烷烃、芳烃及环烷烃的长侧链烷基有适宜的裂化作用和很好的异构作用，中间馏分油选择性好，催化活性很高，可在保证柴油收率的前提下，明显地降低柴油馏分的凝点，提高柴油的十六烷值。Secondly, the hydrocracking catalyst of the invention has suitable cracking action and good isomerization effect on long-chain alkyl groups of long-chain alkanes, aromatic hydrocarbons and naphthenes, good middle distillate selectivity and high catalytic activity. Under the premise of ensuring diesel oil yield, the freezing point of diesel fraction is obviously reduced, and the cetane number of diesel is improved.
其三，本发明优化了加氢功能和酸性功能之间的匹配，形成强加氢功能与中酸或弱酸性功能组合，正碳离子能更多地在加氢活性中心上加氢饱和向异构化方向进行，减少了裂解产物的二次裂化。Thirdly, the invention optimizes the matching between the hydrogenation function and the acidic function, forms a combination of strong hydrogenation function and medium acid or weak acid function, and the positive carbon ion can be more hydrogenated and saturated at the hydrogenation active center. The direction of the formation proceeds, reducing the secondary cracking of the cracked product.
具体实施方式detailed description
下面结合具体实施例对本发明作进一步的详细说明，便于更清楚地了解本发明，但它们不对本发明构成限定。The present invention will be further described in detail with reference to the preferred embodiments of the invention.
以下实施例中，比表面积和孔容采用低温液氮物理吸附法，硅铝摩尔比采用化学法，骨架硅铝采由NMR法测定；红外酸量，B酸量及L酸量采用吡啶吸附红外光谱法，钠含量采用等离子发射光谱法，分子筛相对结晶度采用XRD方法测定。In the following examples, the specific surface area and pore volume are measured by low temperature liquid nitrogen physical adsorption, the molar ratio of silicon to aluminum is determined by chemical method, and the framework silica aluminum is determined by NMR; the amount of infrared acid, B acid and L acid are adsorbed by pyridine. The spectroscopy method, the sodium content is determined by plasma emission spectroscopy, and the relative crystallinity of the molecular sieve is determined by the XRD method.
以下实施例中制备催化剂载体的主要步骤如下：The main steps in preparing the catalyst support in the following examples are as follows:
1)通过水热合成法制备改性β分子筛(比表面积为450～750m 2/g，总孔容为0.3～0.5cm 3/g)，改性Y型分子筛(比表面积为750～860m 2/g，总孔容为0.35～0.55cm 3/g)，改性MOR分子筛(比表面积为300～560m 2/g，总孔容为0.3～0.45cm 3/g)，改性ZSM-5分子筛，改性ZSM-22分子筛及改性ZSM-23分子筛中的一种或几种，依据分子筛配料摩尔比，将模板剂或导向剂、铝盐、和水混合并搅拌至澄清溶液(其中改性Y型分子筛需要使用盐酸进行调节混合溶液的碱度)，然后在搅拌下向所得的澄清溶液中加入硅源，并继续搅拌得到均匀的硅铝凝胶，最后将硅铝凝胶进行晶化(分子筛为β分子筛时，晶化温度为135～145℃，分子筛为MOR分子筛时，晶化温度为140～160℃，分子筛为Y型分子筛时，晶化温度为80～120℃)，晶化结束后将所得固体产物经洗涤、离心、干燥，焙烧脱模板(焙烧条件为：以升温速率2℃/min升温至550℃后，焙烧7～9h)，脱完模板的分子筛进行铵交换(温度为60～90℃，铵盐为0.4～0.6mol/L的氯化铵或硝酸铵)，水热处理(温度为630～750℃，处理时间为1～4小时，表压为0.05～0.4MPa)，铝盐处理(Al 3+ 浓度为0.5～1.5mol/L，铝盐与分子筛比重4～30∶1，处理温度为70～100℃，时间为1～5小时)，得到改性分子筛。 