WO2022063203A1 - 一种催化裂化催化剂及其制备方法与应用 - Google Patents

一种催化裂化催化剂及其制备方法与应用 Download PDF

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WO2022063203A1
WO2022063203A1 PCT/CN2021/120144 CN2021120144W WO2022063203A1 WO 2022063203 A1 WO2022063203 A1 WO 2022063203A1 CN 2021120144 W CN2021120144 W CN 2021120144W WO 2022063203 A1 WO2022063203 A1 WO 2022063203A1
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catalytic cracking
weight
heat capacity
specific heat
matrix material
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French (fr)
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刘倩倩
达志坚
宋海涛
陈振宇
朱玉霞
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中国石油化工股份有限公司
中国石油化工股份有限公司石油化工科学研究院
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
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    • 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
    • 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
    • B01J29/80—Mixtures of different zeolites
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    • 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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
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    • B01J35/635—0.5-1.0 ml/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01J35/647—2-50 nm
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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
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J37/08—Heat treatment
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to a catalytic cracking catalyst and its preparation method and application.
  • metal trapping components are added in the prior art to eliminate or weaken its impact.
  • most of the metal trapping components also affect the activity of the catalyst. Therefore, it is mostly introduced into the catalyst system in the form of a separate co-agent. When directly introduced into the catalyst, it may cause some adverse effects on the performance of the catalyst, and the addition is strictly limited.
  • CN101939095A discloses a molecular sieve catalyst and a preparation method thereof for preparing light olefins by catalytic cracking of naphtha in a harsh environment of high temperature and high humidity.
  • the catalyst is prepared by spray-drying and calcining a mixed slurry in which 0.01-5.0 wt % MnO 2 and 1-15 wt % P 2 O are mixed 5 Simultaneously embedded in a catalyst composed of zeolite, clay and inorganic composites.
  • the method of simultaneously intercalating manganese and phosphate into zeolite and inorganic composites can be used to improve the thermal stability of the obtained spherical catalyst, and to improve hydrocarbons (eg naphtha) by protecting the acidic sites of the zeolite Olefin yield after cracking.
  • hydrocarbons eg naphtha
  • the important steps are the mixing ratio and mixing order of Mn, P, zeolite and inorganic complex. Mixing manganese and phosphorus in the catalyst slurry in a dissolved form has very limited improvement effect on the catalyst, which is mainly used for naphtha conversion, and does not involve how to improve its heavy oil conversion performance.
  • the technical problem to be solved by the present invention is to provide a new catalytic cracking catalyst with better heavy oil conversion ability and metal pollution resistance ability.
  • Another technical problem to be solved by the present invention is to provide the preparation method of the catalytic cracking catalyst and the application of the catalytic cracking catalyst in the catalytic cracking of heavy oil.
  • the present invention provides a catalytic cracking catalyst, wherein the catalytic cracking catalyst contains a cracking active component, a high specific heat capacity matrix material, clay and a binder; the high specific heat capacity matrix material contains at least 5 wt % of oxidized MnO2 Manganese, the high specific heat capacity matrix material has a specific heat capacity of 1.3-2.0 J/(g ⁇ K) at a temperature of 1000K, and the cracking active component includes Y-type molecular sieve.
  • the high specific heat capacity matrix material contains 5-95 wt % alumina based on Al 2 O 3 , 5-95 wt % manganese oxide based on MnO 2 and 0-40 wt % boron compound based on dry basis.
  • the boron compound is boron nitride and/or boron oxide.
  • the specific surface area of the high specific heat capacity matrix material is 150-500 m 2 ⁇ g -1 .
  • the pore volume of the high specific heat capacity matrix material is 0.3-1.5 cm 3 ⁇ g -1 .
  • the average pore diameter of the high specific heat capacity matrix material is 3-20 nm.
  • the intensity ratio of peaks at 2 ⁇ angles of 18 ⁇ 0.5° and 2 ⁇ angles of 37 ⁇ 0.5° is 1:(3-10).
  • the high specific heat capacity matrix material can be prepared according to a preparation method comprising the following steps:
  • the mixing of the aluminum source and the alkali to form a gel includes: mixing the aluminum source solution and the alkali solution to form a solution with a temperature ranging from room temperature to 85° C. and a pH value of 7-11. colloid.
  • the concentration of alumina in the aluminum source solution is 150-350 gAl 2 O 3 /L, and the concentration of the alkali in the alkali solution is 0.1-1 mol/L.
  • Described aluminium source is selected from one or more in aluminium nitrate, aluminium sulfate, aluminium phosphate and aluminium chloride etc.;
  • Described alkali is (can be) water-soluble carbonate, (can be) water-soluble One or more of bicarbonate, () water soluble hydroxide.
  • the alkali solution is selected from an alkaline aqueous solution containing one or more of CO 3 2- , HCO 3 - or OH - , and the concentration of CO 3 2- in the alkali solution is 0-0.6mol/L , the concentration of OH - is 0-0.5mol/L, and the concentration of HCO 3 - is 0-1mol/L, provided that the sum of the concentration of CO 3 2- , OH - and HCO 3 - is not zero .
  • the concentration of CO 3 2- , the concentration of OH- , and the concentration of HCO 3- are obtained by dividing the molar amount (mol) of anionic groups in the base used to form the alkaline aqueous solution by the alkaline aqueous solution volume (L).
  • urea and manganese ion mol ratio are 1-5, for example 2-4, the concentration of manganese salt in the manganese salt solution can be 50-500g in terms of MnO 2 L -1 .
  • step (2) urea is added to the manganese salt solution, and then stirred at room temperature for 30-60 minutes to obtain a manganese source solution.
  • the boron compound is, for example, boron nitride and/or boron oxide and/or boron oxide precursor.
  • the boron nitride can be one or more of hexagonal boron nitride, cubic boron nitride, rhombohedral boron nitride and wurtzite boron nitride;
  • the boron oxide precursor can be ammonium borate , one or more of ammonium biborate or boric acid.
  • the process of aging is also included after mixing the aluminum-containing colloid and the manganese source solution, and the aging temperature is from room temperature to 120 ° C, and the aging time is 4-72 hours.
  • the ageing temperature is 60-100° C., and the ageing time is 12-36 hours.
  • the roasting temperature in step (4) is 500°C-900°C, and the roasting time is 4-8 hours.
  • the present invention also provides a method for preparing the catalytic cracking catalyst, which comprises mixing and beating the active cracking component, a matrix material with a high specific heat capacity and/or its precursor, clay and a binder, spray drying, washing, filtering and dry.
  • the precursor of the high specific heat capacity matrix material refers to the high specific heat capacity matrix material obtained without calcination in step (4); thus in the present invention, "high specific heat capacity matrix material” may refer to the calcination in step (4) and the The general term for the obtained high specific heat capacity matrix material and the high specific heat capacity matrix material obtained without the calcination in step (4), or only refers to the high specific heat capacity matrix material obtained through the calcination in step (4).
  • the present invention also provides the application of the catalytic cracking catalyst in the catalytic cracking of heavy oil.
  • the catalytic cracking catalyst provided by the invention can improve the specific heat capacity of the catalytic cracking catalyst by using a specific high specific heat capacity material in combination with a cracking active component, clay and a binder, which is beneficial to the atomization and cracking of heavy oil macromolecules in the reactor.
  • the catalyst provided by the invention has better wear resistance performance.
  • the catalytic cracking catalyst provided by the invention is used for catalytic cracking of heavy oil, and has higher conversion rate of heavy oil, higher yield of light oil, and higher yield of liquid.
  • the catalyst provided by the invention has the ability to resist various metal pollution, and can have higher total liquid yield, higher light oil yield and higher gasoline yield in the case of pollution of iron, vanadium and nickel. .
  • FIG. 1 is an X-ray diffraction pattern of the high specific heat capacity host material of Example 1.
  • the high specific heat capacity matrix material refers to a material whose specific heat capacity at 1000K is not less than 1.3 J/(g ⁇ K).
  • the sum of the contents of the components of the catalyst when referring to the content of the components of the catalyst, the sum of the contents of the components of the catalyst is 100% by weight; when referring to the content of the components of the high specific heat capacity matrix material, the components of the high specific heat capacity matrix material The sum of the content is 100% by weight; when referring to the anhydrous chemical expression of the high specific heat capacity matrix material, the coefficients of each component in the anhydrous chemical expression are based on weight, and the sum of the coefficients of each component is 100.
  • the catalytic cracking catalyst provided by the present invention, wherein, based on the total weight of the catalytic cracking catalyst, on a dry basis, the catalytic cracking catalyst contains 1-60% by weight of cracking active components, 1-50% by weight of High specific heat capacity matrix material, 1-70 wt % clay and 1-70 wt % binder; the high specific heat capacity matrix material contains at least 5 wt % manganese oxide, and at a temperature of 1000K, the high specific heat capacity matrix material The specific heat capacity is 1.3-2.0J/(g ⁇ K).
  • the dry basis refers to the solid product after the substance is calcined at 800°C for 1 hour.
  • the room temperature in the present invention is 15-40°C, for example, 15°C.
  • the catalytic cracking catalyst preferably, based on the total weight of the catalytic cracking catalyst, contains 10-50 wt % of cracking active components on a dry basis, 5 wt % on a dry basis - 40 wt% high specific heat capacity matrix material, 10-60 wt% clay on a dry basis and 10-60 wt% binder on a dry basis. Controlling the content of the above components within the preferred range can make the resulting catalytic cracking catalyst have better physicochemical properties and reaction performance.
  • the cracking active components and the high specific heat capacity matrix material are in the same particle, that is, in the same catalytic cracking catalyst
  • the particles contain the cracking active component, high specific heat capacity matrix material, clay and binder.
  • the high specific heat capacity matrix material does not contain boron compounds. Based on the weight of the high specific heat capacity matrix material, the high specific heat capacity matrix material contains 5-95 wt % alumina based on Al 2 O 3 and 5-95 wt % manganese oxide based on MnO 2 , such as the The high specific heat capacity matrix material is mainly composed of 15-70% by weight or 20-65% by weight or 30-61% by weight of manganese oxide and 30-85% by weight or 35-80% by weight or 39-70% by weight of alumina .
  • the specific surface area of the high specific heat capacity matrix material can be 180-300m 2 ⁇ g -1 , such as 200-250m 2 ⁇ g -1 or 220-245m 2 ⁇ g -1 ; the pore volume of the high specific heat capacity matrix material is 0.35 -0.75, such as 0.4-0.65 cm 3 ⁇ g -1 ; the average pore diameter of the high specific heat capacity matrix material is 5-13 nm, such as 6-11 nm.
  • the high specific heat capacity matrix material may or may not contain a boron compound.
  • the high specific heat capacity matrix material provided by the present invention (referred to as the matrix material) contains a boron compound, which can have better anti-metal pollution performance than the high specific heat capacity matrix material without boron compound.
  • the boron compound in the high specific heat capacity matrix material, is boron nitride, and its specific heat capacity is 1.3-2.0J/(g ⁇ K), for example, 1.35-1.95J/(g ⁇ K) or 1.51-1.95J/(g ⁇ K).
  • the anhydrous chemical expression of the high specific heat capacity host material in terms of weight ratio can be expressed as (5-94.5)Al 2 O 3 ⁇ (5-94.5)MnO 2 ⁇ (0.5-40)BN, for example, it can be (20- 80) Al 2 O 3 ⁇ (15-75)MnO 2 ⁇ (5-30)BN.
  • the high specific heat capacity matrix material contains 5-94.5 wt % alumina, 5-94.5 wt % manganese oxide calculated as MnO 2 and as well as dry basis more than 0 and not more than 40% by weight such as 0.5-35% by weight of boron nitride; more preferably, the high specific heat capacity matrix material contains 15-80% by weight of alumina, 15-70% by weight of manganese oxide and 5- 30 wt% boron nitride; more preferably, the high specific heat capacity matrix material contains 19-74 wt% alumina, 14-66 wt% manganese oxide and 8-26 wt% boron nitride.
  • the high specific heat capacity matrix material contains boron nitride, which can improve the wear resistance of the catalyst.
  • the specific surface area of the high specific heat capacity matrix material is 150-350 m 2 ⁇ g -1 , for example, 180-300 m 2 ⁇ g -1 or 200-250 m 2 ⁇ g -1 or 220-245m 2 ⁇ g -1
  • the pore volume of the high specific heat capacity matrix material is 0.35-0.75, for example, 0.4-0.65cm 3 ⁇ g -1 or 0.45-0.75 or 0.5-0.7cm 3 ⁇ g -1
  • the high The average pore diameter of the specific heat capacity matrix material is 3-20 nm, eg, 4-18 nm or 5-15 nm or 6-13 nm or 6-8.5 nm, preferably 5-13 nm or 6-11 nm.
  • the second embodiment of the catalytic cracking catalyst of the present invention a preparation method of the matrix material, comprises the following steps:
  • step (3) mixing the product obtained in step (1), the product obtained in step (2), and boron nitride, and aging at room temperature to 120° C. for 4-72 hours; and optionally,
  • step (3) Washing the product obtained in step (3) with water, preferably, the washing makes the washing liquid after washing neutral (neutrality refers to a pH value of 6.5-7.5), for example, washing with deionized water until after washing The deionized water is neutralized, dried, and calcined to obtain a matrix material with high specific heat capacity.
  • neutrality refers to a pH value of 6.5-7.5
  • the optional range of the alkaline solution in step (1) is wide.
  • the alkaline solution is an alkaline aqueous solution containing at least one of CO 3 2- , HCO 3 2- and OH- , more preferably, the alkaline aqueous solution includes ammonium bicarbonate, ammonium carbonate, sodium hydroxide, hydrogen An aqueous solution of one or more of potassium oxide, or a mixed solution of one or more of ammonium carbonate, sodium hydroxide, potassium hydroxide and ammonia water.
  • the total concentration of alkali in the alkali solution is 0.1-1 mol/L.
  • the concentration of CO 3 2- is 0-0.6 mol/L, such as 0.3-0.5 mol/L; the concentration of OH- is 0-0.5 mol/L, such as 0.2-0.35mol/L, the concentration of HCO 3 2- is 0-1.0mol/L, for example, 0.4-1.0mol/L.
  • the pH value of step (1) gel formation is preferably 8-11, such as 8.5-11 or 9-10.
  • the types of the aluminum sources can be selected in a wide range, and water-soluble aluminum sources that can dissolve in water can be used for
  • the aluminum source may be selected from one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
  • a manganese salt solution with a specific pH value is mixed with urea to form a mixture, and the manganese salt solution is mixed with urea to form a mixture.
  • the pH value is 3-7, preferably 5-7.
  • the method for mixing described in step (2) comprises: adding urea to the manganese salt solution, stirring at room temperature for 40- For 60 minutes, the molar ratio of urea and manganese ions is preferably between 2-4.
  • the manganese salt solution can be selected from an aqueous solution of a water-soluble manganese salt, and/or a salt solution formed by contacting a water-soluble manganese salt, manganese oxide, and/or manganese hydroxide with an acid.
  • the optional range of the type of the manganese salt is wide, and all water-soluble manganese salts that can dissolve in water can be used in the present invention, and the manganese salt is one or more of manganese nitrate, manganese sulfate or manganese chloride, etc. .
  • Manganese salt solutions can also be prepared by contacting manganese oxides and/or manganese hydroxides and/or water-soluble manganese salts, such as manganese monoxide, manganese tetroxide, manganese One or more of manganese oxide, such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, preferably one or more of hydrochloric acid, sulfuric acid, and nitric acid.
  • manganese oxides and/or manganese hydroxides and/or water-soluble manganese salts such as manganese monoxide, manganese tetroxide, manganese
  • manganese oxide such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, preferably one or more of hydrochloric acid, sulfuric acid, and nitric acid.
  • the product obtained in the step (1) in the step (3) is calculated as Al 2 O 3
  • the step (2) The obtained product is calculated as MnO 2 and the ratio of boron nitride by weight on a dry basis is (5-95) Al 2 O 3 : (5-95) MnO 2 : (0.5-40) BN, for example, (20-80 ) Al 2 O 3 : (15-75) MnO 2 : (5-30) BN.
  • the amount of the product obtained in step (1), the product obtained in step (2) and boron nitride is such that the prepared matrix material contains 5-94.5% by weight, such as 15-80% by weight or 19-74 wt % or 20-80 wt % or 19-60 wt % alumina, 5-94.5 wt % as MnO 2 for example 15-75 wt % or 10-70 wt % or 14-66 wt % or 19 - 66 wt % manganese oxide and and on a dry basis greater than 0 and not more than 40 wt % eg 0.5-35 wt % or 5-30 wt % or 8-26 wt % boron nitride.
  • the prepared matrix material contains 5-94.5% by weight, such as 15-80% by weight or 19-74 wt % or 20-80 wt % or 19-60 wt % alumina, 5-94.5 wt % as MnO
  • the optional range of the aging conditions in step (3) is wide (for example, the aging temperature is room temperature) To 120 ° C, the aging time is 4-72 hours), preferably, the aging conditions described in the step (3) include: the aging temperature is 60-100 ° C, the aging time is 12-36 hours, and the aging is performed under stirring. . There is no special requirement for the stirring method, for example, the stirring speed can be 50-300 rpm.
