CN114425400A - Wear-resistant catalytic cracking catalyst, and preparation method and application thereof - Google Patents

Wear-resistant catalytic cracking catalyst, and preparation method and application thereof Download PDF

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CN114425400A
CN114425400A CN202011020394.9A CN202011020394A CN114425400A CN 114425400 A CN114425400 A CN 114425400A CN 202011020394 A CN202011020394 A CN 202011020394A CN 114425400 A CN114425400 A CN 114425400A
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catalytic cracking
cracking catalyst
molecular sieve
heat capacity
specific heat
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CN114425400B (en
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刘倩倩
宋海涛
陈振宇
刘守军
朱玉霞
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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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    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
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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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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
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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
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta

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Abstract

The invention provides a wear-resistant catalytic cracking catalyst and a preparation method and application thereof, wherein the catalytic cracking catalyst contains 1-60 wt% of cracking active components, 1-50 wt% of high specific heat capacity matrix material, 1-70 wt% of clay and 1-70 wt% of binder; the matrix material contains 5-94.5 wt.% alumina, 5-94.5 wt.% manganese oxide, and 0.5-10 wt.% phosphorus oxide, and the cracking active component includes a first molecular sieve and optionally a second molecular sieve. The preparation method comprises the following steps: and (3) spray drying the cracking active component, the high specific heat capacity matrix material, the clay and the binder to form slurry. The catalytic cracking catalyst has good abrasion resistance, better heavy oil conversion capacity in the heavy oil catalytic cracking process and good selectivity.

Description

Wear-resistant catalytic cracking catalyst, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalytic cracking, and relates to a catalytic cracking catalyst, and a preparation method and application thereof.
Background
With the increasing shortage of petroleum resources and the rising price of crude oil, large refineries can achieve maximum benefit by deeply processing heavy oil and using inferior oil to reduce cost, and catalytic cracking is an important means for processing heavy oil at present.
However, the heavy metal (such as vanadium and nickel) content of the crude oil with poor quality is generally high, and particularly in recent years, the phenomenon of metal poisoning of the catalytic cracking catalyst is increasingly common due to the heavy conversion and the increased deterioration degree of the crude oil and the processing of the opportunity crude oil. Many research results show that once metals such as iron and nickel are deposited on the surface, the metals are difficult to migrate and can interact with elements such as silicon, aluminum, vanadium, sodium and the like to form low-melting-point eutectic substances, so that the surface of the catalyst is sintered, a dense layer with the thickness of 2-3 mu m is further formed on the surface, channels for reactants to enter the catalyst and products to diffuse are blocked, and the product distribution is deteriorated. Serious metal pollution can lead to the problems of poor fluidization performance of the catalyst, reduced accessibility of active centers, poor selectivity of the catalyst, increased yield of dry gas and coke and the like, and the risk of shutdown of the existing device is even faced.
In order to reduce the influence of metals in oil products on catalytic cracking, metal trapping components are added in the prior art to eliminate or weaken the influence, however, most of the metal trapping components also influence the activity of the catalyst, so that the metal trapping components are mostly introduced into a catalyst system in a form of a single auxiliary agent, and when the metal trapping components are directly introduced into the catalyst, the addition is strictly limited, and the metal trapping components often cannot exert the expected effect.
CN101939095A discloses a molecular sieve catalyst and a preparation method thereof to prepare light olefins by catalytically cracking naphtha in a severe environment of high temperature and high humidity. Specifically, the catalyst is prepared by spray-drying and calcining a mixed slurry in which 0.01 to 5.0 wt% of MnO is added2And 1-15% by weight of P2O5While being embedded in a catalyst composed of zeolite, clay and an inorganic composite. Which mixes manganese and phosphorus in a catalyst slurry in a dissolved form, has a very limited effect on the improvement of the catalyst, and is mainly used for naphtha conversion without involving heavy oil conversion.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a wear-resistant heavy oil catalytic cracking catalyst, which has better wear resistance and good catalytic cracking performance. The invention aims to solve the other technical problems of providing a preparation method of the catalytic cracking catalyst and an application of the catalytic cracking catalyst in heavy oil catalytic cracking.