1) Preparation of modified β molecular sieve by hydrothermal synthesis method (specific surface area: 450-750 m 2 /g, total pore volume: 0.3-0.5 cm 3 /g), modified Y-type molecular sieve (specific surface area of 750-860 m 2 / g, total pore volume is 0.35-0.55 cm 3 /g), modified MOR molecular sieve (specific surface area is 300-560 m 2 /g, total pore volume is 0.3-0.45 cm 3 /g), modified ZSM-5 molecular sieve, One or more of the modified ZSM-22 molecular sieve and the modified ZSM-23 molecular sieve, according to the molecular sieve compounding molar ratio, the template or the guiding agent, the aluminum salt, and the water are mixed and stirred to a clear solution (where the modified Y The molecular sieve needs to adjust the alkalinity of the mixed solution with hydrochloric acid, and then the silicon source is added to the obtained clear solution under stirring, and stirring is continued to obtain a uniform silica-alumina gel, and finally the silica-alumina gel is crystallized (molecular sieve) In the case of β molecular sieve, the crystallization temperature is 135-145 ° C, the molecular sieve is MOR molecular sieve, the crystallization temperature is 140-160 ° C, and the molecular sieve is Y-type molecular sieve, the crystallization temperature is 80-120 ° C), after the crystallization The obtained solid product is washed, centrifuged, dried, and calcined to remove the template (the calcination condition is: a heating rate of 2 ° C /min is heated to 550 ° C, calcined for 7 ~ 9h), the template is removed from the molecular sieve for ammonium exchange (temperature is 60 ~ 90 ° C, ammonium salt is 0.4 ~ 0.6 mol / L ammonium chloride or ammonium nitrate), hydrothermal treatment (temperature is 630 ~ 750 ° C, treatment time is 1 ~ 4 hours, gauge pressure is 0.05 ~ 0.4MPa), aluminum salt treatment (Al 3 + concentration is 0.5 ~ 1.5mol / L, aluminum salt and molecular sieve specific gravity 4 ~ 30: 1. The treatment temperature is 70 to 100 ° C for 1 to 5 hours to obtain a modified molecular sieve.
2)将铝盐溶液和碱沉淀剂混合，把上述改性分子筛加入混合溶液中，搅拌，温度控制在50～70℃，pH值控制在3～7，于50～90℃温度条件下进行蒸发，100℃干燥，将沉淀进行焙烧，温度为300～600℃，时间为2～4小时，得到改性分子筛与氧化铝复合材料。2) mixing the aluminum salt solution and the alkali precipitating agent, adding the above modified molecular sieve to the mixed solution, stirring, the temperature is controlled at 50 to 70 ° C, the pH is controlled at 3 to 7, and the evaporation is carried out at a temperature of 50 to 90 ° C. The mixture was dried at 100 ° C, and the precipitate was calcined at a temperature of 300 to 600 ° C for 2 to 4 hours to obtain a modified molecular sieve and an alumina composite material.
3)最后，按催化剂的物料比例，将改性分子筛与氧化铝复合材料，无定形硅铝，活性金属氧化物及粘结剂进行混合、碾压、成型、干燥、活化得到催化剂，碾压时间为20～60分钟，挤条成柱状，长度为3～8mm，120℃干燥20小时，450～600℃下焙烧5～6小时，得到催化剂。3) Finally, according to the proportion of the catalyst material, the modified molecular sieve and the alumina composite material, the amorphous silicon aluminum, the active metal oxide and the binder are mixed, compacted, formed, dried and activated to obtain a catalyst, and the rolling time is obtained. For 20 to 60 minutes, the strip is extruded into a column shape, the length is 3 to 8 mm, dried at 120 ° C for 20 hours, and calcined at 450 to 600 ° C for 5 to 6 hours to obtain a catalyst.