  • the boron nitride in the preparation method of the high specific heat capacity matrix material, can be selected from hexagonal boron nitride (h-BN), cubic boron nitride (c -BN), one or more of rhombohedral boron nitride (r-BN) and wurtzite boron nitride (w-BN).
  • h-BN hexagonal boron nitride
  • c -BN cubic boron nitride
  • r-BN rhombohedral boron nitride
  • w-BN wurtzite boron nitride
  • the optional ranges of the drying conditions and calcination conditions in step (4) are wide.
  • the drying and roasting methods can be carried out with reference to the prior art, and the present invention has no special requirements for this.
  • the drying conditions in step (4) include: drying at 100-150°C for 6-24 hours; the roasting conditions in step (4) include: roasting at 550-800°C, such as 550-750°C for 4- 8 hours.
  • the boron compound in the high specific heat capacity matrix material, is boron oxide, and its specific heat capacity is 1.3-2.0J/(g ⁇ K), for example, 1.35-1.95J /(g ⁇ K) or 1.51-1.95J/(g ⁇ K),
  • the composition expression of the anhydrous compound of the mesoporous matrix material with high specific heat capacity provided by the present invention is (5-94.5)Al 2 O in terms of oxide weight ratio 3 ⁇ (5-94.5) MnO2 ⁇ (0.5-10)B2O3, for example (20-80) Al2O3 ⁇ (15-75) MnO2 ⁇ (0.5-10 ) B2O3 or It is (20-80)Al 2 O 3 ⁇ (15-75)MnO 2 ⁇ (1-8)B 2 O 3 .
  • the high specific heat capacity matrix material contains 5-94.5 wt % alumina, 5-94.5 wt % manganese oxide calculated as MnO 2 and B 2 0.5-10 wt % boron oxide based on O 3 ; more preferably, the high specific heat capacity matrix material contains 15-80 wt % alumina, 15-80 wt % manganese oxide based on MnO 2 and B 2 O 0.8-8% by weight of boron oxide based on 3 or said high specific heat capacity matrix material containing 20-62% by weight of alumina, 34-72% by weight of manganese oxide based on MnO 2 and 2-8% based on B 2 O 3 wt% boron oxide.
  • the high specific heat capacity matrix material has a specific surface area of 300-500m 2 /g such as 310-370m 2 /g or 330-370m 2 /g, and a pore volume of 0.5-1.5cm 3 /g such as 0.7-1.4cm 3 / g or 0.6-1.3 cm 3 /g or 0.7-1.2 cm 3 /g.
  • the matrix material is a mesoporous matrix material with an average pore diameter of 3-20 nm, such as 5-18 nm or 8-18 nm or 7-15 nm or 8-14 nm or 10-15 nm or 10-13 nm.
  • the boron compound in the high specific heat capacity matrix material, is boron oxide, which can have higher pore volume and specific surface area, and the introduction of boron oxide modulates the matrix Acidity, improve matrix pre-cracking ability, as matrix material of catalytic cracking catalyst or auxiliary agent, used in heavy oil catalytic cracking, can reduce the particle temperature during catalytic cracking catalyst regeneration, slow down the collapse of molecular sieve, improve the activity of the catalyst and the ability to resist metal pollution And heavy oil conversion ability, reduce the coke selectivity of the catalyst, so that the catalyst fluidization performance is good.
  • a preparation method of the high specific heat capacity matrix material comprises the following steps:
  • step (3) mixing the product obtained in step (1) and the product obtained in step (2), and ageing; for example, ageing at room temperature to 120° C. for 4-72 hours; mixing the ageing solid product with boron oxide
  • the source is mixed or mixed with the boron oxide source after the aging solid product is washed, and optionally also reacts; wherein the boron oxide source charging amount in terms of B 2 O 3 and the high specific heat capacity matrix material weight ratio in terms of dry basis are: (0.005-0.1): 1;
  • step (3) the solid precipitate obtained in step (3) (or called solid product) is directly dried, calcined, or the solid precipitate in step (3) is washed and then dried and calcined; for the washing, step (3) can be treated with water.
  • the solid product is washed, for example, it can be washed with water to make the washed water neutral.
  • the prepared matrix material in the method for preparing the high specific heat capacity matrix material, not only has a higher specific heat capacity than other methods to obtain the high specific heat capacity matrix material within the scope of the present invention , it can also have a higher average pore size, a higher specific surface area, and a higher pore volume. It can be used for catalytic cracking of heavy oil with high metal content, especially high iron content, with higher liquid product yield and lower dryness. Gas and coke yields. Compared with the catalyst using the high specific heat capacity matrix material without boron oxide, it can have higher heavy oil conversion activity and can have higher gasoline yield.
  • the optional range of the alkaline solution in step (1) is wide, preferably, in step (1)
  • the alkaline solution is an alkaline aqueous solution containing at least one of HCO 3 2- , CO 3 2- and OH- , and the alkaline aqueous solution preferably includes ammonium bicarbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide
  • ammonium bicarbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide One or more aqueous solutions of ammonium bicarbonate, ammonium carbonate, sodium hydroxide, potassium hydroxide and ammonia water.
  • the total concentration of alkali in the alkali solution is 0.1-1 mol/L.
  • the concentration of CO 3 2- is 0-0.6mol/L, such as 0.3-0.5mol/L; the concentration of OH- is preferably 0-0.5mol/L, such as 0.2-0.35mol /L, the concentration of HCO 3 2- is 0-1.0 mol/L, for example, 0.4-1.0 mol/L.
  • concentration of CO 3 2- is 0-0.6mol/L, such as 0.3-0.5mol/L; the concentration of OH- is preferably 0-0.5mol/L, such as 0.2-0.35mol /L, the concentration of HCO 3 2- is 0-1.0 mol/L, for example, 0.4-1.0 mol/L.
  • ammonia water it is assumed that the ammonia water is completely ionized, and the required addition amount of ammonia water can be calculated according to the calculated hydroxide radicals.
  • the pH value of the gel obtained by gel formation is preferably 9-11 or 10-11.
  • the optional range of the types of the aluminum sources is wide, and the water-soluble aluminum sources that can dissolve in water can be used for
  • the soluble aluminum salt can be selected from one or more of aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride, etc., preferably one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, etc. variety.
  • the manganese salt solution in step (2) can be selected from an aqueous solution of a water-soluble manganese salt, and/or a water-soluble manganese salt, manganese oxide, and/or manganese hydroxide in contact with acid; the pH value of the manganese salt solution is 3-7, preferably 5-7.
  • the mixture is stirred at room temperature for 40-60 minutes, and the molar ratio of urea and manganese ions is between 2-4.
  • the manganese salt solution in step (2) can be selected from the aqueous solution of water-soluble manganese salt and/or the salt solution formed by manganese oxide, manganese hydroxide and/or water-soluble manganese salt in contact with acid.
  • the optional range of the type of the manganese salt is wide, and all water-soluble manganese salts that can be dissolved in water can be used in the present invention, such as manganese nitrate, manganese sulfate, manganese phosphate or manganese chloride. one or more.
  • the manganese salt solution can also be prepared by contacting water-soluble manganese salts, manganese oxides and/or manganese hydroxides, such as manganese monoxide, manganese tetraoxide, manganese One or more of manganese oxide, such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid, preferably one or more of hydrochloric acid, sulfuric acid, and nitric acid.
  • the optional range of the aging conditions in step (3) is wide (for example, the aging temperature is room temperature) to 120 ° C, the aging time is 4-72 hours), preferably, the aging conditions described in step (3) include: the aging temperature is 60-100 ° C, stirring and aging, and the aging time is 12-36 hours .
  • the stirring method is the existing method, for example, the stirring speed is 50-300 rev/min.
  • the aged product is filtered or washed after filtration to obtain aged solid product.
  • H 2 O 1: 5-30.
  • the aged solid product in the preparation method of the high specific heat capacity matrix material, is contacted with a boron source, and the contact treatment method can be various.
  • the ageing product can be filtered to obtain a filter cake, that is, the ageing solid product is directly mixed with the boron source or the ageing solid product obtained after washing the filter cake obtained by filtration is mixed with the boron source; preferably, the formed mixture is also carried out for a period of time. For example, stirring or standing for 0.2-5 hours at room temperature to 90 °C.
  • One embodiment mixing and beating the aged solid product with water, wherein the weight ratio of the aged solid product (on a dry basis):H 2 O is 1:(5-20), and then adding the boron source to the above-mentioned In the slurry, stand or stir at room temperature to 90° C. for 0.2-5 hours, preferably 0.5-3 hours, and filter to obtain a solid precipitate. It is also possible to mix the aged solid product or the washed aged solid product with the boron source in proportion, and grind uniformly to obtain a solid precipitate.
  • the boron oxide source is preferably a substance that can obtain boron oxide after calcination, such as ammonium borate, ammonium hydrogen borate or one or more of boric acid.
  • the product obtained in the step (1) in the step (3) is calculated as Al 2 O 3 , and the step (2)
  • the weight and dosage ratio of the obtained product in terms of MnO 2 and the boron source in terms of B 2 O 3 is (5-94.5) Al 2 O 3 : (5-94.5) MnO 2 : (0.5-10) B 2 O 3 , for example, (20-80) Al 2 O 3 : (15-75) MnO 2 : (1-8) B 2 O 3 .
  • the high specific heat capacity matrix material contains 5-94.5 wt % such as 15-80 wt % or 20-75 wt % or 20-62 wt % of alumina, 5-94.5 wt % such as 15- 80 wt % or 22-72 wt % or 30-72 wt % manganese oxide as MnO 2 and 0.5-10 wt % or 0.8-8 wt % or 2-8 wt % boron oxide as B 2 O 3 .
  • the solid precipitate obtained in step (3) is directly dried and roasted, or washed and then dried and roasting.
  • the washing can be washed with water, for example, it can be mixed with water and washed with water, or washed with water.
  • the solid precipitate after washing is neutral, that is, the pH value of the water after contacting with water is 6.5-7.5.
  • the drying and roasting methods can be carried out with reference to the prior art, and the optional range is wide, and the present invention has no special requirements for this.
  • the drying can be carried out at 100-150°C for 12-24 hours; and the calcination can be carried out at 550-800°C, such as 550-750°C, for 4-8 hours.
  • the cracking active component contains Y-type molecular sieve.
  • the types of the Y-type molecular sieves may include various types of Y-type molecular sieves in which NaY is ion-modified or ultra-stable, and the ion-modification includes rare earth ions, alkaline earth metal ions, transition metal ions, phosphorus modification, etc.
  • Ultra-stable modification includes hydrothermal ultra-stable, gas-phase ultra-stable, chemical ultra-stable, etc.
  • it can be Y-type molecular sieve containing rare earth such as REHY molecular sieve, Y-type molecular sieve containing phosphorus and rare earth such as DOSY molecular sieve, ultra-stable Y molecular sieve
  • rare earth such as REHY molecular sieve
  • Y-type molecular sieve containing phosphorus and rare earth such as DOSY molecular sieve
  • ultra-stable Y molecular sieve For example, one or more of DASY molecular sieves, ultrastable Y molecular sieves containing phosphorus and/or rare earth, and the like.
  • the cracking active component also contains a second molecular sieve, such as other faujasite zeolite, Beta zeolite, MFI molecular sieve (such as ZRP-1 molecular sieve) and one or more of mordenite.
  • a second molecular sieve such as other faujasite zeolite, Beta zeolite, MFI molecular sieve (such as ZRP-1 molecular sieve) and one or more of mordenite.
  • the content of the Y-type molecular sieve may be more than 75% by weight, preferably more than 90% by weight, more preferably more than 95% by weight; the content of the second molecular sieve
  • the content may be 25 wt% or less, preferably 10 wt% or less, more preferably 5 wt% or less.
  • the clay can be various existing clays that can be used in the catalytic cracking catalyst, for example, can be selected from kaolin, halloysite, montmorillonite, diatomite, Eello One or more of stone, soapstone, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
  • the binder can be various existing binders that can be used in the catalytic cracking catalyst, for example, can be selected from silica sol, alumina sol and pseudo-boehmite one or more of them.
  • the catalytic cracking catalyst may also contain additional rare earths.
  • the additional rare earth may be formed by additionally adding rare earth chloride during the preparation of the catalytic cracking catalyst.
  • the additional rare earth is usually present in the form of rare earth oxide (RE 2 O 3 ). Based on the dry weight of the catalytic cracking catalyst, the content of the additional rare earth in terms of rare earth oxide may be 0-3 wt %, preferably 0.5-2 wt %.
  • the rare earth element in the added rare earth refers to various conventional rare earth elements involved in the field of catalytic cracking catalysts, such as lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium and the like.
  • the preparation method of the catalytic cracking catalyst provided by the present invention comprises the steps of mixing and beating cracking active components, high specific heat capacity matrix material, clay and binder, and then performing spray drying, washing, filtering and drying in sequence.
  • the preparation method of the catalytic cracking catalyst provided by the present invention further comprises combining the rare earth chloride with the cracking active component, a high specific heat capacity matrix material, clay and a binder The pulp is mixed together and then spray dried, washed, filtered and dried in sequence.
  • the active components for cracking, the high specific heat capacity matrix material, the clay and the binder and the rare earth chloride optionally contained are mixed and slurried, and the subsequent spray drying, washing, filtering and drying, the implementation methods of these procedures can be implemented by conventional methods, and their specific implementation methods are described in detail in CN1916166A, CN1098130A, CN1362472A, CN1727442A, CN1132898C and CN1727445A, which are incorporated into the present invention as refer to.
  • the preparation method of the catalytic cracking catalyst usually further comprises the step of calcining the spray-dried product.
  • the calcination conditions generally include that the calcination temperature can be 500-700° C., and the calcination time can be 1-4 hours.
  • the present invention also provides the application of the above catalytic cracking catalyst in the catalytic cracking of heavy oil.
  • the application method of the catalytic cracking catalyst in the catalytic cracking of heavy oil provided by the present invention includes the step of contacting and reacting the catalytic cracking catalyst with a heavy oil, such as vacuum residue, vacuum gas oil, and atmospheric residue.
  • a heavy oil such as vacuum residue, vacuum gas oil, and atmospheric residue.
  • the reaction conditions of the contact reaction include: the reaction temperature is 480-530° C., the ratio of agent to oil (weight ratio) is 3-10, and the reaction time is 0.1-5 seconds.
  • the heavy oil satisfies one or more or all of the following conditions: (a) specific gravity (20°C) 0.82-0.95, preferably greater than 0.91 and not greater than 0.95; (b) carbon content 85 wt% -89wt%; (c) hydrogen content of 10wt% to 13wt%; (d) sulfur content of 0.1% to 4wt%; (e) solidification temperature of -10 to 40°C.
  • the present invention provides the following technical solutions:
  • a high specific heat capacity matrix material comprising at least 5% by weight of manganese oxide, said high specific heat capacity matrix material having a specific heat capacity of 1.3-2.0 J/(g ⁇ K) at a temperature of 1000K.
  • the high specific heat capacity matrix material contains 5-95% by weight of Al 2 O 3 , such as 19.6-74.8% by weight of alumina, 5-95% by weight, for example 15.3-71.8% by weight of manganese oxide based on MnO2 , and 0-40% by weight, 0-25.2% by weight of a boron compound on a dry basis; for example the high specific heat capacity matrix material contains Al2 19.6-74.8 wt% alumina based on O3 , 15.3-71.8 wt% manganese oxide based on MnO2 , and 0-25.2 wt% boron compound on a dry basis.
  • the boron compound is boron nitride and/or boron oxide.
  • the average pore diameter of the high specific heat capacity matrix material is 3-20 nm, such as 5-15 nm, such as 6.4-13.6 nm.
  • the XRD pattern of the high specific heat capacity host material at 2 ⁇ angle is 18 ⁇ 0.5° and 2 ⁇ angle is the intensity of the peak at 37 ⁇ 0.5°
  • the ratio is 1:(3-10).
  • the mixing of the aluminum source and the alkali to form a gel comprises: mixing the aluminum source solution and the alkali solution, and the forming temperature is from room temperature to 85°C, and the pH value is 7- 11 colloids.
  • the aluminum source is selected from aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride and mixtures thereof;
  • the The base is selected from the group consisting of water-soluble carbonates, water-soluble bicarbonates, water-soluble hydroxides, and mixtures thereof.
  • the solution of the alkali is selected from one or more of containing CO 3 2- , HCO 3 - and OH -
  • the alkaline aqueous solution the concentration of CO 3 2- in the alkali solution is 0-0.6mol/L, the concentration of OH- is 0-0.5mol/L , the concentration of HCO 3- is 0-1mol/L, the premise is is that the sum of the concentration of CO 3 2- , the concentration of OH- , and the concentration of HCO 3- is not zero, where the concentration of CO 3 2- , the concentration of OH- , and the concentration of HCO 3- are determined by applying the It is obtained by dividing the molar amount (mol) of the anion group in the base of the alkaline aqueous solution by the volume (L) of the alkaline aqueous solution.
  • the manganese concentration of manganese salt in the salt solution can be 50-500 g ⁇ L -1 in terms of MnO 2 .
  • step (2) urea is added to the manganese salt solution, and then stirred at room temperature for 30-60 minutes to obtain Manganese source solution.
  • the catalytic cracking catalyst according to technical scheme 16 wherein the boron nitride is one or more of hexagonal boron nitride, cubic boron nitride, rhombohedral boron nitride and wurtzite boron nitride.