The invention provides a catalytic cracking catalyst, which comprises 1-60 wt% of cracking active components, 1-50 wt% of high specific heat capacity matrix material, 1-70 wt% of clay and 1-70 wt% of binder, wherein the total weight of the catalytic cracking catalyst is taken as a reference; the high specific heat capacity matrix material contains 5-94.5 wt% of alumina in MnO25-94.5% by weight, calculated as P, of manganese oxide2O50.5-10 wt% phosphorus oxide, the high specific heat capacity host material has a specific heat capacity of 1.3-2.0J/(g.K) at a temperature of 1000K, the cracking active component comprises a first molecular sieve and optionally a second molecular sieve, and the first molecular sieve is a Y-type molecular sieve.
The catalytic cracking catalyst according to the above technical scheme, wherein the specific surface area of the high specific heat capacity matrix material is 300-500m2·g-1Or 330-400m2·g-1。
The catalytic cracking catalyst according to any of the preceding claims, wherein the high specific heat capacity matrix material has a pore volume of 0.5-1.5cm3/g。
The catalytic cracking catalyst according to any of the preceding claims, wherein the high specific heat capacity matrix material has an average pore diameter of 3-20nm or 9-13 nm.
The catalytic cracking catalyst of any of the above claims, wherein the XRD pattern of the high specific heat capacity matrix material has an intensity ratio of 1 for peaks at an angle 2 θ of 18 ± 0.5 ° and an angle 2 θ of 37 ± 0.5 °: (3-10).
The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the steps of mixing and pulping the cracking active component, the high specific heat capacity matrix material, the clay and the binder, and then carrying out spray drying, washing, filtering and drying.
The preparation method of the catalytic cracking catalyst according to the above technical scheme, wherein the high specific heat capacity matrix material can be prepared by a preparation method comprising the following steps:
(5) mixing an aluminum source and alkali into glue to obtain an aluminum-containing colloid, wherein the pH value of the aluminum-containing colloid is 7-11;
(6) mixing a manganese salt solution with the pH value of 3-7 with urea to obtain a manganese source solution;
(7) forming a mixture of an aluminum-containing colloid, a manganese source solution and optionally boron nitride, and aging;
(8) the aged solid precipitate is contacted with a source of phosphorus, optionally washed and/or dried and/or calcined.
The preparation method of the catalytic cracking catalyst according to any of the above technical solutions, wherein the mixing the aluminum source and the alkali into the gel comprises: mixing the aluminum source solution and the alkali solution to form colloid with the temperature of room temperature to 85 ℃ and the pH value of 7-11.
According to the invention, the room temperature is 15-40 ℃.
The method for preparing a catalytic cracking catalyst according to any of the above technical solutions, wherein the concentration of alumina in the aluminum source solution is preferably 150-350gAl2O3/L。
The method for preparing a catalytic cracking catalyst according to any of the preceding claims, wherein the concentration of the base in the base solution is preferably 0.1-1 mol/L.
The method for preparing a catalytic cracking catalyst according to any of the above claims, wherein the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride, etc.; the alkali can be one or more of carbonate dissolved in water, bicarbonate dissolved in water and hydroxide dissolved in water.
The method for preparing a catalytic cracking catalyst according to any of the preceding claims, wherein the solution of the base preferably contains CO3 2-、HCO3 -Or OH-An alkaline aqueous solution of one or more of (a) and (b), the solution of the base being CO3 2-Has a concentration of 0-0.6mol/L, OH-The concentration of (A) is 0-0.5mol/L, HCO3 -The concentration of (b) is 0 to 1 mol/L.
The method for preparing a catalytic cracking catalyst according to any of the above technical solutions, wherein in the step (2), the molar ratio of urea to manganese ions is preferably 1-5, for example 2-4. The concentration of manganese salt in the manganese salt solution is MnO2The amount can be 50-500 g.L-1。
The preparation method of the catalytic cracking catalyst according to any one of the above technical schemes, wherein in one embodiment, the step (2) comprises adding urea into the manganese salt solution, and then stirring at room temperature for 30-60 minutes to obtain a manganese source solution.
The preparation method of the catalytic cracking catalyst according to any of the above technical solutions, wherein in the step (3), the aging temperature may be room temperature to 120 ℃, preferably 60-100 ℃. Preferably, aging is carried out with stirring.
The preparation method of the catalytic cracking catalyst according to any of the above technical solutions, wherein the aging time of the aging is preferably 4-72 hours, and the aging time is preferably 12-36 hours.