实施例1Example 1
称取201.3g四乙基溴化铵(工业级)，27.39g氢氧化钠，7.2g拟薄水铝石(70wt％，工业级)，870g水混合并搅拌至澄清溶液，然后在不断搅拌下向溶液中加入180g白炭黑(工业级)，并继续搅拌以得到均匀的硅铝凝胶；将硅铝凝胶于145℃动态晶化7天，经固液分离和洗涤干燥后，在空气流中于550℃焙烧8小时，得到β分子筛，脱完模板后，使用浓度为0.5mol/L氯化铵溶液在80℃下进行铵交换2次，液固比为10∶1，水洗干燥后再进行水热处理，在水蒸汽压力0.15MPa，处理温度为600℃，处理时间为2.5小时，之后进行铝盐处理，将水热处理后的分子筛放入带有回流装置并可以密闭的烧瓶中，加入含浓度0.8mol/L硫酸铝水溶液1000ml，在95℃下恒温搅拌1.0小时，水洗，过滤，以洗涤液的pH值接近7后停止洗涤。滤饼在烘箱中100℃干燥12小时，得到β改性分子筛，性质见表1。Weigh 201.3 g of tetraethylammonium bromide (technical grade), 27.39 g of sodium hydroxide, 7.2 g of pseudoboehmite (70 wt%, technical grade), mix 870 g of water and stir to a clear solution, then with constant stirring 180g of white carbon black (industrial grade) was added to the solution, and stirring was continued to obtain a uniform silica-alumina gel; the silica-alumina gel was dynamically crystallized at 145 ° C for 7 days, after solid-liquid separation and washing and drying, in air. The mixture was calcined at 550 ° C for 8 hours to obtain β molecular sieve. After the template was removed, the ammonium exchange was carried out twice at a concentration of 0.5 mol/L ammonium chloride solution at 80 ° C, and the liquid-solid ratio was 10:1. Further, hydrothermal treatment is carried out at a water vapor pressure of 0.15 MPa, a treatment temperature of 600 ° C, and a treatment time of 2.5 hours, followed by treatment with an aluminum salt, and the hydrothermally treated molecular sieve is placed in a flask with a reflux device and can be sealed, and added. 1000 ml of an aluminum sulfate aqueous solution having a concentration of 0.8 mol/L was stirred at a constant temperature of 95 ° C for 1.0 hour, washed with water, and filtered, and the washing was stopped after the pH of the washing liquid was close to 7. The filter cake was dried in an oven at 100 ° C for 12 hours to obtain a β-modified molecular sieve. The properties are shown in Table 1.
称取140g草酸铵与3000ml氯化铝溶液(浓度为1.5mol/L)混合于5000ml烧杯中，将28.9g(干基98％)改性分子筛加入混合液中，恒温70℃，不断加入2mol/L的氨水直至pH值为4，于85℃下蒸发，将吸出的白色固体于100℃下干燥3小时，500℃下焙烧4小时得到分子筛与γ-Al 2O 3复合材料274.5g(干基93％)，转化率为73％。将分子筛与γ-Al 2O 3的复合材料195.5g(干基93％)、无定形硅铝238.6g(干基88％)、MoO 3 90.5g(99.1wt％)、Ni(NO 3) 2·6H 2O(NiO,26.6wt％)116.7g、粘结剂360g(干基25％)进行混合，在轮碾机中进行碾压40分钟，碾压为可挤膏状，挤条成型，形状为柱状，长度为3～8mm，并于120℃干燥20小时，500℃下焙烧5～6小时，得到加氢裂化催化剂，编号 为C-1，性质见表2。 Weigh 140g of ammonium oxalate and 3000ml of aluminum chloride solution (concentration of 1.5mol / L) in 5000ml beaker, add 28.9g (dry 98%) modified molecular sieve to the mixture, constant temperature 70 ° C, continue to add 2mol / The ammonia water of L was evaporated to 85 ° C until the pH was 4, and the aspirated white solid was dried at 100 ° C for 3 hours and calcined at 500 ° C for 4 hours to obtain molecular sieve and γ-Al 2 O 3 composite material of 274.5 g (dry basis). 93%), the conversion rate was 73%. The composite material of molecular sieve and γ-Al 2 O 3 was 195.5 g (dry basis 93%), amorphous silicon aluminum 238.6 g (dry basis 88%), MoO 3 90.5 g (99.1 wt%), Ni(NO 3 ) 2 · 6H 2 O (NiO, 26.6wt%) 116.7g, binder 360g (dry basis 25%) were mixed, crushed in a wheel mill for 40 minutes, crushed into a squeezeable paste, extruded into strips, The shape is columnar, the length is 3-8 mm, and dried at 120 ° C for 20 hours, and calcined at 500 ° C for 5-6 hours to obtain a hydrocracking catalyst, numbered C-1, and the properties are shown in Table 2.
实施例2Example 2
改性分子筛同实施例1中的β改性分子筛；分子筛与γ-Al 2O 3复合材料同实施例1；将复合材料195.5g(干基93％)、无定形硅铝204.5g(干基88％)、MoO 3为108.5g(99.1wt％)、Ni(NO 3) 2·6H 2O(NiO,26.6wt％)为163.4g、粘结剂360g(干基25％)进行混合，在轮碾机中进行碾压40分钟，碾压为可挤膏状，挤条成型，形状为柱状，长度为3～8mm，并于120℃干燥20小时，500℃下焙烧5～6小时，得到加氢裂化催化剂，编号为C-2，性质见表2。 The modified molecular sieve was the same as the β modified molecular sieve in Example 1; the molecular sieve and the γ-Al 2 O 3 composite were the same as in Example 1; the composite material was 195.5 g (dry basis 93%), amorphous silicon aluminum 204.5 g (dry basis) 88%), MoO 3 is 108.5 g (99.1 wt%), Ni(NO 3 ) 2· 6H 2 O (NiO, 26.6 wt%) is 163.4 g, and binder 360 g (dry basis 25%) is mixed. The roller mill is rolled for 40 minutes, crushed into a squeezing paste, extruded into strips, and shaped into a column shape, having a length of 3 to 8 mm, dried at 120 ° C for 20 hours, and calcined at 500 ° C for 5 to 6 hours to obtain Hydrocracking catalyst, numbered C-2, properties are shown in Table 2.