  • the boron oxide precursor is one or more of ammonium borate, ammonium hydrogen borate and boric acid.
  • step (3) after mixing the aluminum-containing colloid and the manganese source solution, the process of ageing is also included, and the The aging temperature is from room temperature to 120 ° C, the aging time is 4-72 hours, and the aging is performed under stirring or standing for aging; preferably, the aging is performed under stirring, and the aging temperature is 60-100 ° C. Aging time is 12-36 hours.
  • step (3) makes aluminum-containing colloid, manganese source solution, and boron compound to form
  • the method of the mixture is as follows: the aluminum-containing colloid, the manganese source solution and the boron compound are mixed and aged.
  • the boron compound is boron oxide and/or a precursor of boron oxide
  • the aluminum-containing compound is The colloid, the manganese source solution, and the boron compound form the mixture as follows: the aluminum-containing colloid, the manganese source solution are mixed, aged, optionally washed, and then mixed with the boron compound.
  • a catalytic cracking catalyst wherein the catalytic cracking catalyst contains a cracking active component comprising Y-type molecular sieve, the high specific heat capacity matrix material described in any one of the foregoing technical solutions 1-7 or by the foregoing technical solutions 8-20
  • the high specific heat capacity matrix material, clay and binder obtained by any one of the preparation methods.
  • the catalytic cracking catalyst according to the aforementioned technical solution 21, wherein, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 1-60 wt % of cracking active components, 1-50 wt % high specific heat capacity matrix material, 1-70 wt % clay and 1-70 wt % binder, or, based on the total weight of the catalytic cracking catalyst, the catalytic cracking catalyst contains 10-50 wt % Cracking active components, 5-40 wt % high specific heat capacity matrix material, 10-60 wt % clay and 10-60 wt % binder, wherein the mass of the catalytic cracking catalyst is 100 wt %.
  • the catalytic cracking catalyst according to any one of technical solutions 21 to the previous technical solution, wherein the cracking active component also contains a second molecular sieve, and the second molecular sieve is faujasite, Beta zeolite, One or more of MFI structured molecular sieves and mordenite.
  • the method comprises mixing and beating the cracking active component, the high specific heat capacity matrix material, the clay and the binder, and then carrying out successively. Spray dried, calcined, washed, filtered and dried.
  • Hydrochloric acid is produced by Beijing Chemical Plant, chemically pure, and the concentration is 36% by weight;
  • Soda water glass is commercially available, the SiO2 concentration is 26.0 wt%, and the modulus is 3.2;
  • Kaolin is a product of Suzhou Kaolin Company, and the solid content is 74.0% by weight;
  • the pseudo-boehmite is an industrial product of Shandong Aluminum Factory, with a solid content of 62.0% by weight;
  • the aluminum sol is a product of Sinopec Catalyst Qilu Branch, and the Al 2 O 3 content is 21.5% by weight;
  • DASY molecular sieve (solid content 92.0 wt%, RE 2 O 3 1.8 wt %, Na 2 O 1.0 wt %, crystallinity 60%), ZRP-1 molecular sieve (solid content 97.8 wt %, Na 2 O 1.1 wt%, crystallinity 70%), REHY molecular sieve (solid content 88.0 wt%, RE 2 O 3 5.0 wt %, Na 2 O 0.9 wt %, crystallinity 65%), Beta molecular sieve (solid content 95.2 wt %) %, Na 2 O 1.2 wt %, crystallinity 60%), DOSY molecular sieve (solid content 93.5 wt %, RE 2 O 3 8.0 wt %, Na 2 O 0.8 wt %, crystallinity 80%), HSY Molecular sieves (solid content 91.5 wt%, RE 2 O 3 10.5 wt %, Na 2 O 0.9 wt
  • Rare earth chloride was purchased from Baotou Steel Rare Earth High-Tech Co., Ltd., and the rare earth elements were La and Ce.
  • the catalyst oil ratio refers to the mass ratio of the catalyst to the feedstock oil.
  • ppm is ppm by weight.
  • the BN used is hexagonal boron nitride.
  • the contents of Al 2 O 3 , MnO 2 , B, N, and Fe in the samples were determined by X-ray fluorescence method (see "Petrochemical Analysis Method (RIPP Experimental Method)", edited by Yang Cuiding et al. Science Press, 1990).
  • the phase of the sample was determined by X-ray diffraction.
  • the specific surface area, pore volume, and average pore diameter of the samples were measured by the low-temperature nitrogen adsorption-desorption method, and the pore size distribution was calculated by the BJH method.
  • This preparation example illustrates the preparation process of the high specific heat capacity matrix material provided by the present invention.
  • the Al 2 (SO 4 ) 3 solution with a concentration of 300gAl 2 O 3 /L and the ammonium carbonate solution with a CO 3 2- concentration of 0.10mol/L were mixed into a gel at 20° C.
  • the pH value of the obtained colloid was 7.5, and a slurry A was obtained .
  • Add hydrochloric acid to the MnCl 2 solution with a concentration of 450 gMnO 2 /L, control pH 3.5, then add urea to the solution, the urea to manganese ion molar ratio is 2, and stir at room temperature for 30 minutes to obtain solution B.
  • AM-1 high specific heat capacity matrix material provided by the present invention
  • the X-ray diffraction pattern of AM-1 is shown in Figure 1, in which there are characteristic peaks at 2 ⁇ angles of 18 ⁇ 0.5° and 2 ⁇ angles of 37 ⁇ 0.5°, and the intensity ratio (I 1 /I 2 ) of the two is 1 : 5.2; its elemental analytical chemical composition expression (by weight) is 60.5MnO 2 ⁇ 39.5Al 2 O 3 ; its specific heat capacity is 1.36J/(g ⁇ K), its specific surface area is 238m 2 /g, and its pore volume is 0.38cm 3 /g , the average pore size is 6.4nm.
  • Preparation Examples 2-4 are used to illustrate the preparation process of the high specific heat capacity matrix material provided by the present invention.
  • the high specific heat capacity matrix materials AM-2 to AM-4 were prepared according to the method of Preparation Example 1, except that the ratio of raw materials, preparation condition parameters, elemental composition of products, specific heat capacity, specific surface area, pore volume and average pore diameter are listed in Table 1 , wherein solution B is added to slurry A, then boron nitride is added, and the aging is performed.
  • Example 5 is used to illustrate the preparation process of the high specific heat capacity matrix material provided by the present invention.
  • Al(NO 3 ) 3 solution with a concentration of 350gAl 2 O 3 /L and a solution with a CO 3 2- concentration of 0.1mol/L (ammonium carbonate) and an OH - concentration of 0.1mol/L (ammonia) at a temperature of 25 °C
  • the mixture was mixed to form a gel, and the pH value was controlled to be 10.5 to obtain slurry A.
  • Mix Mn 3 O 4 with hydrochloric acid and water to obtain a manganese chloride solution with a concentration of 116.5gMnO 2 /L, control pH 6, then add urea to the solution, the urea to manganese ion molar ratio is 3, and stir at room temperature for 40 minutes to obtain solution B.
  • the X-ray diffraction pattern of AM-5 is the same as Figure 1, in which there are characteristic peaks at the 2 ⁇ angle of 18 ⁇ 0.5° and the 2 ⁇ angle of 37 ⁇ 0.5°, and the intensity ratio of the two is 1:6.6; the expression of the chemical composition of AM-5
  • the formula is 20.6MnO 2 ⁇ 59.4Al 2 O 3 ⁇ 19.4BN by weight; the specific heat capacity is 1.48J/(g ⁇ K), the specific surface area is 243m 2 /g, the pore volume is 0.46cm 3 /g, and the average pore diameter is 7.6nm.
  • Preparation Example 6 is used to illustrate the preparation process of the high specific heat capacity matrix material provided by the present invention.
  • the matrix material AM-6 was prepared according to the method of Preparation Example 5.
  • the composition, specific heat capacity, specific surface area, pore volume and average pore diameter of different raw material ratios and preparation condition parameters are listed in Table 1.
  • the CO 3 2- concentration was 0.2 mol/L, and the OH- concentration was 0.15 mol/L.
  • the X-ray diffraction patterns of AM-2 to AM-6 are shown in FIG. 1, with peaks at 2 ⁇ angles of 18 ⁇ 0.5° and 2 ⁇ angles of 37 ⁇ 0.5°.
  • Al(NO 3 ) 3 solution with a concentration of 350gAl 2 O 3 /L and a manganese nitrate solution with a concentration of 525gMnO 2 /L were prepared with deionized water, and mixed uniformly to obtain solution A.
  • Prepare ammonium bicarbonate solution, control pH 10.0, record as solution B.
  • the solution A and the solution B are mixed to obtain the mother liquor C, and the pH of the mother liquor C is controlled to be 8-9 by controlling the addition of the solution B during the mixing process.
  • DAM-1 X-ray diffraction pattern of DAM-1, in which there are characteristic peaks at 2 ⁇ angles of 18 ⁇ 0.5° and 2 ⁇ angles of 37 ⁇ 0.5°, and the intensity ratio of the two is 1:1.9; the expression of elemental analysis chemical composition of DAM-1
  • the formula is 60.6MnO 2 ⁇ 39.4Al 2 O 3 ; the specific heat capacity is 0.62 J/(g ⁇ K), the specific surface area is 224 m 2 /g, the pore volume is 0.31 cm 3 /g, and the average pore diameter is 5.5 nm.
  • a solution of Al 2 (SO 4 ) 3 with a concentration of 350 g Al 2 O 3 /L was mixed with ammonium carbonate to form a gel, and the pH was controlled to be 10.0 to obtain slurry A.
  • a MnSO 4 solution with a concentration of 209.7 g MnO 2 /L was added to the slurry A, and stirred at room temperature for 30 minutes to obtain a slurry B.
  • 95.4g of boron nitride (solid content of 80% by weight) was added to slurry B, aged at 80°C for 24 hours, after the temperature of the system dropped to room temperature, rinsed with deionized water until neutral, and dried at 120°C for 12 hours.
  • the manganese-aluminum matrix precursor was then calcined at 900° C. for 6 hours, and cooled to room temperature with the furnace to obtain a sample of the comparative matrix material, which was denoted as DAM-2.
  • the elemental analysis chemical composition expression of DAM-2 is 33.3MnO 2 ⁇ 54.7Al 2 O 3 ⁇ 11.7BN by weight; the specific heat capacity is 0.85J/(g ⁇ K), the specific surface area is 219m 2 /g, and the pore volume is 0.25cm 3 / g, The average pore diameter is 4.6 nm.
  • I 1 /I 2 is the ratio of the peak intensity at the 2 ⁇ angle of 18 ⁇ 0.5° to the peak intensity at the 2 ⁇ angle of 37 ⁇ 0.5° in the XRD pattern
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • catalytic cracking catalyst C1 contains 10% by weight of high specific heat capacity matrix material, 29% by weight of DASY molecular sieve, 28% by weight of kaolin, and 33% by weight of Al 2 O 3 binder.
  • This comparative example is used to illustrate the reference catalytic cracking catalyst and its preparation method.
  • the catalytic cracking catalyst was prepared according to the method of Example 1, except that the high specific heat capacity matrix material AM-1 prepared in Preparation Example 1 was replaced by the same weight portion of the matrix material DAM-1 prepared in Comparative Preparation Example 1 to obtain a reference Catalytic cracking catalyst CB1, wherein, based on the total weight of the reference catalytic cracking catalyst CB1, the reference catalytic cracking catalyst CB1 contains 10% by weight of comparative matrix material, 29% by weight of DASY molecular sieve, 28% by weight of DASY kaolin, 33 wt% Al 2 O 3 binder.
  • This comparative example is used to illustrate the reference catalytic cracking catalyst and its preparation method.
  • the catalytic cracking catalyst was prepared according to the method of Example 1, except that the high specific heat capacity matrix material AM-1 prepared in Preparation Example 1 was replaced by the same weight portion of matrix material DAM-2 prepared in Comparative Preparation Example 1 to obtain a reference Catalytic cracking catalyst CB2, wherein, based on the total weight of the reference catalytic cracking catalyst CB2, the reference catalytic cracking catalyst CB2 contains 10% by weight of comparative matrix material, 29% by weight of DASY molecular sieve, 28% by weight of DASY kaolin, 33 wt% Al 2 O 3 binder.
  • This comparative example is used to illustrate the reference catalytic cracking catalyst and its preparation method.
  • the catalytic cracking catalyst was prepared according to the method of Example 1, except that the high specific heat capacity matrix material AM-1 was not added, but the high specific heat capacity matrix material AM-1 was replaced with kaolin of the same dry basis weight to obtain a reference catalytic cracking catalyst CB3 , wherein, based on the total weight of the reference catalytic cracking catalyst CB3, the reference catalytic cracking catalyst CB3 contains 29% by weight of DASY molecular sieve, 38% by weight of kaolin, 33% by weight of Al 2 O 3 clay binding agent.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • the slurry (solid content of 20% by weight) of the high specific heat capacity matrix material AM-2 prepared in Preparation Example 2 was stirred for 20 minutes, and then 20 parts by weight of DASY molecular sieve on a dry basis, DASY molecular sieve on a dry basis was added to it for 20 minutes.
  • the mixed slurry of 5 parts by weight of ZRP-1 molecular sieve (solid content is 35% by weight) is continuously stirred and spray-dried to prepare a microsphere catalyst.
  • the microsphere catalyst was then calcined at 500°C for 1 hour, and then washed with (NH 4 ) 2 SO 4 solution at 60° C.
  • catalytic cracking catalyst C2 wherein the total amount of the catalytic cracking catalyst C2 Based on weight, the catalytic cracking catalyst C2 contains 30% by weight of high specific heat capacity matrix material, 20% by weight of DASY molecular sieve, 5% by weight of ZRP-1 molecular sieve, 20% by weight of kaolin, 25% by weight of Al 2 O 3 Binder.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • catalytic cracking catalyst C3 contains 20% by weight of high specific heat capacity matrix material, 15% by weight of REHY molecular sieve, 5% by weight of Beta molecular sieve, 28% by weight of kaolin, 30% by weight of Al 2 O 3 clay. Binder, 2 wt% rare earth oxide.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • catalytic cracking catalyst C4 contains 15% by weight of high specific heat capacity matrix material, 30% by weight of DOSY molecular sieve, 40% by weight of kaolin, and 15% by weight of Al 2 O 3 binder.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • hydrochloric acid 1.7L hydrochloric acid is diluted with 8.0kg decationized water, 7.7kg sodium water glass is diluted with 8.0kg decationized water, and the diluted sodium water glass is slowly added to the above-mentioned dilute hydrochloric acid solution under stirring to obtain SiO Concentration is : 7.8 wt% silica sol, pH 2.8.
  • catalytic cracking catalyst C5 contains 40% by weight of high specific heat capacity matrix material, 30% by weight of DASY molecular sieve, 10% by weight of kaolin, and 20% by weight of SiO 2 binder.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • the catalytic cracking catalyst C6 contains 15% by weight of high specific heat capacity matrix material, 30% by weight of HSY molecular sieve, 40% by weight of kaolin, and 15% by weight of Al 2 O 3 binder.
  • Examples 7-12 are used to illustrate the tests for the performance of the catalytic cracking catalyst provided by the present invention.
  • the catalytic cracking catalysts C1-C6 prepared above are respectively adopted Mitchell method to impregnate pollution iron 5000ppm, nickel 5000ppm, vanadium 5000ppm, namely take vanadium naphthenate as vanadium source, nickel naphthenate as nickel source, and iron naphthenate as iron source , toluene is used as a solvent to prepare a metal-containing solution, the catalyst is immersed in the metal-containing solution, then dried, and then calcined at about 600° C. to remove organic matter. After aging treatment at 780°C and 100% water vapor for 6 hours, the cracking performance was evaluated on a small fixed fluidized bed.
  • the evaluation process of each sample was carried out five times of reaction-regeneration cycles, that is, the same catalyst was not discharged. In this case, the feedstock oil reaction and regeneration process were continuously carried out for five times, and the result of the last reaction was taken as the evaluation result of the catalyst cracking performance.
  • the evaluation conditions of heavy oil micro-reaction are: agent-oil ratio 5 (weight ratio), sample loading 9g, reaction temperature 520 °C, WHSV 8 hours -1 , oil feeding time 70 seconds, regeneration temperature 720 °C, raw material oil is decompressed gas oil.
  • the properties of the feedstock oil are shown in Table 2. The evaluation results are listed in Table 3.
  • catalytic cracking reference agents CB1-CB3 prepared above were tested for performance in the same manner as in Examples 7-12, and the evaluation results are listed in Table 3.
  • conversion rate gasoline yield + liquefied gas yield + dry gas yield + coke yield
  • total liquid yield gasoline yield + diesel yield + liquefied gas yield
  • coke selectivity coke yield/conversion rate
  • dry gas selectivity dry gas yield/conversion rate
  • This example illustrates the preparation process of the high specific heat capacity mesoporous matrix material provided by the present invention.
  • the Al 2 (SO 4 ) 3 solution with a concentration of 350 g Al 2 O 3 /L and the ammonium carbonate solution with a CO 3 2- concentration of 0.10 mol/L were mixed at 30°C to form a gel, and the pH value was controlled to be 7.5 to obtain a slurry BA.