The method for preparing a catalytic cracking catalyst according to any of the above technical solutions, wherein the aging solid precipitate is contacted with a phosphorus source, according to an embodiment, the method comprises the following steps: mixing the aged solid precipitate with water according to the dry basis of the aged solid precipitate: water 1: (2-5), pulping, mixing the phosphorus source and the slurry at room temperature to 90 ℃, and stirring or standing for 0.2-5 hours.
The preparation method of the catalytic cracking catalyst according to any of the above technical solutions, wherein the manganese salt may be selected from one or more of manganese nitrate, manganese sulfate, manganese phosphate, manganese chloride, and the like, the boron nitride may be selected from at least one of hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), rhombohedral boron nitride (r-BN), and wurtzite boron nitride (w-BN), and the phosphorus source may be selected from one or more of ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate, or phosphoric acid.
The preparation method of the catalytic cracking catalyst according to any one of the above technical schemes, wherein the calcination in the step (4), in one embodiment, is carried out at a calcination temperature of 500-900 ℃ for 4-8 hours.
The 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 matching the cracking active component with a specific high specific heat capacity material, clay and a binder, is beneficial to the atomization and cracking of heavy oil macromolecules in a reactor, and has better wear resistance. The catalytic cracking catalyst provided by the invention is used for heavy oil catalytic cracking, and has better heavy oil conversion capacity and higher light oil yield; the catalyst also has higher capacity of resisting pollution of various metals, and has higher heavy oil conversion rate, higher light oil yield, higher total liquid yield and good selectivity of dry gas and coke under the condition of pollution of vanadium, Ni and iron.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention provides a catalytic cracking catalyst, wherein the catalytic cracking catalyst comprises, based on the total weight of the catalytic cracking catalyst, on a dry basis, from 1 to 60% by weight of cracking active components, from 1 to 50% by weight, for example from 5 to 45% by weight, of a high specific heat capacity matrix material, from 1 to 70% by weight of clay, and from 1 to 70% by weight of a binder. The high specific heat capacity matrix material contains 5-94.5 wt% of alumina in MnO25-94.5% by weight, calculated as P, of manganese oxide2O50.5-10 wt% of phosphorus oxide, wherein the specific heat capacity of the high specific heat capacity matrix material at the temperature of 1000K is 1.3-2.0J/(g.K). The high specific heat capacity matrix material and the cracking active component are in the same particle.
The dry basis is a nonvolatile solid product obtained after the material is roasted for 1 hour at 800 ℃.
According to the catalytic cracking catalyst provided by the invention, preferably, the catalytic cracking catalyst contains 10-50 wt% of cracking active components, 5-45 wt% or 5-40 wt% or 10-45 wt% of high specific heat capacity matrix material, 10-60 wt% of clay and 10-60 wt% of binder, based on the total weight of the catalytic cracking catalyst, and the content of the components is controlled within the preferable range, so that the obtained catalytic cracking catalyst has better comprehensive performance.
According to the catalytic cracking catalyst provided by the invention, the high specific heat capacity matrix material contains Al2O35-94.5% by weight of alumina and in MnO25-94.5% by weight manganese oxide, 0-40% by weight boron nitride on a dry basis and P2O50.5-10 wt% phosphorus oxide, for example, the high specific heat capacity matrix material comprises 15-70 wt%, or 20-65 wt%, or 30-61 wt% manganese oxide and 29-84 wt%, or 35-80 wt%, or 39-70 wt% alumina, 5-35 wt% boron nitride and 1-8 wt% phosphorus oxide.
According to the catalytic cracking catalyst provided by the invention, the specific heat capacity of the high specific heat capacity matrix material is 1.3-2.0J/(g.K). The high specific heat capacity matrix material (for short, matrix material) may or may not contain boron nitride.
According to the present invention, there is provided a catalytic cracking catalyst, in a first embodiment, the matrix material with high specific heat capacity comprises Al2O35-94.5% by weight of alumina, expressed as MnO25-94.5% by weight calculated as oxides of manganese and in P2O50.5-10 wt% calculated phosphorus oxide, and no boron nitride. For example, the high specific heat capacity matrix material comprises 15-70 wt% or 20-65 wt% or 25-60 wt% manganese oxide, 29-84 wt% or 35-80 wt% or 39-74 wt% alumina, and 0.8-8 wt% phosphorus oxide.