实施例3Example 3
改性分子筛同实施例1中的β改性分子筛；称取140g草酸铵与3000ml氯化铝溶液(浓度为1.5mol/L)混合于5000ml烧杯中，将52.6g(干基98％)改性分子筛加入混合液中，恒温70℃，不断加入2mol/L的氨水直至pH值为4，于85℃下蒸发，将吸出的白色固体于100℃下干燥3小时，500℃下焙烧4小时得到分子筛γ-Al 2O 3复合材料272.8g(干基93％)，转化率为72.3％。将分子筛与γ-Al 2O 3的复合材料173.2g(干基93％)、无定形硅铝238.6g(干基88％)、MoO 3为108.5g(99.1wt％)、Ni(NO 3) 2·6H 2O(NiO,26.6wt％)为116.7g、粘结剂360g(干基25％)进行混合，在轮碾机中进行碾压40分钟，碾压为可挤膏状，挤条成型，形状为柱状，长度为3～8mm，并于120℃干燥20小时，500℃下焙烧5～6小时，得到加氢裂化催化剂，编号为C-3，性质见表2。 The modified molecular sieve was the same as the β-modified molecular sieve in Example 1; 140 g of ammonium oxalate and 3000 ml of aluminum chloride solution (concentration: 1.5 mol/L) were weighed and mixed in a 5000 ml beaker to modify 52.6 g (dry basis 98%). Molecular sieves were added to the mixture, kept at a constant temperature of 70 ° C, and continuously added with 2 mol/L of ammonia water until the pH was 4, and evaporated at 85 ° C. The aspirated white solid was dried at 100 ° C for 3 hours and calcined at 500 ° C for 4 hours to obtain a molecular sieve. The γ-Al 2 O 3 composite material was 272.8 g (dry basis 93%), and the conversion rate was 72.3%. The composite material of molecular sieve and γ-Al 2 O 3 was 173.2 g (dry basis 93%), amorphous silicon aluminum 238.6 g (dry basis 88%), MoO 3 was 108.5 g (99.1 wt%), Ni(NO 3 ) 2· 6H 2 O (NiO, 26.6wt%) was 116.7g, binder 360g (dry basis 25%) was mixed, crushed in a wheel mill for 40 minutes, crushed into a squeezing paste, extruded The molding has a columnar shape and a length of 3 to 8 mm, and is dried at 120 ° C for 20 hours and calcined at 500 ° C for 5 to 6 hours to obtain a hydrocracking catalyst, which is numbered C-3, and the properties are shown in Table 2.
实施例4Example 4
改性分子筛同实施例1中的β改性分子筛；分子筛与γ-Al 2O 3的复合材料同实施例3，将复合材料173.2g(干基93％)、无定形硅铝204.5g(干基88％)、MoO 3为108.5g(99.1wt％)、Ni(NO 3) 2·6H 2O(NiO,26.6wt％)为233.4g、粘结剂360g(干基25％)进行混合，在轮碾机中进行碾压40分钟，碾压为可挤膏状，挤条成型，形状为柱状，长度为3～8mm，并于120℃干燥20小时，500℃下焙烧5～6小时，得到加氢裂化催化剂，编号为C-4，性质见表2。 The modified molecular sieve was the same as the β modified molecular sieve in Example 1; the composite material of molecular sieve and γ-Al 2 O 3 was the same as in Example 3, and the composite material was 173.2 g (dry basis 93%) and amorphous silicon aluminum 204.5 g (dry). 88%), MoO 3 is 108.5 g (99.1 wt%), Ni(NO 3 ) 2· 6H 2 O (NiO, 26.6 wt%) is 233.4 g, and binder 360 g (dry basis 25%) is mixed. It is rolled in a wheel mill for 40 minutes, crushed into a squeezable paste, extruded into strips, shaped like a column, and has a length of 3 to 8 mm, dried at 120 ° C for 20 hours, and calcined at 500 ° C for 5 to 6 hours. A hydrocracking catalyst was obtained, numbered C-4, and the properties are shown in Table 2.