  • Urea was added to the MnCl 2 solution with a concentration of 145 gMnO 2 /L, the molar ratio of urea to manganese ions was 2, and the solution was stirred at room temperature for 30 minutes to obtain solution BB.
  • the elemental analysis chemical composition expression of BAM-1 is 29.7MnO 2 ⁇ 69.2Al 2 O 3 ⁇ 1.1B 2 O 3 by weight; specific heat capacity 1.3J/(g ⁇ K), specific surface area 310m 2 /g, pore volume 0.65 cm 3 /g, the average pore diameter is 8.4 nm.
  • Preparation examples B2-B4 are used to illustrate the preparation process of the high specific heat capacity mesoporous matrix material provided by the present invention.
  • the high specific heat capacity mesoporous matrix materials BAM-2 to BAM-4 were prepared according to the method of Preparation Example B1. The difference was the formulation and preparation parameters.
  • the elemental composition, specific heat capacity, specific surface area, pore volume and average pore diameter are listed in Table 4.
  • Preparation Example B5 is used to illustrate the preparation process of the high specific heat capacity mesoporous matrix material provided by the present invention.
  • the Al(NO 3 ) 3 solution with a concentration of 350gAl 2 O 3 /L, the ammonium carbonate with a CO 3 2- concentration of 0.30mol/L, and the ammonia solution with an OH - concentration of 0.1mol/L were mixed to form a gel, and the pH was controlled to be 10.5. , to obtain slurry BA.
  • Mix Mn 3 O 4 with hydrochloric acid and water to obtain a manganese chloride solution with a concentration of 201.7gMnO 2 /L, control pH 6, then add urea to the solution, the urea to manganese ion molar ratio is 3, and stir at room temperature for 40 minutes to obtain solution BB.
  • the elemental analysis chemical composition expression of BAM-5 is 34.8MnO 2 ⁇ 60.4Al 2 O 3 ⁇ 4.8B 2 O 3 by weight; specific heat capacity 1.43J/(g ⁇ K), specific surface area 338m 2 /g, pore volume 0.94 cm 3 /g, the average pore diameter is 11.1 nm.
  • Preparation Example B6 is used to illustrate the preparation process of the high specific heat capacity mesoporous matrix material provided by the present invention.
  • the matrix material BAM-6 was prepared according to the method of Preparation Example B5, except that the formula and preparation parameters were different, and its elemental composition, specific surface area, pore volume and average pore diameter were listed in Table 4.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • the catalytic cracking catalyst C19 contains 15% by weight of high specific heat capacity matrix material, 32% by weight of DASY molecular sieve, 35% by weight of kaolin, and 18% by weight of Al 2 O 3 binder.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • the slurry (solid content of 20% by weight) of the high specific heat capacity matrix material BAM-2 prepared by Preparation Example B2 was stirred for 20 minutes, and then 35 parts by weight of the REHY molecular sieve (solid content) was added to it on a dry basis. 35% by weight), continue stirring and spray drying to prepare a microsphere catalyst.
  • the catalytic cracking catalyst C20 contains 20% by weight of high specific heat capacity matrix material, 35% by weight of REHY molecular sieve, 21% by weight of kaolin, and 24% by weight of Al 2 O 3 binder.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • the catalytic cracking catalyst C21 contains 25% by weight of high specific heat capacity matrix material, 27% by weight of HSY molecular sieve, 28% by weight of kaolin, and 20% by weight of Al 2 O 3 binder.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • catalytic cracking catalyst C22 contains 10% by weight of high specific heat capacity matrix material, 28% by weight of DASY molecular sieve, 42% by weight of kaolin, and 20% by weight of Al 2 O 3 binder.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • hydrochloric acid 1.7L hydrochloric acid is diluted with 8.0kg decationized water, 7.7kg sodium water glass is diluted with 8.0kg decationized water, and the diluted sodium water glass is slowly added to the above-mentioned dilute hydrochloric acid solution under stirring to obtain SiO Concentration is : 7.8 wt% silica sol, pH 2.8.
  • catalytic cracking catalyst C23 contains 10% by weight of high specific heat capacity matrix material, 25% by weight of DASY molecular sieve, 35% by weight of kaolin, and 30% by weight of SiO 2 binder.
  • This example is used to illustrate the catalytic cracking catalyst provided by the present invention and its preparation method.
  • the catalytic cracking catalyst C24 contains 40% by weight of high specific heat capacity matrix material, 33% by weight of REHY molecular sieve, 42% by weight of kaolin, and 15% by weight of Al 2 O 3 binder.
  • Examples 25-30 are used to illustrate the tests of the performance of the catalytic cracking catalyst provided by the present invention.
  • the catalytic cracking catalysts C19-C24 prepared above were impregnated with contaminated iron 5000ppm, nickel 5000ppm and vanadium 5000ppm respectively by the Mitchell method, aged at 780 ° C and 100% water vapor for 6 hours, and the cracking performance was carried out on a small fixed fluidized bed. Evaluation, the evaluation process of each sample was carried out five times of reaction-regeneration cycle, that is, the same catalyst was continuously carried out five times of raw oil reaction and regeneration process without unloading, and the result of the last reaction was taken as the evaluation result of catalyst cracking performance. .
  • agent-oil ratio 5 weight ratio
  • sample loading 9g sample loading 9g
  • reaction temperature 520 °C reaction temperature 520 °C
  • WHSV 8 hours -1 oil feeding time 70 seconds
  • regeneration temperature 720 °C raw material oil is decompressed gas oil.
  • the properties of the feedstock oil are shown in Table 2. The evaluation results are listed in Table 5.
  • Example number 19 20 twenty one twenty two twenty three twenty four catalyst number C19 C20 C21 C22 C23 C24 Conversion rate/w% 69.32 69.57 68.81 68.45 68.37 69.18
  • Example number 19 20 twenty one twenty two twenty three twenty four Dry gas/w% 1.56 1.52 1.52 1.50 1.59 1.54 LPG/w% 12.86 13.07 12.82 12.71 12.54 12.76 Gasoline/w% 49.26 49.36 48.94 48.88 48.62 49.17 Diesel/w% 16.81 16.87 16.71 16.52 16.36 16.58 Oil slurry/w% 13.87 13.56 14.48 15.03 15.27 14.24 Coke/w% 5.64 5.62 5.53 5.36 5.62 5.71 Total liquid yield/w% 78.93 79.30 78.47 78.11 77.52 78.51 Dry gas selectivity 2.25 2.18 2.21 2.19 2.33 2.23 Coke selectivity 8.14 8.08 8.04 7.83 8.22 8.25 H 2 /CH 4 0.11 0.1 0.12 0.13 0.12 0.11
  • the catalyst provided by the invention has excellent anti-metal pollution ability, the heavy oil conversion ability is greatly improved, and the product distribution is obviously improved.
  • the selectivity of dry gas and coke can be significantly improved, the total liquid yield is increased, and the light oil yield is increased.
  • the dry gas and coke yield of the catalyst provided by the present invention is reduced, and the dry gas and coke selectivity is obviously improved.
  • the catalytic cracking catalyst provided by the present invention can exhibit better metal pollution resistance, catalytic cracking activity and dry gas and coke selectivity in the process of heavy oil catalytic cracking.
  • the catalyst provided by the invention is used for the conversion of heavy oil and can have higher total liquid yield and higher yield of gasoline and liquefied gas.
  • the boron compound is boron oxide, it can have higher gasoline yield and conversion.

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Abstract

一种催化裂化催化剂及其制备方法和应用，所述催化裂化催化剂含有裂化活性组元、高比热容基质材料、粘土和粘结剂；所述高比热容基质材料含有至少5重量％的氧化锰，其比热容为1.3-2.0J/(g·K)。所述催化裂化催化剂的制备方法包括将所述裂化活性组元、高比热容基质材料和/或其前驱物、粘土和粘结剂混合打浆，喷雾干燥、焙烧、洗涤、过滤和干燥。所述催化裂化催化剂优异的抗金属污染能力，具有较好的重油转化能力，用于重油催化裂化，具有较高的轻质油收率。

Description

一种催化裂化催化剂及其制备方法与应用 技术领域
本发明涉及一种催化裂化催化剂及其制备方法与应用。
背景技术
随着石油资源的日益短缺，原油价格不断攀升，各大炼厂通过深度加工重质油和使用劣质油来降低成本，以使效益最大化，目前催化裂化是重油加工的重要手段。
然而，劣质原油的重金属(如钒、镍)含量一般较高，尤其近年来，由于原料油的重质化、劣质化程度加重以及机会原油的加工，催化裂化催化剂金属中毒的现象日益普遍。众多研究结果表明，铁、镍等金属一旦在表面沉积就难以迁移，而且会与硅、铝、钒、钠等元素相互作用形成低熔点共熔物，使催化剂表面烧结，进而在表面形成一层2-3μm厚的致密层，堵塞反应物进入催化剂以及产物扩散的孔道，恶化产品分布。严重的金属污染会导致催化剂流化性能变差，活性中心的可接近性降低，催化剂选择性变差，干气、焦炭产率增加等突出问题，有的装置甚至面临停工的风险。