对比例1Comparative example 1
对比实施例1，改性分子筛同实施例1中的β改性分子筛；将20.5g改性分子筛(干基98％)、氧化铝169.8g(干基96％)、无定形硅铝238.6g(干基88％)、MoO 3为 90.5g(99.1wt％)、Ni(NO 3) 2·6H 2O(NiO,26.6wt％)为116.7g、粘结剂360g(干基25％)进行混合，在轮碾机中进行碾压40分钟，碾压为可挤膏状，挤条成型，形状为柱状，长度为3～8mm，并于120℃干燥20小时，500℃下焙烧5～6小时，得到加氢裂化催化剂，编号为C-5，性质见表2。 Comparative Example 1, the modified molecular sieve was the same as the β-modified molecular sieve of Example 1; 20.5 g of modified molecular sieve (dry basis 98%), alumina 169.8 g (dry basis 96%), amorphous silica aluminum 238.6 g ( Dry base 88%), MoO 3 is 90.5 g (99.1 wt%), Ni(NO 3 ) 2· 6H 2 O (NiO, 26.6 wt%) is 116.7 g, and binder 360 g (dry basis 25%) is mixed. Grinding in a wheel mill for 40 minutes, crushing into a squeezing paste, extruding, forming a column shape, length 3 to 8 mm, drying at 120 ° C for 20 hours, baking at 500 ° C for 5 to 6 hours , a hydrocracking catalyst was obtained, numbered C-5, and the properties are shown in Table 2.
对比例2Comparative example 2
对比实施例3，改性分子筛同实施例1中的β改性分子筛；将33.4g改性分子筛(干基98％)、氧化铝135.3g(干基96％)、无定形硅铝238.6g(干基88％)、MoO 3为108.5g(99.1wt％)、Ni(NO 3) 2·6H 2O(NiO,26.6wt％)为116.7g、粘结剂360g(干基25％)进行混合，在轮碾机中进行碾压40分钟，碾压为可挤膏状，挤条成型，形状为柱状，长度为3～8mm，并于120℃干燥20小时，500℃下焙烧5～6小时，得到加氢裂化催化剂，编号为C-6，性质见表2。 Comparative Example 3, the modified molecular sieve was the same as the β-modified molecular sieve of Example 1; 33.4 g of modified molecular sieve (dry basis 98%), alumina 135.3 g (dry basis 96%), amorphous silica aluminum 238.6 g ( Dry base 88%), MoO 3 is 108.5 g (99.1 wt%), Ni(NO 3 ) 2· 6H 2 O (NiO, 26.6 wt%) is 116.7 g, and binder 360 g (dry basis 25%) is mixed. Grinding in a wheel mill for 40 minutes, crushing into a squeezing paste, extruding, forming a column shape, length 3 to 8 mm, drying at 120 ° C for 20 hours, baking at 500 ° C for 5 to 6 hours , obtained a hydrocracking catalyst, numbered C-6, and the properties are shown in Table 2.
将实施例1和对比例1中的催化剂在固定床加氢实验装置上进行评价，评价条件为：反应总压为10MPa，氢油体积比为1000，体积空速1.0h -1，使用减压馏分油(VGO)为原料油，该原料油性质见表3。将催化剂C-1、C-5在相同的工艺条件下进行评价，评价结果见表4，从表4数据可以看出，在相同的工艺条件下，实施例1的催化剂具有更好中间馏分油选择性，且在保证柴油收率的前提下，明显地降低柴油馏分的凝点，提高柴油的十六烷值。 The catalysts of Example 1 and Comparative Example 1 were evaluated on a fixed bed hydrogenation experimental apparatus under the following conditions: a total reaction pressure of 10 MPa, a hydrogen oil volume ratio of 1000, a volumetric space velocity of 1.0 h -1 , and a reduced pressure. Distillate oil (VGO) is a feedstock oil, and the properties of the feedstock oil are shown in Table 3. Catalysts C-1 and C-5 were evaluated under the same process conditions, and the evaluation results are shown in Table 4. As can be seen from the data in Table 4, the catalyst of Example 1 had better middle distillate oil under the same process conditions. Selectively, and under the premise of ensuring diesel oil yield, significantly reduce the freezing point of the diesel fraction and increase the cetane number of the diesel.