为了减少油品中的金属对催化裂化的影响，现有技术中采用添加金属捕集组分以消除或弱化其影响，然而，由于大部分金属捕集组分同时也会对催化剂的活性造成影响，因而大多以单独助剂的形式引入到催化剂系统，当直接引入催化剂中时，可能会对催化剂性能造成某些不利影响，添加受到严格限制。
CN101939095A公开一种分子筛催化剂及其制备方法以在高温高湿的恶劣环境中通过催化裂解石脑油而制备轻质烯烃。具体来说，所述催化剂是通过对混合浆料进行喷雾干燥并煅烧而制备的，其中在所述混合浆料中，将0.01-5.0重量％的MnO 2和1-15重量％的P 2O 5同时嵌入到由沸石、粘土和无机复合物构成的催化剂中。根据该发明，将锰和磷酸盐同时嵌入到沸石和无机复合物中的方法可用于提高所获得的球形催化剂的热稳定性，并且通过保护沸石的酸性部位而提高烃类(例如石脑油)裂解后的烯烃产量。为了合成所需的催化剂，重要的步骤是Mn、P、沸石和无机复合物的混合比例和混合顺序。将锰和磷以溶解的形式混合在催化剂浆料中，对催化剂的改进效果非常有限，该催 化剂主要用于石脑油转化，没有涉及如何改善其重油转化性能。
发明内容
本发明要解决的技术问题是提供一种新的具有较好的重油转化能力和抗金属污染能力的催化裂化催化剂。本发明要解决的另外技术问题是提供所述催化裂化催化剂的制备方法以及所述催化裂化催化剂在重油催化裂化中的应用。
本发明提供一种催化裂化催化剂，其中，所述催化裂化催化剂含有裂化活性组元、高比热容基质材料、粘土和粘结剂；所述高比热容基质材料含有以MnO 2计至少5重量％的氧化锰，所述高比热容基质材料在温度为1000K的比热容为1.3-2.0J/(g·K)，所述裂化活性组元包括Y型分子筛。
优选的，所述高比热容基质材料含有以Al 2O 3计5-95重量％的氧化铝，以MnO 2计5-95重量％氧化锰以及以干基计0-40重量％的硼化合物。
优选的，所述的高比热容基质材料中，所述的硼化合物为氮化硼和/或氧化硼。
优选的，所述高比热容基质材料的比表面积为150-500m 2·g -1。
优选的，所述高比热容基质材料的孔体积为0.3-1.5cm 3·g -1。
优选的，所述高比热容基质材料的平均孔直径为3-20nm。
优选的，所述高比热容基质材料的XRD图谱，在2θ角为18±0.5°和2θ角为37±0.5°处峰的强度比为1:(3-10)。
所述高比热容基质材料，可以按照包括下述步骤的制备方法制备得到：
(1)使铝源与碱混合成胶，得到含铝胶体，所得含铝胶体的pH值为7-11；
(2)使pH值为3-7的锰盐溶液与尿素混合，得到锰源溶液；
(3)使含铝胶体、锰源溶液、任选的硼化合物形成混合物；和任选的
(4)洗涤和/或干燥和/或焙烧。
所述高比热容基质材料制备步骤(1)中，所述使铝源与碱混合成胶包括：将铝源溶液、碱的溶液混合，形成温度为室温至85℃、pH值为7-11的胶体。
所述铝源溶液中氧化铝的浓度为150-350gAl 2O 3/L，碱的溶液中碱的浓度为0.1-1mol/L。所述的铝源选自硝酸铝、硫酸铝、磷酸铝和氯化铝等中的一种或多种；所述的碱为(可)溶于水的碳酸盐、(可)溶于水的碳酸氢盐、(可)溶于水的氢氧化物中的一种或多种。
所述碱的溶液选自含有CO 3 2-、HCO 3 -或OH -中的一种或多种的碱性水溶液，所述碱的溶液中CO 3 2-的浓度为0-0.6mol/L，OH -的浓度为0-0.5mol/L，HCO 3 -的浓度为0-1mol/L，前提是CO 3 2-的浓度、OH -的浓度、和HCO 3 -的浓度之和不为零。在本文中，CO 3 2-的浓度、OH -的浓度、和HCO 3 -的浓度是通过将用于形成碱性水溶液的碱中的阴离子基团的摩尔量(mol)除以碱性水溶液的体积(L)而得到的。
所述高比热容基质材料制备步骤(2)中，尿素与锰离子摩尔比为1-5,例如为2-4，所述锰盐溶液中锰盐的浓度以MnO 2计可以为50-500g·L -1。
优选的，步骤(2)在所述锰盐溶液中加入尿素，然后在室温搅拌30-60分钟，得到锰源溶液。
所述的硼化合物例如为氮化硼和/或氧化硼和/或氧化硼前驱体。其中，所述的氮化硼可以为六方氮化硼、立方氮化硼、菱方氮化硼和纤锌矿氮化硼中的一种或多种；所述氧化硼前驱体可以为硼酸铵、硼酸氢铵或硼酸中的一种或多种。
步骤(3)中在将含铝胶体、锰源溶液混合后还包括陈化的过程，所述陈化温度为室温至120℃，陈化时间为4-72小时，在搅拌下陈化或静置陈化；优选的，所述陈化在搅拌下进行，陈化温度为60-100℃，陈化时间为12-36小时。
一种实施方式，步骤(4)中所述焙烧温度500℃-900℃，焙烧时间为4-8小时。
本发明还提供所述催化裂化催化剂的制备方法，该方法包括将所述裂化活性组元、高比热容基质材料和/或其前驱物、粘土和粘结剂混合打浆，喷雾干燥，洗涤、过滤和干燥。高比热容基质材料的前驱物是指未经步骤(4)中的焙烧而获得的高比热容基质材料；因而在本发明中，“高比热容基质材料”可以是指经过步骤(4)中的焙烧而获得的高比热容基质材料与未经步骤(4)中的焙烧而获得的高比热容基质材料的总称，或者仅仅是指经过步骤(4)中的焙烧而获得的高比热容基质材料。
本发明还提供了所述催化裂化催化剂在重油催化裂化中的应用。
本发明提供的催化裂化催化剂通过将特定的高比热容材料与裂化活性组元、粘土和粘结剂配合使用，可以提高催化裂化催化剂的比热容，有利于反应器中重油大分子的雾化和裂化。本发明提供的催化剂具有较好的耐磨损性能。本发明提供的催化裂化催化剂用于重油催化裂化，具有较高的重油转化率，具有较高的轻质油收率，具有较高的液体收率。本发明提供的催化剂具有抗多种金属污染能力，在污染铁、钒、镍的情况下，可以具有更高的总液收，具有更高的轻质油收率，具有更高的汽油收率。
本发明的其他特征和优点将在随后的具体实施方式部分予以详细说明。
附图说明
附图是用来提供对本发明的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本发明，但并不构成对本发明的限制。其中：
图1为实施例1的高比热容基质材料的X射线衍射谱图。谱图中2θ角为18±0.5°、37±0.5°、48±0.5°、59±0.5°、66±0.5°处具有衍射峰。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
在本发明中，高比热容基质材料是指在1000K的比热容不小于1.3J/(g·K)的材料。
在本发明中，当涉及催化剂的组分的含量时，催化剂的各组分的含量之和为100重量％；当涉及高比热容基质材料的组分的含量时，高比热容基质材料的各组分的含量之和为100重量％；当涉及高比热容基质材料的无水化学表达式时，无水化学表达式中各组分的系数是基于重量的，并且各组分的系数之和为100。
本发明提供的催化裂化催化剂，其中，以所述催化裂化催化剂的总重量为基准，以干基计，所述催化裂化催化剂含有1-60重量％的裂化活性组元、1-50重量％的高比热容基质材料、1-70重量％的粘土和1-70重量％的粘结剂；所述高比热容基质材料含有至少5重量％的氧化锰，在温度为1000K时，所述高比热容基质材料的比热容为 1.3-2.0J/(g·K)。
其中干基是指物质于800℃焙烧1小时后的固体产物。
本发明所述室温为15-40℃，例如为15℃。
根据本发明提供的催化裂化催化剂，优选地，以所述催化裂化催化剂的总重量为基准，所述催化裂化催化剂含有以干基计10-50重量％的裂化活性组元、以干基计5-40重量％的高比热容基质材料、以干基计10-60重量％的粘土和以干基计10-60重量％的粘结剂。将上述各组分的含量控制在该优选的范围内能够使得到的催化裂化催化剂具有更好的物化性质及反应性能。
根据本发明提供的催化裂化催化剂，当催化剂以颗粒(一个个颗粒或离散颗粒)的形式存在时，所述的裂化活性组元、高比热容基质材料处于同样的颗粒中，即在同一催化裂化催化剂颗粒中，含有所述的裂化活性组元、高比热容基质材料、粘土和粘结剂。
根据本发明提供的催化裂化催化剂，第一种实施方式，所述高比热容基质材料不含硼化合物。以所述高比热容基质材料的重量为基准，所述高比热容基质材料含有以Al 2O 3计5-95重量％的氧化铝和以MnO 2计5-95重量％锰氧化物，例如所述的高比热容基质材料主要由15-70重量％或20-65重量％或30-61重量％的锰氧化物和30-85重量％或35-80重量％或39-70重量％的氧化铝组成。所述高比热容基质材料的比表面积可以为180-300m 2·g -1，例如200-250m 2·g -1或220-245m 2·g -1；所述高比热容基质材料的孔体积为0.35-0.75，例如0.4-0.65cm 3·g -1；所述高比热容基质材料的平均孔直径为5-13nm，例如6-11nm。
根据本发明提供的催化裂化催化剂，所述的高比热容基质材料中，可以含或不含硼化合物。优选的，本发明提供的所述高比热容基质材料(简称所述基质材料)含有硼化合物，与不含硼化合物的高比热容基质材料相比，可以具有更好的抗金属污染性能。
根据本发明提供的催化裂化催化剂，第二种实施方式，所述的高比热容基质材料中，所述的硼化合物为氮化硼，其比热容为1.3-2.0J/(g·K)，例如为1.35-1.95J/(g·K)或1.51-1.95J/(g·K)。所述高比热容基质材料以重量比计的无水化学表达式可表示为(5-94.5)Al 2O 3·(5-94.5)MnO 2·(0.5-40)BN，例如可以为(20-80)Al 2O 3·(15-75)MnO 2·(5-30)BN。优选情况下，以所述高比热容基 质材料的重量为基准，所述高比热容基质材料含有5-94.5重量％的氧化铝，以MnO 2计5-94.5重量％的氧化锰和以及以干基计大于0且不超过40重量％例如0.5-35重量％的氮化硼；更优选的，所述高比热容基质材料含有15-80重量％的氧化铝，15-70重量％的氧化锰和5-30重量％的氮化硼；更更优选的，所述高比热容基质材料含有19-74重量％的氧化铝，14-66重量％的氧化锰和以及8-26重量％的氮化硼。所述的高比热容基质材料含有氮化硼，可以提高催化剂的耐磨损性能。
本发明所述催化裂化催化剂第二种实施方式，所述高比热容基质材料的比表面积为150-350m 2·g -1例如180-300m 2·g -1或200-250m 2·g -1或220-245m 2·g -1，所述高比热容基质材料的孔体积为0.35-0.75例如0.4-0.65cm 3·g -1或0.45-0.75或0.5-0.7cm 3·g -1，所述高比热容基质材料的平均孔直径为3-20nm例如为4-18nm或5-15nm或6-13nm或6-8.5nm优选为5-13nm或6-11nm。
本发明所述催化裂化催化剂第二种实施方式，所述基质材料的一种制备方法，包括下述步骤：
(1)将铝源溶液与碱溶液在室温至85℃下混合成胶，并控制成胶形成的胶体的pH值为7-11；
(2)配置pH值为3-7的锰盐溶液，将锰盐溶液与尿素混合，搅拌；尿素与锰离子摩尔比为1-5，该锰盐溶液与尿素混合的温度没有特殊要求，在室温下进行即可，搅拌的时间例如30-60分钟；
(3)将步骤(1)得到的产物、步骤(2)得到的产物和氮化硼混合，在室温至120℃下陈化4-72小时；和任选的，
(4)用水洗涤步骤(3)得到的产物，优选的，所述洗涤使洗涤后的洗涤液为中性(中性是指pH值为6.5-7.5)，例如用去离子水冲洗至洗涤后的去离子水为中性，干燥，焙烧得到高比热容基质材料。
本发明所述催化裂化催化剂第二种实施方式，所述高比热容基质材料的的制备方法中，步骤(1)中所述碱溶液的可选范围较宽，优选的，步骤(1)中所述碱溶液为含有CO 3 2-、HCO 3 2-和OH -的至少一种的碱性水溶液，更优选地，所述的碱性水溶液为包括碳酸氢铵、碳酸铵、氢氧化钠、氢氧化钾中的一种或多种的水溶液，或者为碳酸铵、氢氧化钠、氢氧化钾中的一种或多种与氨水的混合溶液。优选的，所述碱溶液中碱的总浓度为0.1-1mol/L。于一种实施方式，所述的碱溶液中，CO 3 2- 的浓度为0-0.6mol/L，例如为0.3-0.5mol/L；OH -的浓度为0-0.5mol/L，例如为0.2-0.35mol/L，HCO 3 2-的浓度为0-1.0mol/L例如为0.4-1.0mol/L。步骤(1)成胶pH值优选为8-11例如8.5-11或9-10。在选用氨水时，假设氨水全部电离，根据计算得到的氢氧根计算氨水需要的加入量。
本发明所述催化裂化催化剂第二种实施方式，所述高比热容基质材料的的制备方法中，所述铝源的种类的可选范围较宽，能够溶于水的水溶性铝源均可用于本发明，例如所述铝源可选自硝酸铝、硫酸铝和氯化铝中的一种或多种。
本发明所述催化裂化催化剂第二种实施方式，所述高比热容基质材料的的制备方法中，步骤(2)中使特定pH值的锰盐溶液与尿素混合形成混合物，所述锰盐溶液的pH值为3-7优选为5-7。使尿素与锰盐溶液混合的条件的可选范围较宽，针对本发明，一种实施方式，步骤(2)中所述混合的方法包括：在锰盐溶液中加入尿素，于室温搅拌40-60分钟，尿素和锰离子摩尔比优选在2-4之间。步骤(2)中所述锰盐溶液可选自水溶性锰盐的水溶液，和/或，水溶性锰盐、锰氧化物、和/或锰氢氧化物与酸接触后形成的盐溶液。所述锰盐的种类的可选范围较宽，能够溶于水的水溶性锰盐均可用于本发明，所述锰盐例如硝酸锰、硫酸锰或氯化锰等中的一种或多种。锰盐溶液也可由锰氧化物和/或锰氢氧化物和/或水溶性锰盐与酸接触而制得，所述锰氧化物例如一氧化锰、四氧化三锰、三氧化二锰、二氧化锰中的一种或多种，所述酸例如盐酸、硫酸、磷酸、硝酸中的一种或多种，优选盐酸、硫酸、硝酸中的一种或多种。
本发明所述催化裂化催化剂第二种实施方式，所述高比热容基质材料的的制备方法中，步骤(3)中所述步骤(1)得到的产物以Al 2O 3计、步骤(2)得到的产物以MnO 2计和氮化硼以干基计的重量用量比例为(5-95)Al 2O 3：(5-95)MnO 2：(0.5-40)BN例如为(20-80)Al 2O 3：(15-75)MnO 2：(5-30)BN。优选的，步骤(3)中所述步骤(1)得到的产物、步骤(2)得到的产物和氮化硼用量使制备得到的基质材料中含有5-94.5重量％例如15-80重量％或19-74重量％或20-80重量％或19-60重量％的氧化铝，以MnO 2计5-94.5重量％例如15-75重量％或10-70重量％或14-66重量％或19-66重量％的氧化锰和以及以干基计大于0且不超过40重量％例如0.5-35重量％或5-30重量％或8-26重量％的氮化硼。
本发明所述催化裂化催化剂第二种实施方式，所述高比热容基质材料的的制备方法中，步骤(3)中所述陈化条件的可选范围较宽(例如所述陈化温度为室温至120℃，陈化时间为4-72小时)，优选的，步骤(3)中所述陈化条件包括：陈化温度为60-100℃，陈化时间12-36小时，搅拌下陈化。对于搅拌的方式没有特殊要求，例如，搅拌速度可以为50-300转/分钟。
根据本发明所述催化裂化催化剂第二种实施方式，所述高比热容基质材料的的制备方法中，所述氮化硼可选自六方氮化硼(h-BN)、立方氮化硼(c-BN)、菱方氮化硼(r-BN)和纤锌矿氮化硼(w-BN)中的一种或多种。
根据本发明所述催化裂化催化剂第二种实施方式，所述高比热容基质材料的的制备方法中，步骤(4)中所述干燥条件和焙烧条件的可选范围较宽。所述干燥、焙烧的方法均可参照现有技术进行，本发明对此无特殊要求。例如，步骤(4)中所述干燥条件包括：在100-150℃下干燥6-24小时；步骤(4)中所述焙烧条件包括：在550-800℃例如550-750℃下焙烧4-8小时。
本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料中，所述的硼化合物为氧化硼，其比热容为1.3-2.0J/(g·K)，例如为1.35-1.95J/(g·K)或1.51-1.95J/(g·K)，本发明提供的高比热容介孔基质材料的无水化合物组成表达式以氧化物重量比计为(5-94.5)Al 2O 3·(5-94.5)MnO 2·(0.5-10)B 2O 3，例如为(20-80)Al 2O 3·(15-75)MnO 2·(0.5-10)B 2O 3或为(20-80)Al 2O 3·(15-75)MnO 2·(1-8)B 2O 3。优选的情况下，以所述高比热容基质材料的重量为基准，所述的高比热容基质材料含有5-94.5重量％的氧化铝、以MnO 2计5-94.5重量％的氧化锰以及以B 2O 3计0.5-10重量％的氧化硼；更优选的，所述的高比热容基质材料含有15-80重量％的氧化铝、以MnO 2计15-80重量％的氧化锰以及以B 2O 3计0.8-8重量％的氧化硼或者所述的高比热容基质材料含有20-62重量％的氧化铝、以MnO 2计34-72重量％的氧化锰以及以B 2O 3计2-8重量％的氧化硼。优选的，该高比热容基质材料的比表面积为300-500m 2/g例如310-370m 2/g或330-370m 2/g，孔容为0.5-1.5cm 3/g例如0.7-1.4cm 3/g或0.6-1.3cm 3/g或0.7-1.2cm 3/g。优选的，所述基质材料为介孔基质材料， 其平均孔径为3-20nm例如5-18nm或8-18nm或7-15nm或8-14nm或10-15nm或10-13nm。
本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料中，所述的硼化合物为氧化硼，可以具有更高的孔体积和比表面积，并且引入氧化硼，调变了基质酸性，提高基质预裂化能力，作为催化裂化催化剂或助剂的基质材料，应用于重油催化裂化中，能降低催化裂化催化剂再生时的颗粒温度，减缓分子筛崩塌，提高催化剂的活性、抗金属污染能力及重油转化能力，降低催化剂的焦炭选择性，使催化剂流化性能良好。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料的一种制备方法包括下述步骤：
(1)将铝源溶液与碱的溶液在室温至85℃下混合成胶，并控制成胶得到的胶体的pH值为7-11；
(2)配置pH值为3-7的锰盐溶液，将所述锰盐溶液与尿素混合，搅拌例如于室温搅拌30-60分钟；其中尿素与锰离子摩尔比为1-5；
(3)将步骤(1)得到的产物、步骤(2)得到的产物混合，陈化；所述陈化例如在室温至120℃下陈化4-72小时；将陈化固体产物与氧化硼源混合或将陈化固体产物洗涤后与氧化硼源混合，任选还进行反应；其中以B 2O 3计的所述氧化硼源投料量与以干基计的高比热容基质材料重量比为(0.005-0.1)：1；