表1Table 1
硅铝比(Si/Al)Silicon to aluminum ratio (Si/Al) 34.534.5
相对结晶度，％Relative crystallinity, % 103103
比表面，m 2/g Specific surface, m 2 /g 625625
总孔容，ml/gTotal pore volume, ml/g 0.290.29
红外酸量，mmol/gInfrared acid amount, mmol/g 0.280.28
B酸/L酸B acid / L acid 0.560.56
Na 2O，wt％ Na 2 O, wt% ＜0.01<0.01
表2Table 2
Figure PCTCN2018083510-appb-000001
Figure PCTCN2018083510-appb-000001
表3table 3
原料油Raw material oil 减压馏分油Vacuum distillate
密度(20℃)，kg/m 3 Density (20 ° C), kg / m 3 912.3912.3
馏程，℃Distillation range, °C  
IBP/10％IBP/10% 315/403315/403
30％/50％30%/50% 442/461442/461
70％/90％70%/90% 495/526495/526
95％/EBP95%/EBP 532/544532/544
凝点，℃Freezing point, °C 3232
氮，μg/gNitrogen, μg/g 15681568
碳，wt％Carbon, wt% 84.5384.53
氢，wt％Hydrogen, wt% 11.7211.72
残炭，wt％Carbon residue, wt% 0.320.32
BMCI值BMCI value 4343
表4Table 4
Figure PCTCN2018083510-appb-000002
Figure PCTCN2018083510-appb-000002

Claims (16)

  1. 一种优化型柴油加氢裂化催化剂，其特征在于：所述催化剂原料包括以下组分及其重量百分比：1～25％的改性分子筛，10～65％的γ-Al 2O 3，15～70％的无定形硅铝，9～40％的粘结剂及10～35％的活性金属氧化物；所述催化剂的比表面积为200～400m 2/g，总孔容为0.30～0.65cm 3/g。 An optimized diesel hydrocracking catalyst characterized in that the catalyst raw material comprises the following components and their weight percentages: 1 to 25% modified molecular sieve, 10 to 65% γ-Al 2 O 3 , 15～ 70% amorphous silicon aluminum, 9-40% binder and 10-35% active metal oxide; the catalyst has a specific surface area of 200-400 m 2 /g, and a total pore volume of 0.30-0.65 cm 3 /g.
  2. 根据权利要求1所述优化型柴油加氢裂化催化剂，其特征在于：所述催化剂原料包括以下组分及其重量百分比：3.3～5.4％的改性分子筛，21.6～27％的γ-Al 2O 3，29.7～35％的无定形硅铝，15～25％的粘结剂及20～28％的活性金属氧化物；所述催化剂的比表面积为341～375m 2/g，总孔容为0.49～0.57cm 3/g；所述催化剂呈柱状，长度为3～8mm。 The optimized diesel hydrocracking catalyst according to claim 1, wherein the catalyst raw material comprises the following components and their weight percentages: 3.3 to 5.4% of modified molecular sieves, and 21.6 to 27% of γ-Al 2 O 3 , 29.7 to 35% amorphous silicon aluminum, 15 to 25% binder and 20 to 28% active metal oxide; the catalyst has a specific surface area of 341 to 375 m 2 /g, and a total pore volume of 0.49 ～0.57 cm 3 /g; the catalyst is columnar and has a length of 3 to 8 mm.
  3. 根据权利要求1或2所述优化型柴油加氢裂化催化剂，其特征在于：所述改性分子筛为改性β分子筛、改性Y型分子筛、改性MOR分子筛、改性ZSM-5分子筛、改性ZSM-22分子筛及改性ZSM-23分子筛中的一种或几种。The optimized diesel hydrocracking catalyst according to claim 1 or 2, wherein the modified molecular sieve is modified beta molecular sieve, modified Y molecular sieve, modified MOR molecular sieve, modified ZSM-5 molecular sieve, modified One or more of ZSM-22 molecular sieves and modified ZSM-23 molecular sieves.
  4. 根据权利要求1或2所述优化型柴油加氢裂化催化剂，其特征在于：所述活性金属氧化物中的活性金属为W、Mo、Ni和Co的一种或几种。The optimized diesel hydrocracking catalyst according to claim 1 or 2, wherein the active metal in the active metal oxide is one or more of W, Mo, Ni and Co.
  5. 根据权利要求3所述优化型柴油加氢裂化催化剂，其特征在于：所述改性β分子筛比表面积为450～750m 2/g，总孔容为0.3～0.5cm 3/g。 The optimized diesel hydrocracking catalyst according to claim 3, wherein the modified β molecular sieve has a specific surface area of 450 to 750 m 2 /g and a total pore volume of 0.3 to 0.5 cm 3 /g.
  6. 根据权利要求3所述优化型柴油加氢裂化催化剂，其特征在于：所述改性Y型分子筛比表面积为750～860m 2/g，总孔容为0.35～0.55cm 3/g。 The optimized diesel hydrocracking catalyst according to claim 3, wherein the modified Y-type molecular sieve has a specific surface area of 750 to 860 m 2 /g and a total pore volume of 0.35 to 0.55 cm 3 /g.
  7. 根据权利要求3所述优化型柴油加氢裂化催化剂，其特征在于：所述改性MOR分子筛比表面积为300～560m 2/g，总孔容为0.3～0.45cm 3/g。 The optimized diesel hydrocracking catalyst according to claim 3, wherein the modified MOR molecular sieve has a specific surface area of 300 to 560 m 2 /g and a total pore volume of 0.3 to 0.45 cm 3 /g.
  8. 一种权利要求1所述优化型柴油加氢裂化催化剂的制备方法，其特征在于：包括以下步骤：A method for preparing an optimized diesel hydrocracking catalyst according to claim 1, comprising the steps of:
    1)水热合成法制备改性分子筛：将四乙基溴化铵溶液、氢氧化钠、铝源和水混合并搅拌至澄清溶液，然后加入硅源，继续搅拌得到硅铝凝胶；所述硅源、铝源、氢氧化钠、四乙基溴化铵溶液及水按配料摩尔比SiO 2∶Al 2O 3∶Na 2O∶四乙基溴化铵∶H 2O为50～70∶1∶5～8∶15～20∶1000～1200的比例加入；接着，将硅铝凝胶进行晶化和提纯，再进行焙烧脱模板处理，得分子筛；然后，将脱完模板后的分子筛依次进行铵交换、水 热处理和铝盐处理，得到改性分子筛； 1) preparing a modified molecular sieve by hydrothermal synthesis: mixing tetraethylammonium bromide solution, sodium hydroxide, aluminum source and water and stirring to a clear solution, then adding a silicon source, and continuing to stir to obtain a silica-alumina gel; The silicon source, the aluminum source, the sodium hydroxide, the tetraethylammonium bromide solution and the water have a molar ratio of SiO 2 :Al 2 O 3 :Na 2 O:tetraethylammonium bromide:H 2 O of 50 to 70: Adding in a ratio of 1:5 to 8:15 to 20:1000 to 1200; then, crystallization and purification of the silica-alumina gel, followed by calcination and de-template treatment to obtain a molecular sieve; then, the molecular sieve after the template is removed Performing ammonium exchange, hydrothermal treatment and aluminum salt treatment to obtain a modified molecular sieve;
    2)制备改性分子筛与γ-Al 2O 3复合材料：将步骤1)所得改性分子筛加入铝盐和碱的混合溶液中进行沉淀，充分沉淀后取浆液依次进行干燥和焙烧处理，得改性分子筛与γ-Al 2O 3复合材料； 2) preparing modified molecular sieve and γ-Al 2 O 3 composite material: adding the modified molecular sieve obtained in step 1) to a mixed solution of aluminum salt and alkali for precipitation, fully precipitating, and then taking the slurry to be sequentially dried and calcined, and then changed. Molecular sieve and γ-Al 2 O 3 composite;
    3)制备催化剂：将改性分子筛与γ-Al 2O 3复合材料、无定形硅铝、粘结剂及活性金属氧化物按所述原料比例进行混合，依次碾压、成型、干燥及活化，即可得所述加氢裂化催化剂。 3) preparing a catalyst: mixing the modified molecular sieve with the γ-Al 2 O 3 composite material, the amorphous silicon aluminum, the binder and the active metal oxide according to the ratio of the raw materials, sequentially rolling, forming, drying and activating, The hydrocracking catalyst can be obtained.
  9. 根据权利要求8所述优化型柴油加氢裂化催化剂的制备方法，其特征在于：所述步骤1)中，铵交换条件为：温度为60～90℃，所用铵盐为0.4～0.6mol/L的氯化铵或硝酸铵。The method for preparing an optimized diesel hydrocracking catalyst according to claim 8, wherein in the step 1), the ammonium exchange condition is: the temperature is 60 to 90 ° C, and the ammonium salt used is 0.4 to 0.6 mol/L. Ammonium chloride or ammonium nitrate.