(4)将步骤(3)得到的固体沉淀物(或称固体产物)直接干燥、焙烧或者将步骤(3)的固体沉淀物洗涤后干燥，焙烧；所述洗涤，可以用水对步骤(3)的固体产物进行洗涤，例如可以用水冲洗，使洗涤后的水呈中性。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料的制备方法，制备得到的基质材料与其它方法得到本发明范围内的高比热容基质材料相比不仅具有较高的比热容，还可具有更高的平均孔径，可以具有更高的比表面积、具有更高的孔体积，将其用于高金属含量尤其高铁含量的重油催化裂化具有较高液体产品收率，较低干气及焦炭收率。与使用不含氧化硼的高比热容基质材料的催化剂相比，可以具有更高的重油转化活性，可以具有更高的汽油收率。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热 容基质材料的制备方法中，步骤(1)中所述碱溶液的可选范围较宽，优选的，步骤(1)中所述碱溶液为含有HCO 3 2-、CO 3 2-和OH -中至少一种的碱性水溶液，所述的碱性水溶液优选为包括碳酸氢铵、碳酸铵、氢氧化钠、氢氧化钾中的一种或多种的水溶液，或者为包括碳酸氢铵、碳酸铵、氢氧化钠、氢氧化钾中的一种或多种与氨水的混合溶液。优选的，所述碱溶液中碱的总浓度为0.1-1mol/L。优选的，所述碱溶液中，CO 3 2-的浓度为0-0.6mol/L，例如为0.3-0.5mol/L；OH -的浓度优选0-0.5mol/L，例如为0.2-0.35mol/L，HCO 3 2-的浓度为0-1.0mol/L例如为0.4-1.0mol/L。在选用氨水时，假设氨水全部电离，根据计算得到的氢氧根计算氨水需要的加入量即可。成胶得到的胶体的pH值优选为9-11或10-11。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料的制备方法中，所述铝源的种类的可选范围较宽，能够溶于水的水溶性铝源均可用于本发明，例如所述可溶性铝盐可选自硝酸铝、硫酸铝、磷酸铝和氯化铝等中的一种或多种，优选为硝酸铝、硫酸铝和氯化铝等中的一种或多种。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料的制备方法中，步骤(2)中所述锰盐溶液可选自水溶性锰盐的水溶液，和/或，水溶性锰盐、锰氧化物、和/或锰氢氧化物与酸接触后形成的盐溶液；所述锰盐溶液的pH值为3-7，优选为5-7。优选的，步骤(2)中将锰盐溶液与尿素混合后，于室温搅拌40-60分钟，尿素和锰离子摩尔比在2-4之间。步骤(2)中所述锰盐溶液可选自水溶性锰盐的水溶液和/或锰氧化物、锰氢氧化物和/或水溶性锰盐与酸接触后形成的盐溶液。所述锰盐的种类的可选范围较宽，能够溶于水的水溶性锰盐均可用于本发明，所述水溶性锰盐例如硝酸锰、硫酸锰、磷酸锰或氯化锰等中的一种或多种。所述锰盐溶液也可由水溶性锰盐、锰氧化物和/或锰氢氧化物与酸接触而制得，所述锰氧化物例如一氧化锰、四氧化三锰、三氧化二锰、二氧化锰中的一种或多种，所述酸例如盐酸、硫酸、磷酸、硝酸中的一种或多种，优选盐酸、硫酸、硝酸中的一种或多种。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料的制备方法中，步骤(3)中所述陈化条件的可选范围较宽(例 如所述陈化温度为室温至120℃，陈化时间为4-72小时)，优选的，步骤(3)中所述陈化条件包括：陈化温度为60-100℃，搅拌陈化，陈化时间为12-36小时。搅拌的方法为现有方法，例如搅拌速度为50-300转/分钟。陈化产物的经过过滤或过滤后洗涤得到陈化固体产物。一种实施方式，所述洗涤，按陈化固体产物(干基)：H 2O＝1：(5-30)重量比将陈化所得陈化固体产物(也称沉淀物)与水在室温下接触1-3次，每次接触0.5-1小时，直至洗涤后的洗涤液为中性，通常pH为6.5-7.5。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料的制备方法中，将陈化固体产物与硼源接触处理，接触处理的方法可以有多种。可以将陈化产物过滤得到滤饼即陈化固体产物直接与硼源混合或者将过滤得到的滤饼洗涤后得到的陈化固体产物与硼源混合；优选的，所形成的混合物还进行一段时间的反应，例如在室温至90℃下搅拌或静置0.2-5小时。一种实施方式，将陈化固体产物与水混合打浆，其中所述陈化固体产物(按干基计)：H 2O的重量比为1：(5-20)，再将硼源加入上述浆液中，在室温至90℃下静置或搅拌0.2-5小时，优选0.5-3小时，过滤得到固体沉淀物。也可以是将所述陈化固体产物或洗涤后的陈化固体产物与硼源按比例混合，研磨均匀，得到固体沉淀物。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料的制备方法中，所述氧化硼源优选为焙烧后能够得到氧化硼的物质例如可以是硼酸铵、硼酸氢铵或硼酸中的一种或多种。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料的制备方法中，步骤(3)中所述步骤(1)得到的产物以Al 2O 3计、步骤(2)得到的产物以MnO 2计和硼源以B 2O 3计的重量用量比为(5-94.5)Al 2O 3：(5-94.5)MnO 2：(0.5-10)B 2O 3例如为(20-80)Al 2O 3：(15-75)MnO 2：(1-8)B 2O 3。优选的，所得到的高比热容基质材料中高比热容基质材料含有5-94.5重量％例如15-80重量％或20-75重量％或20-62重量％的氧化铝，5-94.5重量％例如15-80重量％或22-72重量％或30-72重量％以MnO 2计的氧化锰以及0.5-10重量％或0.8-8重量％或2-8重量％以B 2O 3计的氧化硼。
根据本发明提供的催化裂化催化剂第三种实施方式，所述高比热容基质材料的制备方法中，步骤(4)将步骤(3)得到的固体沉淀物直接进 行干燥和焙烧，或者洗涤后进行干燥和焙烧。其中所述洗涤，可以用水洗涤，例如可以与水混合后洗涤，或者用水冲洗，通常，洗涤后的固体沉淀物为中性即与水接触后水的pH值为6.5-7.5。其中所述干燥、焙烧的方法均可参照现有技术进行，可选范围较宽，本发明对此无特殊要求。例如，所述干燥可以在100-150℃下干燥12-24小时；所述焙烧，可以在550-800℃例如550-750℃下焙烧4-8小时。
根据本发明提供的催化裂化催化剂，所述裂化活性组元含有Y型分子筛。其中，所述Y型分子筛的种类可以包括NaY经离子改性或超稳改性的各类Y型分子筛，所述离子改性包括稀土离子、碱土金属离子、过渡金属离子、磷改性等，超稳改性包括水热超稳、气相超稳、化学超稳等方式，例如，可以为含稀土的Y型分子筛例如REHY分子筛、含磷和稀土的Y型分子筛例如DOSY分子筛、超稳Y分子筛例如DASY分子筛、含磷和/或稀土的超稳Y分子筛等中的一种或多种。此外，除了Y型分子筛之外，任选地，所述裂化活性组元还含有第二分子筛，所述第二分子筛例如为其它八面沸石、Beta沸石、MFI结构分子筛(如ZRP-1分子筛)和丝光沸石中的一种或多种。其中，以所述裂化活性组元的总重量为基准，所述Y型分子筛的含量可以为75重量％以上，优选为90重量％以上，更优选为95重量％以上；所述第二分子筛的含量(其它八面沸石、Beta沸石、MFI结构分子筛和丝光沸石的总含量)可以为25重量％以下，优选为10重量％以下，更优选为5重量％以下。
根据本发明提供的催化裂化催化剂，所述粘土可以为现有的各种能够用于催化裂化催化剂中的粘土，例如，可以选自高岭土、多水高岭土、蒙脱土、硅藻土、埃洛石、皂石、累托土、海泡石、凹凸棒石、水滑石和膨润土中的一种或几种。
根据本发明提供的催化裂化催化剂，所述粘结剂可以为现有的各种能够用于催化裂化催化剂中的粘结剂，例如，可以选自硅溶胶、铝溶胶和拟薄水铝石中的一种或几种。
此外，所述催化裂化催化剂还可以含有外加稀土。所述外加稀土可以是在制备所述催化裂化催化剂的过程中通过额外加入氯化稀土而形成的。在所述催化裂化催化剂中，所述外加稀土通常以稀土氧化物(RE 2O 3)的形式存在。以所述催化裂化催化剂的干基重量为基准，以稀 土氧化物计的所述外加稀土的含量可以为0-3重量％，优选为0.5-2重量％。其中，所述外加稀土中的稀土元素是指催化裂化催化剂领域中涉及的各种常规的稀土元素，例如可以为镧、铈、镨、钕、钷、钐、铕等。
本发明提供的催化裂化催化剂的制备方法包括将裂化活性组元、高比热容基质材料、粘土和粘结剂混合打浆，然后再依次进行喷雾干燥、洗涤、过滤和干燥。此外，当所述催化裂化催化剂还含有外加稀土时，本发明提供的催化裂化催化剂的制备方法还包括将所述氯化稀土与所述裂化活性组元、高比热容基质材料、粘土和粘结剂一起混合打浆，然后再依次进行喷雾干燥、洗涤、过滤和干燥。
根据本发明提供的催化裂化催化剂的制备方法，将所述裂化活性组元、高比热容基质材料、粘土和粘结剂以及选择性含有的氯化稀土混合打浆，以及后续的喷雾干燥、洗涤、过滤和干燥，这些工序的实施方法均可采用常规的方法实施，它们的具体实施方法例如在CN1916166A、CN1098130A、CN1362472A、CN1727442A、CN1132898C和CN1727445A中都有详尽的描述，这里一并引入本发明中以作参考。此外，一般地，在所述喷雾干燥之后、洗涤之前，所述催化裂化催化剂的制备方法通常还包括将喷雾干燥产物进行焙烧的步骤。所述焙烧的条件通常包括焙烧温度可以为500-700℃，焙烧时间可以为1-4小时。
此外，本发明还提供了上述催化裂化催化剂在重油催化裂化中的应用。
本发明提供的所述催化裂化催化剂在重油催化裂化中的应用方法，包括将所述催化裂化催化剂与重油接触反应的步骤，所述的重油例如减压渣油、减压瓦斯油、常压渣油、常压瓦斯油、脱沥青油中的一种或多种。所述接触反应的反应条件，包括：反应温度为480-530℃，剂油比(重量比)为3-10，反应时间为0.1-5秒。
在本发明的一种实施方案中，重油满足以下条件中的一个或多个或全部：(a)比重(20℃)0.82-0.95，优选大于0.91并且不大于0.95；(b)碳含量85wt％-89wt％；(c)氢含量10wt％-13wt％；(d)硫含量0.1％-4wt％；(e)凝固温度为-10至40℃。
具体来说，本发明提供了下述技术方案：
1.一种高比热容基质材料，其含有至少5重量％的氧化锰，所述 高比热容基质材料温度为1000K的比热容为1.3-2.0J/(g·K)。
2.按照前述技术方案中任一项所述的高比热容基质材料，其中，所述高比热容基质材料含有以Al 2O 3计5-95重量％、例如19.6-74.8重量％的氧化铝，以MnO 2计5-95重量％、例如15.3-71.8重量％的氧化锰，以及以干基计0-40重量％、0-25.2重量％的硼化合物；例如所述高比热容基质材料含有以Al 2O 3计19.6-74.8重量％的氧化铝，以MnO 2计15.3-71.8重量％的氧化锰，以及以干基计0-25.2重量％的硼化合物。
3.按照前述技术方案中任一项所述的高比热容基质材料，其中，所述的高比热容基质材料中，所述的硼化合物为氮化硼和/或氧化硼。
4.按照前述技术方案中任一项所述的高比热容基质材料，其中，所述高比热容基质材料的比表面积为150-500m 2·g -1，例如200-400m 2·g -1，如221-365m 2·g -1。
5.按照前述技术方案中任一项所述的高比热容基质材料，其中，所述高比热容基质材料的孔体积为0.3-1.5cm 3·g -1，例如0.35-1.2cm 3·g -1，例如0.38-1.17cm 3·g -1。
6.按照前述技术方案中任一项所述的高比热容基质材料，其中，所述高比热容基质材料的平均孔直径为3-20nm，例如5-15nm，如6.4-13.6nm。
7.按照前述技术方案中任一项所述的高比热容基质材料，其中，所述高比热容基质材料的XRD图谱，在2θ角为18±0.5°和2θ角为37±0.5°处峰的强度比为1:(3-10)。
8.按照前述技术方案1-7中任一项所述的高比热容基质材料的制备方法，包括下述步骤：
(1)使铝源与碱混合成胶，得到含铝胶体，所得含铝胶体的pH值为7-11；
(2)使pH值为3-7的锰盐溶液与尿素混合，得到锰源溶液；
(3)使含铝胶体、锰源溶液、任选的硼化合物形成混合物；和任选的
(4)洗涤和/或干燥和/或焙烧。
9.按照技术方案8中所述的制备方法，其中，所述使铝源与碱混合成胶包括：将铝源溶液、碱的溶液混合，形成温度为室温至85℃、pH值为7-11的胶体。
10.按照技术方案8至前一项技术方案中任一项所述的制备方法，其中，所述铝源溶液中氧化铝的浓度为150-350gAl 2O 3/L，碱的溶液中碱的浓度为0.1-1mol/L。
11.按照技术方案8至前一项技术方案中任一项所述的制备方法，其中，所述的铝源选自硝酸铝、硫酸铝、磷酸铝、氯化铝和其混合物；所述的碱选自可溶于水的碳酸盐、可溶于水的碳酸氢盐、可溶于水的氢氧化物、和其混合物。
12.按照技术方案8至前一项技术方案中任一项所述的制备方法，其中，所述碱的溶液选自含有CO 3 2-、HCO 3 -和OH -中的一种或多种的碱性水溶液，所述碱的溶液中CO 3 2-的浓度为0-0.6mol/L，OH -的浓度为0-0.5mol/L，HCO 3 -的浓度为0-1mol/L，前提是CO 3 2-的浓度、OH -的浓度、和HCO 3 -的浓度之和不为零，其中CO 3 2-的浓度、OH -的浓度、和HCO 3 -的浓度是通过将用于形成碱性水溶液的碱中的阴离子基团的摩尔量(mol)除以碱性水溶液的体积(L)而得到的。
13.按照技术方案8至前一项技术方案中任一项所述的制备方法，其中，步骤(2)中，尿素与锰离子摩尔比为1-5，例如为2-4，所述锰盐溶液中锰盐的浓度以MnO 2计可以为50-500g·L -1。
14.按照技术方案8至前一项技术方案中任一项所述的制备方法，其中，步骤(2)中，在所述锰盐溶液中加入尿素，然后在室温搅拌30-60分钟，得到锰源溶液。
15.按照技术方案8至前一项技术方案中任一项所述的制备方法，其中，所述的硼化合物为氮化硼和/或氧化硼和/或氧化硼前驱体。
16.按照技术方案16所述的催化裂化催化剂，其中，所述的氮化硼为六方氮化硼、立方氮化硼、菱方氮化硼和纤锌矿氮化硼中的一种或多种；所述氧化硼前驱体为硼酸铵、硼酸氢铵和硼酸中的一种或多种。
17.按照技术方案8至前一项技术方案中任一项所述的制备方法，其中，步骤(3)中，在将含铝胶体、锰源溶液混合后还包括陈化的过程，所述陈化温度为室温至120℃，陈化时间为4-72小时，在搅拌下陈化或静置陈化；优选的，所述陈化在搅拌下进行，陈化温度为60-100℃，陈化时间为12-36小时。
18.按照技术方案8至前一项技术方案中任一项所述的制备方法， 其中，所述的硼化合物为氮化硼；步骤(3)使含铝胶体、锰源溶液、硼化合物形成混合物的方法如下：将含铝胶体、锰源溶液和硼化合物混合，陈化。
19.按照技术方案8至前一项技术方案中任一项所述的制备方法，其中，所述的硼化合物为氧化硼和/或氧化硼的前身物，步骤(3)所述使含铝胶体、锰源溶液、硼化合物形成混合物的方法如下：将含铝胶体、锰源溶液混合，陈化，任选洗涤，然后与硼化合物混合。
20.按照技术方案8至前一项技术方案中任一项所述的制备方法，其中，步骤(4)中所述焙烧温度500℃-900℃，焙烧时间为4-8小时。
21.一种催化裂化催化剂，其中所述催化裂化催化剂含有包括Y型分子筛的裂化活性组元、前述技术方案1-7中任一项所述的高比热容基质材料或通过前述技术方案8-20中任一项所述的制备方法得到的高比热容基质材料、粘土和粘结剂。
22.按照前述技术方案21所述的催化裂化催化剂，其中，以所述催化裂化催化剂的总重量为基准，所述催化裂化催化剂含有1-60重量％的裂化活性组元、1-50重量％的高比热容基质材料、1-70重量％的粘土和1-70重量％的粘结剂，或者，以所述催化裂化催化剂的总重量为基准，所述催化裂化催化剂含有10-50重量％的裂化活性组元、5-40重量％的高比热容基质材料、10-60重量％的粘土和10-60重量％的粘结剂，其中催化裂化催化剂的质量为100重量％。
23.按照技术方案21至前一项技术方案中任一项所述的催化裂化催化剂，其中，所述裂化活性组元含有Y型分子筛。
24.按照技术方案21至前一项技术方案中任一项所述的催化裂化催化剂，其中，所述裂化活性组元还含有第二分子筛，所述第二分子筛为八面沸石、Beta沸石、MFI结构分子筛和丝光沸石中的一种或多种。
25.按照技术方案21至前一项技术方案中任一项所述的催化裂化催化剂，其中，以所述裂化活性组元的总重量为基准，所述Y型分子筛的含量为75重量％以上，所述第二分子筛的含量为25重量％以下。
26.按照技术方案21-25中任一项所述的催化裂化催化剂的制备方法，该方法包括将所述裂化活性组元、高比热容基质材料、粘土和粘结剂混合打浆，然后再依次进行喷雾干燥、焙烧、洗涤、过滤和干 燥。
27.按照技术方案21-25中任一项所述的催化裂化催化剂在重油催化裂化中的应用。
以下将通过实施例对本发明进行详细描述。
以下制备例、对比制备例、实施例和对比例中使用的原料如下：
盐酸由北京化工厂生产，化学纯，浓度为36重量％；
钠水玻璃为市售，SiO 2浓度为26.0重量％，模数为3.2；
高岭土为苏州高岭土公司产品，固含量为74.0重量％；
拟薄水铝石为山东铝厂工业产品，固含量为62.0重量％；
铝溶胶为中国石化催化剂齐鲁分公司产品，Al 2O 3含量为21.5重量％；
DASY分子筛(固含量为92.0重量％，RE 2O 3为1.8重量％，Na 2O为1.0重量％，结晶度60％)、ZRP-1分子筛(固含量为97.8重量％，Na 2O为1.1重量％，结晶度70％)、REHY分子筛(固含量为88.0重量％，RE 2O 3为5.0重量％，Na 2O为0.9重量％，结晶度65％)、Beta分子筛(固含量为95.2重量％，Na 2O为1.2重量％，结晶度60％)、DOSY分子筛(固含量为93.5重量％，RE 2O 3为8.0重量％，Na 2O为0.8重量％，结晶度80％)、HSY分子筛(固含量91.5重量％，RE 2O 3为10.5重量％，Na 2O为0.9重量％，结晶度85％)均由中国石化催化剂齐鲁分公司生产；
氯化稀土购自包钢稀土高科技股份有限公司，其中的稀土元素为La和Ce。
下面通过实施例对本发明予以进一步说明，但并不因此而限制本发明。
本发明中，剂油比指的是催化剂与原料油的质量比。
本发明中，如未特别说明，ppm为以重量计的ppm。
所用BN，为六方氮化硼。
在各实施例和对比例中，样品中Al 2O 3、MnO 2、B、N、Fe的含量用X射线荧光法测定(参见《石油化工分析方法(RIPP实验方法)》，杨翠定等编，科学出版社，1990年出版)。样品物相采用X射线衍射法测定。样品比表面积、孔体积、平均孔径由低温氮吸附－脱附法测定、BJH法计算得到孔径分布。
制备例1
本制备例说明本发明提供的高比热容基质材料的制备过程。
将浓度300gAl 2O 3/L的Al 2(SO 4) 3溶液与CO 3 2-浓度为0.10mol/L的碳酸铵溶液在20℃下混合成胶，所得胶体pH值＝7.5，得到浆液A。向浓度450gMnO 2/L的MnCl 2溶液中加入盐酸，控制pH值＝3.5，然后向溶液中加入尿素，尿素与锰离子摩尔比为2，室温下搅拌30分钟，得到溶液B。将溶液B加入浆液A中，80℃下搅拌陈化4小时，待体系温度降至室温，用去离子水冲洗至洗涤后的水为中性，于120℃下干燥12小时得基质材料前驱体，然后于550℃下焙烧6小时，随炉冷却至室温得到本发明提供的高比热容基质材料，记为AM-1。AM-1的配比、制备条件参数、比热容、比表面积、孔容及平均孔径列于表1中。
AM-1的X射线衍射谱图如图1所示，其中2θ角为18±0.5°和2θ角为37±0.5°处具有特征峰，二者的强度比(I 1/I 2)为1:5.2；其元素分析化学组成表达式(按照重量计)为60.5MnO 2·39.5Al 2O 3；比热容1.36J/(g·K)，比表面积238m 2/g，孔容0.38cm 3/g，平均孔径6.4nm。
制备例2-4