  10. 根据权利要求8所述优化型柴油加氢裂化催化剂的制备方法，其特征在于：所述步骤1)中，水热处理条件为：温度为630～750℃，处理时间为1～4小时，表压为0.05～0.4MPa。The method for preparing an optimized diesel hydrocracking catalyst according to claim 8, wherein in the step 1), the hydrothermal treatment conditions are: a temperature of 630 to 750 ° C, a treatment time of 1 to 4 hours, and a gauge pressure. It is 0.05 to 0.4 MPa.
  11. 根据权利要求8所述优化型柴油加氢裂化催化剂的制备方法，其特征在于：所述步骤1)中，铝盐处理条件为：所用铝盐溶液中，Al 3+浓度为0.5～1.5mol/L，铝盐与改性分子筛质量比为4～30∶1，处理温度为70～100℃，处理时间为1～5小时。 The method for preparing an optimized diesel hydrocracking catalyst according to claim 8, wherein in the step 1), the aluminum salt is treated in the aluminum salt solution, and the Al 3+ concentration is 0.5 to 1.5 mol/ L, the mass ratio of the aluminum salt to the modified molecular sieve is 4 to 30:1, the treatment temperature is 70 to 100 ° C, and the treatment time is 1 to 5 hours.
  12. 根据权利要求8～11中任一项所述优化型柴油加氢裂化催化剂的制备方法，其特征在于：所述步骤1)中，改性分子筛为改性β分子筛，晶化温度为135～145℃，焙烧脱模板处理条件为：以升温速率2℃/min升温至540～560℃后，焙烧7～9h。The method for preparing an optimized diesel hydrocracking catalyst according to any one of claims 8 to 11, wherein in the step 1), the modified molecular sieve is a modified β molecular sieve, and the crystallization temperature is 135-145. °C, roasting and stripping treatment conditions are: heating at a heating rate of 2 ° C / min to 540 ~ 560 ° C, and then roasting for 7 ~ 9h.
  13. 根据权利要求8～11中任一项所述优化型柴油加氢裂化催化剂的制备方法，其特征在于：所述步骤1)中，铝源为拟薄水铝石、硫酸铝和偏铝酸钠中的一种或几种；硅源为白炭黑、硅溶胶和水玻璃中的一种或几种。The method for preparing an optimized diesel hydrocracking catalyst according to any one of claims 8 to 11, wherein in the step 1), the aluminum source is pseudoboehmite, aluminum sulfate and sodium metaaluminate. One or more of them; the silicon source is one or more of white carbon black, silica sol and water glass.
  14. 根据权利要求8～11中任一项所述优化型柴油加氢裂化催化剂的制备方法，其特征在于：所述步骤2)中，铝盐为硫酸铝、硝酸铝和氯化铝中的一种或多种；碱为草酸铵、氨水、氢氧化钠和氢氧化钾中的一种或多种。The method for preparing an optimized diesel hydrocracking catalyst according to any one of claims 8 to 11, wherein in the step 2), the aluminum salt is one of aluminum sulfate, aluminum nitrate and aluminum chloride. Or a plurality; the base is one or more of ammonium oxalate, ammonia, sodium hydroxide and potassium hydroxide.
  15. 根据权利要求8～11中任一项所述优化型柴油加氢裂化催化剂的制备方法，其特征在于：所述步骤2)中，沉淀过程中，控制温度为50～70℃，pH值为3～7；干燥温度为110～130℃；焙烧温度为300～600℃，焙烧时间为2～4小时。The method for preparing an optimized diesel hydrocracking catalyst according to any one of claims 8 to 11, wherein in the step 2), during the precipitation, the control temperature is 50 to 70 ° C, and the pH is 3 ～7; drying temperature is 110-130 ° C; calcination temperature is 300-600 ° C, and baking time is 2 to 4 hours.
  16. 根据权利要求8～11中任一项所述优化型柴油加氢裂化催化剂载体的制备方法，其特征在于：所述步骤3)中，干燥温度为100～120℃，时间为18～22小时；活化温度为450～600℃，活化时间为4～6小时。The method for preparing an optimized diesel hydrocracking catalyst carrier according to any one of claims 8 to 11, wherein in the step 3), the drying temperature is 100 to 120 ° C, and the time is 18 to 22 hours; The activation temperature is 450 to 600 ° C, and the activation time is 4 to 6 hours.
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