制备例2-4用于说明本发明提供的高比热容基质材料的制备过程。
按照制备例1的方法制备高比热容基质材料AM-2至AM-4，不同的是原料配比、制备条件参数、产品的元素组成、比热容、比表面积、孔容及平均孔径列于表1中，其中溶液B加入浆液A中，然后加入氮化硼，再进行所述陈化。
制备例5
实施例5用于说明本发明提供的高比热容基质材料的制备过程。
将浓度350gAl 2O 3/L的Al(NO 3) 3溶液与CO 3 2-浓度为0.1mol/L(碳酸铵)、OH -浓度为0.1mol/L(氨水)的溶液在温度为25℃下混合成胶，控制pH值为10.5，得到浆液A。将Mn 3O 4与盐酸、水混合，得到浓度116.5gMnO 2/L的氯化锰溶液，控制pH值＝6，然后向溶液中加入尿素，尿素与锰离子摩尔比为3，室温下搅拌40分钟，得到溶液B。将溶液B、145.6gBN(固含量80重量％)加入浆液A中，60℃下搅拌陈化24小时，待体系温度降至室温，用去离子水冲洗至洗涤后的水呈中性，于120℃下干燥12小时得基质材料前驱体，然后于650℃下焙烧4小时，随炉冷却至室温得到本发明提供的高比热容基质材料，记为AM-5。AM-5的配方、制备参数、比热容、比表面积、孔容及平均孔径列于表 1中。
AM-5的X射线衍射谱图同图1，其中2θ角为18±0.5°和2θ角为37±0.5°处具有特征峰，二者的强度比1:6.6；AM-5的化学组成表达式按重量计为20.6MnO 2·59.4Al 2O 3·19.4BN；比热容1.48J/(g·K)，比表面积243m 2/g，孔容0.46cm 3/g，平均孔径7.6nm。
制备例6
制备例6用于说明本发明提供的高比热容基质材料的制备过程。
按照制备例5的方法制备基质材料AM-6，不同的原料配比、制备条件参数，其组成、比热容、比表面积、孔容及平均孔径列于表1中，其中成胶用的碱溶液中CO 3 2-浓度为0.2mol/L，OH -浓度为0.15mol/L。
AM-2至AM-6的X射线衍射谱图参见图1所示，2θ角为18±0.5°和2θ角为37±0.5°处具有峰。
对比制备例1
使用去离子水分别配制浓度为350gAl 2O 3/L的Al(NO 3) 3溶液和浓度为525gMnO 2/L的硝酸锰溶液，混合均匀，得到溶液A。配制碳酸氢铵溶液，控制PH＝10.0，记为溶液B。连续搅拌下将溶液A和溶液B混合，得到母液C，混合过程中通过控制溶液B的加入量控制母液C的PH为8-9。混合完毕后180℃下陈化20小时，待体系温度降至室温，用去离子水冲洗至中性，于120℃下干燥12小时得锰铝基质前驱体，然后于1000℃下焙烧4小时，随炉冷却至室温得到对比基质材料，记为DAM-1。
DAM-1的X射线衍射谱图，其中2θ角为18±0.5°和2θ角为37±0.5°处具有特征峰，二者的强度比为1：1.9；DAM-1的元素分析化学组成表达式为60.6MnO 2·39.4Al 2O 3；比热容0.62J/(g·K)，比表面积224m 2/g，孔容0.31cm 3/g，平均孔径5.5nm。
对比制备例2
将浓度350gAl 2O 3/L的Al 2(SO 4) 3溶液与碳酸铵混合成胶，控制pH＝10.0，得到浆液A。将浓度209.7gMnO 2/L的MnSO 4溶液加入浆液A，室温下搅拌30分钟，得到浆液B。将95.4g氮化硼(固含量80重量％)加入浆液B中，80℃下陈化24小时，待体系温度降至室温，用去离子水冲洗至中性，于120℃下干燥12小时得锰铝基质前驱体，然后于900℃下焙烧6小时，随炉冷却至室温得到对比基质材料的样品，记为 DAM-2。
DAM-2的元素分析化学组成表达式以重量计为33.3MnO 2·54.7Al 2O 3·11.7BN；比热容0.85J/(g·K)，比表面积219m 2/g，孔容0.25cm 3/g，平均孔径4.6nm。
表1
Figure PCTCN2021120144-appb-000001
Figure PCTCN2021120144-appb-000002
注：表1、4中，I 1/I 2为XRD图谱中2θ角18±0.5°峰强度与2θ角37±0.5°峰强度比
实施例1
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的20重量份的拟薄水铝石与去离子水混合打浆(浆液固含量为15重量％)，并向得到的浆液中加入盐酸胶溶，酸铝比(36重量％盐酸与以氧化铝计拟薄水铝石重量比)为0.20：1，然后温度升至65℃酸化1小时，接着分别加入以干基计的28重量份高岭土的浆液(固含量为25重量％)、以干基计的13重量份的铝溶胶以及以干基计的10重量份的由制备例1制备的高比热容基质材料AM-1的浆液(固含量为18重量％)，搅拌20分钟，之后再向其中加入以干基计的29重量份的所述DASY分子筛浆液(固含量为35重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C1，其中，以所述催化裂化催化剂C1的总重量为基准，所述催化裂化催化剂C1中含有10重量％的高比热容基质材料、29重量％的DASY分子筛、28重量％的高岭土、33重量％的Al 2O 3粘结剂。
对比例1
该对比例用于说明参比的催化裂化催化剂及其制备方法。
按照实施例1的方法制备催化裂化催化剂，不同的是，将由制备例1制备的高比热容基质材料AM-1用相同重量份的由对比制备例1制备的基质材料DAM-1代替，得到参比催化裂化催化剂CB1，其中，以所述参比催化裂化催化剂CB1的总重量为基准，所述参比催化裂化 催化剂CB1中含有10重量％的对比基质材料、29重量％的DASY分子筛、28重量％的高岭土、33重量％的Al 2O 3粘结剂。
对比例2
该对比例用于说明参比的催化裂化催化剂及其制备方法。
按照实施例1的方法制备催化裂化催化剂，不同的是，将由制备例1制备的高比热容基质材料AM-1用相同重量份的由对比制备例1制备的基质材料DAM-2代替，得到参比催化裂化催化剂CB2，其中，以所述参比催化裂化催化剂CB2的总重量为基准，所述参比催化裂化催化剂CB2中含有10重量％的对比基质材料、29重量％的DASY分子筛、28重量％的高岭土、33重量％的Al 2O 3粘结剂。
对比例3
该对比例用于说明参比的催化裂化催化剂及其制备方法。
按照实施例1的方法制备催化裂化催化剂，不同的是，不加入高比热容基质材料AM-1，而将高比热容基质材料AM-1用相同干基重量的高岭土替代，得到参比催化裂化催化剂CB3，其中，以所述参比催化裂化催化剂CB3的总重量为基准，所述参比催化裂化催化剂CB3中含有29重量％的DASY分子筛、38重量％的高岭土、33重量％的Al 2O 3粘结剂。
实施例2
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的20重量份的高岭土与去离子水混合打浆(浆液固含量40重量％)，再加入以干基计的20重量份的拟薄水铝石，并向得到的浆液中加入盐酸胶溶，酸铝比(重量)为0.20：1，然后将温度升至65℃酸化1小时，接着分别加入以干基计的5重量份的铝溶胶、以干基计的30重量份的由制备例2制备的高比热容基质材料AM-2的浆液(固含量为20重量％)，搅拌20分钟，之后再向其中加入以干基计的20重量份的DASY分子筛、以干基计的5重量份的ZRP-1分子筛的混合浆液(固含量为35重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C2，其中，以所述催化裂化催化剂C2的总重量 为基准，所述催化裂化催化剂C2中含有30重量％的高比热容基质材料、20重量％的DASY分子筛、5重量％的ZRP-1分子筛、20重量％的高岭土、25重量％的Al 2O 3粘结剂。
实施例3
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的28重量份高岭土与去离子水混合打浆(浆液固含量40重量％)，再加入以干基计的25重量份的拟薄水铝石，并向得到的浆液中加入盐酸进行胶溶，酸铝比(重量比)为0.20：1，然后将温度升至65℃酸化1小时，接着分别加入以干基计的20重量份的由制备例3制备的高比热容基质材料AM-3的浆液(固含量为25重量％)和以干基计5重量份的铝溶胶，搅拌20分钟，之后再向其中加入以干基计的15重量份的所述REHY分子筛与以干基计的5重量份的所述Beta分子筛的混合浆液(固含量为35重量％)以及以稀土氧化物计的2重量份的氯化稀土溶液，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C3，其中，以所述催化裂化催化剂C3的总重量为基准，所述催化裂化催化剂C3中含有20重量％的高比热容基质材料、15重量％的REHY分子筛、5重量％的Beta分子筛、28重量％的高岭土、30重量％的Al 2O 3粘结剂、2重量％的氧化稀土。
实施例4
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的40重量份的高岭土与以干基计的15重量份的铝溶胶以及以干基计的15重量份的由制备例4制备的高比热容基质材料AM-4的浆液(固含量为20重量％)混合打浆，搅拌120分钟，之后再向其中加入以干基计的30重量份的所述DOSY分子筛浆液(固含量为35重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C4，其中，以所述催化裂化催化剂C4的总重量为基准， 所述催化裂化催化剂C4中含有15重量％的高比热容基质材料、30重量％的DOSY分子筛、40重量％的高岭土、15重量％的Al 2O 3粘结剂。
实施例5
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
(1)制备硅溶胶：
将1.7L盐酸用8.0kg脱阳离子水进行稀释，将7.7kg钠水玻璃用8.0kg脱阳离子水进行稀释，搅拌下将稀释过的钠水玻璃缓慢加入上述盐酸稀溶液中，得到SiO 2浓度为7.8重量％、pH值为2.8的硅溶胶。
(2)制备催化裂化催化剂：
在以干基计的20重量份的上述硅溶胶中加入以干基计的10重量份的高岭土，搅拌1小时后加入以干基计的40重量份的由制备例5制备的高比热容基质材料AM-5的浆液(固含量为18重量％)混合打浆，之后再向其中加入以干基计的30重量份的所述DASY分子筛浆液(固含量为30重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C5，其中，以所述催化裂化催化剂C5的总重量为基准，所述催化裂化催化剂C5中含有40重量％的高比热容基质材料、30重量％的DASY分子筛、10重量％的高岭土、20重量％的SiO 2粘结剂。
实施例6
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的40重量份的高岭土与以干基计的15重量份的铝溶胶以及以干基计的15重量份的由制备例6制备的高比热容基质材料AM-6的浆液(固含量为20重量％)混合打浆，搅拌120分钟，之后再向其中加入以干基计的30重量份的所述HSY分子筛浆液(固含量为35重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C6，其中，以所述催化裂化催化剂C6的总重量为基准，所述催化裂化催化剂C6中含有15重量％的高比热容基质材料、30重 量％的HSY分子筛、40重量％的高岭土、15重量％的Al 2O 3粘结剂。
实施例7-12
实施例7-12用于说明本发明提供的催化裂化催化剂性能的测试。
将上述制备的催化裂化催化剂C1-C6分别采用Mitchell方法浸渍污染铁5000ppm、镍5000ppm、钒5000ppm，即以环烷酸钒为钒源、环烷酸镍为镍源、环烷酸铁为铁源，甲苯为溶剂，制备含金属溶液，催化剂在含金属溶液中浸渍，然后烘干，再在约600℃下焙烧除去有机质。在780℃、100％水蒸气条件下老化处理6小时，在小型固定流化床上进行裂化性能评价，每个样品的评价过程进行了五次反应-再生循环，即同一个催化剂不卸出的情况下连续进行五次原料油反应和再生过程，取最后一次反应的结果作为催化剂裂化性能评价结果。重油微反的评价条件为：剂油比5(重量比)，样品装量9g，反应温度520℃，WHSV为8小时 -1，进油时间70秒，再生温度720℃，原料油为减压瓦斯油。原料油性质如表2所示。评价结果列于表3中。
对比例4-6
将上述制备的催化裂化参比剂CB1-CB3按照实施例7-12同的方法进行性能测试，评价结果列于表3中。
表2
原料油性质  
密度(20℃)，g/cm 3 0.9154
折光(70℃) 1.4717
凝固点，℃ 37
残炭，m％ 4.3
四组分组成，m％  
饱和烃 63.1
芳烃 21.2
胶质 14.9
沥青质 0.8
元素组成，m％  
C 85.95
H 12.78
原料油性质  
S 0.62
N 0.65
金属元素，(ppm)  
Ca 21.4
Fe 30.6
Mg 0.6
Na 1.5
Ni 7.4
V 11.8
Pb 2.1
表3
实施例编号 7 对比例4 对比例5 对比例6 8 9 10 11 12
催化剂 C1 CB1 CB2 CB3 C2 C3 C4 C5 C6
转化率/w％ 65.19 61.87 62.03 62.47 65.83 64.71 66.78 66.23 64.66
产物收率                  
干气/w％ 1.29 2.28 1.71 1.48 1.31 1.22 1.43 1.30 1.20
液化气/w％ 12.12 9.86 10.03 10.23 12.55 12.45 12.61 12.58 12.17
汽油/w％ 46.52 44.35 44.86 45.21 46.79 46.03 47.28 46.94 46.24
柴油/w％ 19.49 20.16 19.92 19.73 18.64 19.71 18.99 19.07 19.85
油浆/w％ 15.32 17.97 18.05 17.80 15.53 15.58 14.23 14.70 15.49
焦炭/w％ 5.26 5.38 5.43 5.55 5.18 5.01 5.46 5.41 5.05
总液收/w％ 78.13 74.37 74.81 75.17 77.98 78.19 78.88 78.59 78.26
干气选择性 1.98 3.69 2.76 2.36 1.99 1.89 2.14 1.96 1.86
焦炭选择性 8.07 8.70 8.75 8.88 7.87 7.74 8.18 8.17 7.81
H 2/CH 4 0.11 0.2 0.17 0.16 0.13 0.11 0.14 0.12 0.1
表3和表5中，w％为重量％，H 2/CH 4为重量比。
本发明中，转化率＝汽油收率+液化气收率+干气收率+焦炭收率、总液收(又称总液体产品收率)＝汽油收率+柴油收率+液化气收率、焦炭选择性＝焦炭收率/转化率、干气选择性＝干气收率/转化率。
制备例B1
本实例说明本发明提供的高比热容介孔基质材料的制备过程。
将浓度350gAl 2O 3/L的Al 2(SO 4) 3溶液与CO 3 2-浓度为0.10mol/L的碳酸铵溶液于30℃下混合成胶，控制pH值＝7.5，得到浆液BA。向浓度145gMnO 2/L的MnCl 2溶液中加入尿素，尿素与锰离子摩尔比为2，室温下搅拌30分钟，得到溶液BB。将溶液BB加入浆液BA中，80℃、搅拌下陈化24小时，待体系温度降至室温，然后将过滤所得固体沉淀物按固体沉淀物(干基)：H 2O＝1：10的重量比与水混合打浆，并按B 2O 3：高比热容基质材料干基＝0.01:1的重量比加入硼酸铵，再于50℃下搅拌2小时，过滤，将固体沉淀物按沉淀物(干基)：H 2O＝1：8重量比在室温下交换3次，每次交换0.5小时，得到的洗涤后的固体沉淀物为中性，然后于120℃下干燥12小时得基质材料前驱体，然后于550℃下焙烧6小时，随炉冷却至室温得到本发明提供的高比热容基质材料，记为BAM-1。BAM-1的配方、制备参数、比热容、比表面积、孔容及平均孔径列于表4中。
BAM-1的元素分析化学组成表达式以重量计为29.7MnO 2·69.2Al 2O 3·1.1B 2O 3；比热容1.3J/(g·K)，比表面积310m 2/g，孔容0.65cm 3/g，平均孔径8.4nm。
制备例B2-B4
制备例B2-B4用于说明本发明提供的高比热容介孔基质材料的制备过程。
按照制备例B1的方法制备高比热容介孔基质材料BAM-2至BAM-4，不同的是配方、制备参数，其元素组成、比热容、比表面积、孔容及平均孔径列于表4中。
制备例B5
制备例B5用于说明本发明提供的高比热容介孔基质材料的制备过程。
将浓度350gAl 2O 3/L的Al(NO 3) 3溶液与CO 3 2-浓度为0.30mol/L的碳酸铵、OH -浓度为0.1mol/L的氨水溶液混合成胶，控制pH＝10.5，得到浆液BA。将Mn 3O 4与盐酸、水混合，得到浓度201.7gMnO 2/L的氯化锰溶液，控制pH值＝6，然后向溶液中加入尿素，尿素与锰离子摩尔比为3，室温下搅拌40分钟，得到溶液BB。将溶液BB加入浆液BA中，60℃下搅拌陈化24小时，待体系温度降至室温，然后将过滤所得 固体沉淀物按沉淀物(干基)：H 2O＝1：10的重量比与水混合打浆，并按B 2O 3：所得到的高比热容基质材料干基＝0.01：1的重量比加入硼酸铵，再于50℃下搅拌2小时，过滤、水洗(即用水洗涤)，然后于120℃下干燥12小时得基质材料前驱体，然后于650℃下焙烧4小时，随炉冷却至室温得到本发明提供的基质材料，记为BAM-5。BAM-5的配方、制备参数、比热容、比表面积、孔容及平均孔径列于表4中。
BAM-5的元素分析化学组成表达式以重量计为34.8MnO 2·60.4Al 2O 3·4.8B 2O 3；比热容1.43J/(g·K)，比表面积338m 2/g，孔容0.94cm 3/g，平均孔径11.1nm。
制备例B6
制备例B6用于说明本发明提供的高比热容介孔基质材料的制备过程。
按照制备例B5的方法制备基质材料BAM-6，不同的是配方、制备参数，其元素组成、比表面积、孔容及平均孔径列于表4中。
表4
Figure PCTCN2021120144-appb-000003
Figure PCTCN2021120144-appb-000004
实施例13
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的13重量份的拟薄水铝石与去离子水混合打浆(浆液固含量为15重量％)，并向得到的浆液中加入盐酸胶溶，酸铝比(重量比)为0.20：1，然后将温度升至65℃酸化1小时，接着分别加入以干基计的35重量份高岭土的浆液(固含量为25重量％)、以干基计的5重量份的铝溶胶以及以干基计的15重量份的由制备例B1制备的高比热容基质材料BAM-1的浆液(固含量为18重量％)，搅拌20分钟，之后再向其中加入以干基计的32重量份的所述DASY分子筛浆液(固含量为35重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重 量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C19，其中，以所述催化裂化催化剂C19的总重量为基准，所述催化裂化催化剂C19中含有15重量％的高比热容基质材料、32重量％的DASY分子筛、35重量％的高岭土、18重量％的Al 2O 3粘结剂。
实施例14
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的21重量份高岭土与去离子水混合打浆(浆液固含量为40重量％)，再加入以干基计的20重量份的拟薄水铝石，并向得到的浆液中加入盐酸胶溶，酸铝比(重量比)为0.20：1，然后将温度升至65℃酸化1小时，接着分别加入以干基计的4重量份的铝溶胶、以干基计的20重量份的由制备例B2制备的高比热容基质材料BAM-2的浆液(固含量为20重量％)，搅拌20分钟，之后再向其中加入以干基计的35重量份的所述REHY分子筛(固含量为35重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C20，其中，以所述催化裂化催化剂C20的总重量为基准，所述催化裂化催化剂C20中含有20重量％的高比热容基质材料、35重量％的REHY分子筛、21重量％的高岭土、24重量％的Al 2O 3粘结剂。
实施例15
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的28重量份高岭土与去离子水混合打浆(浆液固含量为40重量％)，再加入以干基计的20重量份的拟薄水铝石，并向得到的浆液中加入盐酸进行胶溶，酸铝比(重量比)为0.20：1，然后将温度升至65℃酸化1小时，接着分别加入以干基计的25重量份的由制备例B3制备的高比热容基质材料BAM-3的浆液(固含量为25重量％)，搅拌20分钟，之后再向其中加入以干基计的27重量份的所述HSY分子筛浆液(固含量为35重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下 烘干，得到催化裂化催化剂C21，其中，以所述催化裂化催化剂C21的总重量为基准，所述催化裂化催化剂C21中含有25重量％的高比热容基质材料、27重量％的HSY分子筛、28重量％的高岭土、20重量％的Al 2O 3粘结剂。
实施例16
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的42重量份的高岭土与以干基计的20重量份的铝溶胶以及以干基计的10重量份的由制备例B4制备的高比热容基质材料BAM-4的浆液(固含量为20重量％)混合打浆，搅拌120分钟，之后再向其中加入以干基计的28重量份的所述DASY分子筛浆液(固含量为35重量％)，继续搅拌30分钟后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C22，其中，以所述催化裂化催化剂C22的总重量为基准，所述催化裂化催化剂C22中含有10重量％的高比热容基质材料、28重量％的DASY分子筛、42重量％的高岭土、20重量％的Al 2O 3粘结剂。
实施例17
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
(1)制备硅溶胶：
将1.7L盐酸用8.0kg脱阳离子水进行稀释，将7.7kg钠水玻璃用8.0kg脱阳离子水进行稀释，搅拌下将稀释过的钠水玻璃缓慢加入上述盐酸稀溶液中，得到SiO 2浓度为7.8重量％、pH值为2.8的硅溶胶。
(2)制备催化裂化催化剂：
在以干基计的30重量份的上述硅溶胶中加入以干基计的35重量份的高岭土，搅拌1小时后加入以干基计的10重量份的由制备例B5制备的高比热容基质材料BAM-5的浆液(固含量为18重量％)混合打浆，之后再向其中加入以干基计的25重量份的所述DOSY分子筛浆液(固含量为30重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水 淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C23，其中，以所述催化裂化催化剂C23的总重量为基准，所述催化裂化催化剂C23中含有10重量％的高比热容基质材料、25重量％的DASY分子筛、35重量％的高岭土、30重量％的SiO 2粘结剂。
实施例18
该实施例用于说明本发明提供的催化裂化催化剂及其制备方法。
将以干基计的42重量份的高岭土与以干基计的15重量份的铝溶胶以及以干基计的40重量份的由制备例B6制备的高比热容基质材料BAM-6的浆液(固含量为20重量％)混合打浆，搅拌120分钟，之后再向其中加入以干基计的33重量份的所述REHY分子筛浆液(固含量为35重量％)，继续搅拌后喷雾干燥制成微球催化剂。然后将该微球催化剂在500℃下焙烧1小时，再在60℃下用(NH 4) 2SO 4溶液洗涤(其中，(NH 4) 2SO 4：微球催化剂：H 2O＝0.05：1：10)至Na 2O含量小于0.25重量％，接着用去离子水淋洗并过滤，之后再于110℃下烘干，得到催化裂化催化剂C24，其中，以所述催化裂化催化剂C24的总重量为基准，所述催化裂化催化剂C24中含有40重量％的高比热容基质材料、33重量％的REHY分子筛、42重量％的高岭土、15重量％的Al 2O 3粘结剂。
实施例19-24
实施例25-30用于说明本发明提供的催化裂化催化剂性能的测试。
将上述制备的催化裂化催化剂C19-C24分别采用Mitchell方法浸渍污染铁5000ppm、镍5000ppm、钒5000ppm，在780℃、100％水蒸气条件下老化处理6小时，在小型固定流化床上进行裂化性能评价，每个样品的评价过程进行了五次反应-再生循环，即同一个催化剂不卸出的情况下连续进行五次原料油反应和再生过程，取最后一次反应的结果作为催化剂裂化性能评价结果。重油微反的评价条件为：剂油比5(重量比)，样品装量9g，反应温度520℃，WHSV为8小时 -1，进油时间70秒，再生温度720℃，原料油为减压瓦斯油。原料油性质如表2所示。评价结果列于表5中。
表5
实施例编号 19 20 21 22 23 24
催化剂编号 C19 C20 C21 C22 C23 C24
转化率/w％ 69.32 69.57 68.81 68.45 68.37 69.18
实施例编号 19 20 21 22 23 24
干气/w％ 1.56 1.52 1.52 1.50 1.59 1.54
液化气/w％ 12.86 13.07 12.82 12.71 12.54 12.76
汽油/w％ 49.26 49.36 48.94 48.88 48.62 49.17
柴油/w％ 16.81 16.87 16.71 16.52 16.36 16.58
油浆/w％ 13.87 13.56 14.48 15.03 15.27 14.24
焦炭/w％ 5.64 5.62 5.53 5.36 5.62 5.71
总液收/w％ 78.93 79.30 78.47 78.11 77.52 78.51
干气选择性 2.25 2.18 2.21 2.19 2.33 2.23
焦炭选择性 8.14 8.08 8.04 7.83 8.22 8.25
H 2/CH 4 0.11 0.1 0.12 0.13 0.12 0.11
由表3、表5的结果可见，与沸石含量相同但不含高比热容基质材料的催化剂相比，本发明提供的催化剂具有优异的抗金属污染能力，重油转化能力极大提高，产品分布明显改善，尤其能够明显改善干气、焦炭的选择性，总液收提高，轻质油收率提高。与各组分含量相同但采用的基质材料不同于本发明的基质材料的催化剂相比，本发明提供的催化剂的干气、焦炭产率降低，干气、焦炭选择性得到了明显改善。由此可见，本发明提供的催化裂化催化剂在重油催化裂化的过程中能够表现出更好的抗金属污染能力、催化裂化活性和干气、焦炭选择性较好。本发明提供的催化剂用于重油转化，可以具有更高的总液收，具有更高的汽油和液化气收率。当所述的硼化合物为氧化硼，可以具有更高的汽油收率和转化率。

Claims (15)

  1. 一种催化裂化催化剂，所述催化裂化催化剂含有包括Y型分子筛的裂化活性组元、高比热容基质材料、粘土和粘结剂；所述高比热容基质材料含有至少5重量％的氧化锰，所述高比热容基质材料温度为1000K的比热容为1.3-2.0J/(g·K)，其中，优选地，以所述催化裂化催化剂的总重量为基准，所述催化裂化催化剂含有1-60重量％的裂化活性组元、1-50重量％的高比热容基质材料、1-70重量％的粘土和1-70重量％的粘结剂，或者，以所述催化裂化催化剂的总重量为基准，所述催化裂化催化剂含有10-50重量％的裂化活性组元、5-40重量％的高比热容基质材料、10-60重量％的粘土和10-60重量％的粘结剂。
  2. 按照前述权利要求中任一项所述的催化裂化催化剂，其中，所述高比热容基质材料含有以Al 2O 3计5-95重量％的氧化铝，以MnO 2计5-95重量％氧化锰以及以干基计0-40重量％的硼化合物，其中优选地，所述的硼化合物为氮化硼和/或氧化硼。
  3. 按照前述权利要求中任一项所述的催化裂化催化剂，其中，所述高比热容基质材料的比表面积为150-500m 2·g -1；和/或，所述高比热容基质材料的孔体积为0.3-1.5cm 3·g -1；和/或，所述高比热容基质材料的平均孔直径为3-20nm。
  4. 按照前述权利要求中任一项所述的催化裂化催化剂，其中，所述高比热容基质材料的XRD图谱，在2θ角为18±0.5°和2θ角为37±0.5°处峰的强度比为1:(3-10)。
  5. 按照前述权利要求中任一项所述的催化裂化催化剂，其中，所述高比热容基质材料的制备方法，包括下述步骤:
    (1)使铝源与碱混合成胶，得到含铝胶体，所得含铝胶体的pH值为7-11；
    (2)使pH值为3-7的锰盐溶液与尿素混合，得到锰源溶液；
    (3)使含铝胶体、锰源溶液、任选的硼化合物形成混合物；和任选的
    (4)洗涤和/或干燥和/或焙烧。
  6. 按照前述权利要求5中任一项所述的催化裂化催化剂，其中，在步骤(1)中，
    所述使铝源与碱混合成胶包括：将铝源溶液、碱的溶液混合，形成温度为室温至85℃、pH值为7-11的胶体；和/或，
    所述铝源溶液中氧化铝的浓度为150-350gAl 2O 3/L，碱的溶液中碱的浓度为0.1-1mol/L；和/或，
    所述的铝源选自硝酸铝、硫酸铝、磷酸铝和氯化铝等中的一种或多种；所述的碱为(可)溶于水的碳酸盐、(可)溶于水的碳酸氢盐、(可)溶于水的氢氧化物中的一种或多种，其中，优选地，所述碱的溶液选自含有CO 3 2-、HCO 3 -或OH -中的一种或多种的碱性水溶液，所述碱的溶液中CO 3 2-的浓度为0-0.6mol/L，OH -的浓度为0-0.5mol/L，HCO 3 -的浓度为0-1mol/L。
  7. 按照前述权利要求5-6中任一项所述的催化裂化催化剂，其中，步骤(2)中，
    尿素与锰离子摩尔比为1-5例如为2-4，所述锰盐溶液中锰盐的浓度以MnO 2计可以为50-500g·L -1。
  8. 按照前述权利要求5-7中任一项所述的催化裂化催化剂，其中，步骤(2)在所述锰盐溶液中加入尿素，然后在室温搅拌30-60分钟，得到锰源溶液。
  9. 按照前述权利要求5-8中任一项所述的催化裂化催化剂，其中，所述的硼化合物为氮化硼和/或氧化硼和/或氧化硼前驱体，
    其中，优选地，所述的氮化硼为六方氮化硼、立方氮化硼、菱方氮化硼和纤锌矿氮化硼中的一种或多种；所述氧化硼前驱体为硼酸铵、硼酸氢铵或硼酸中的一种或多种。
  10. 按照前述权利要求5-9中任一项所述的催化裂化催化剂，其中，步骤(3)中在将含铝胶体、锰源溶液混合后还包括陈化的过程，所述陈化温度为室温至120℃，陈化时间为4-72小时，在搅拌下陈化或静置陈化；优选的，所述陈化在搅拌下进行，陈化温度为60-100℃，陈化时间为12-36小时。
  11. 按照前述权利要求5-9中任一项所述的催化裂化催化剂，其中，所述的硼化合物为氮化硼；步骤(3)使含铝胶体、锰源溶液、硼化合物形成混合物的方法如下：将含铝胶体、锰源溶液和硼化合物混合，陈化；或
    所述的硼化合物为氧化硼和/或氧化硼的前身物，步骤(3)所述使含 铝胶体、锰源溶液、硼化合物形成混合物的方法如下：将含铝胶体、锰源溶液混合，陈化，任选洗涤，然后与硼化合物混合。
  12. 按照前述权利要求5-9中任一项所述的催化裂化催化剂，其中，步骤(4)中所述焙烧温度500℃-900℃，焙烧时间为4-8小时。
  13. 按照前述权利要求1-4中任一项所述的催化裂化催化剂，其中，所述裂化活性组元含有Y型分子筛，任选地，所述裂化活性组元还含有第二分子筛，所述第二分子筛为八面沸石、Beta沸石、MFI结构分子筛和丝光沸石中的一种或多种；
    其中，优选地，以所述裂化活性组元的总重量为基准，所述Y型分子筛的含量为75重量％以上，所述第二分子筛的含量为25重量％以下。
  14. 按照前述权利要求1-13中任一项所述的催化裂化催化剂的制备方法，该方法包括将所述裂化活性组元、高比热容基质材料、粘土和粘结剂混合打浆，然后再依次进行喷雾干燥、焙烧、洗涤、过滤和干燥。
  15. 按照前述权利要求1-13中任一项所述的催化裂化催化剂在重油催化裂化中的应用。
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115555011A (zh) * 2022-08-24 2023-01-03 碳中能源科技(北京)有限公司 一种提高fcc催化剂抗重金属污染性能助剂
CN116273142A (zh) * 2023-03-06 2023-06-23 青岛惠城环保科技集团股份有限公司 一种增产柴油催化裂化催化剂的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1566274A (zh) * 2003-06-30 2005-01-19 中国石油化工股份有限公司 一种多产低碳烯烃的烃油裂化方法
CN1566277A (zh) * 2003-06-30 2005-01-19 中国石油化工股份有限公司 一种烃油裂化方法
CN1600839A (zh) * 2003-09-28 2005-03-30 中国石油化工股份有限公司 一种烃油裂化方法
CN101773845A (zh) * 2009-01-08 2010-07-14 中国石油化工股份有限公司 一种重油裂化催化剂及其制备和应用方法
CN101822998A (zh) * 2009-03-02 2010-09-08 中国石油化工股份有限公司 一种重油裂化催化剂及其制备方法
CN106179478A (zh) * 2015-04-29 2016-12-07 中国石油化工股份有限公司 一种裂化气化催化组合物、其制备方法及石油烃的裂化气化方法

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1267190C (zh) * 2003-04-29 2006-08-02 中国石油化工股份有限公司 一种含分子筛和锰的裂化催化剂
TWI277648B (en) * 2004-07-29 2007-04-01 China Petrochemical Technology A cracking catalyst for hydrocarbons and its preparation
US8809216B2 (en) * 2008-01-09 2014-08-19 China Petroleum & Chemical Corporation Catalyst for converting acid-containing inferior crude oil and process for making and using the same
CN105214712B (zh) * 2014-05-29 2017-12-22 中国石油化工股份有限公司 一种催化裂化催化剂及其制备方法和应用
CN105312076B (zh) * 2014-05-29 2018-01-05 中国石油化工股份有限公司 一种催化裂化催化剂及其制备方法和应用
CN105268468B (zh) * 2014-05-29 2018-03-20 中国石油化工股份有限公司 一种催化裂化催化剂及其制备方法和应用
CN105148984B (zh) * 2014-05-29 2018-05-18 中国石油化工股份有限公司 一种催化裂化催化剂及其制备方法和应用
CN106179476B (zh) * 2015-04-29 2018-08-28 中国石油化工股份有限公司 一种催化裂化催化剂及其制备方法和应用
US11111152B2 (en) * 2015-08-05 2021-09-07 Petrochina Company Limited Preparation method for modified molecular sieve and modified molecular sieve-containing catalytic cracking catalyst
CN107303502B (zh) * 2016-04-18 2020-09-04 中国石油天然气股份有限公司 一种高固含量催化裂化催化剂的制备方法
BR112019008626A2 (pt) * 2016-10-31 2019-07-09 Johnson Matthey Plc composição de catalisador, artigo catalítico, sistema e método para tratamento de um gás de escape, motor, e, veículo.

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1566274A (zh) * 2003-06-30 2005-01-19 中国石油化工股份有限公司 一种多产低碳烯烃的烃油裂化方法
CN1566277A (zh) * 2003-06-30 2005-01-19 中国石油化工股份有限公司 一种烃油裂化方法
CN1600839A (zh) * 2003-09-28 2005-03-30 中国石油化工股份有限公司 一种烃油裂化方法
CN101773845A (zh) * 2009-01-08 2010-07-14 中国石油化工股份有限公司 一种重油裂化催化剂及其制备和应用方法
CN101822998A (zh) * 2009-03-02 2010-09-08 中国石油化工股份有限公司 一种重油裂化催化剂及其制备方法
CN106179478A (zh) * 2015-04-29 2016-12-07 中国石油化工股份有限公司 一种裂化气化催化组合物、其制备方法及石油烃的裂化气化方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115555011A (zh) * 2022-08-24 2023-01-03 碳中能源科技(北京)有限公司 一种提高fcc催化剂抗重金属污染性能助剂
CN116273142A (zh) * 2023-03-06 2023-06-23 青岛惠城环保科技集团股份有限公司 一种增产柴油催化裂化催化剂的制备方法

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