According to the catalytic cracking catalyst provided by the invention, in a first embodiment, the specific surface area of the high specific heat capacity matrix material is 250-400m2·g-1E.g. 280-350m2·g-1. The pore volume of the high specific heat capacity substrate material is 0.5-1.0cm3Per g, for example, 0.55 to 0.8cm3(ii) in terms of/g. The high specific heat capacity matrix material has an average pore diameter of 3 to 12nm, for example 6 to 10 nm.
According to a second embodiment of the catalytic cracking catalyst of the present invention, the matrix material with high specific heat capacity comprises boron nitride, and has a specific heat capacity of 1.3-2.0J/(g.K), for example, 1.4-1.96J/(g.K) or 1.51-1.96J/(g.K). The anhydrous chemical expression of the high specific heat capacity matrix material in weight ratio can be expressed as (5-94) Al2O3·(5-94)MnO2·(0.5-40)BN·(0.5-10)P2O5For example, it may be (20-80) Al2O3·(15-75)MnO2·(5-30)BN·(1-8)P2O5. Preferably, the high specific heat capacity matrix material contains 5-94 wt.% alumina, 5-94 wt.% manganese oxide, 0.5-10 wt.% phosphorus oxide, and greater than 0 and not more than 40 wt.%, e.g., 0.5-35 wt.% boron nitride on a dry basis, based on the weight of the high specific heat capacity matrix material. For example, the high specific heat capacity matrix material contains 15-80 wt% of alumina and 15-70 wt%Manganese oxide, 0.8-9 wt% phosphorus oxide and 5-30 wt% boron nitride; further, the high specific heat capacity matrix material contains 19-74 wt% of alumina, 0.8-8 wt% of phosphorus oxide, 15-60 wt% of manganese oxide and 8-26 wt% of boron nitride. The matrix material contains boron nitride, so that the abrasion resistance of the catalyst can be greatly improved.
According to a second embodiment of the catalytic cracking catalyst provided by the present invention, the high specific heat capacity matrix material has a specific surface area of 300-500m2·g-1For example 320-450m2·g-1Or 330-400m2·g-1The pore volume of the high specific heat capacity matrix material is 0.5-1.5cm3·g-1For example 0.8-1.3cm3·g-1Or 0.9-1.25cm3·g-1The high specific heat capacity matrix material has an average pore diameter of 3-20nm, for example 5-18nm or 7-15nm or 9-13nm or 11-13 nm.
According to the catalytic cracking catalyst provided by the invention, the preparation method of the matrix material with high specific heat capacity comprises the following steps:
(1) mixing an aluminum source solution and an alkali solution at room temperature to 85 ℃ to form colloid, and controlling the pH value of the colloid formed by the colloid to be 7-11;
(2) preparing a manganese salt solution with the pH value of 3-7, mixing the manganese salt solution with urea, and stirring; the molar ratio of urea to manganese ions is 1-5; the temperature at which the manganese salt solution is mixed with the urea is not particularly critical, for example the mixing is carried out at room temperature, the stirring time being for example 30 to 60 minutes;
(3) mixing the product obtained in the step (1), the product obtained in the step (2) and optional boron nitride, and aging at room temperature to 120 ℃ for 4-72 hours; and
(4) and (4) filtering the aged product obtained in the step (3), optionally carrying out first washing to obtain aged solid precipitate, contacting the aged solid precipitate with a phosphorus source, optionally carrying out second washing, drying and roasting to obtain the high specific heat capacity matrix material.
In the specific implementation mode of the preparation method of the matrix material with high specific heat capacity, the step (1)The alkali solution can be selected widely, preferably, the alkali solution in the step (1) contains CO3 2-、 HCO3 2-And OH-More preferably, the alkaline aqueous solution is an aqueous solution containing one or more of ammonium bicarbonate, ammonium carbonate, sodium hydroxide and potassium hydroxide, or a mixed solution of one or more of ammonium carbonate, sodium hydroxide and potassium hydroxide and ammonia water. In one embodiment, the alkali solution is CO3 2-The concentration of (B) is 0 to 0.6mol/L, for example 0.3 to 0.5 mol/L; OH group-In a concentration of 0 to 0.5mol/L, for example 0.2 to 0.35mol/L, HCO3 2-The concentration of (B) is 0 to 1.0mol/L, for example, 0.4 to 1.0 mol/L. Preferably, the total concentration of alkali in the alkali solution is 0.1-1 mol/L. The pH of the colloid obtained by gelling in step (1) is preferably from 7.5 to 11, for example from 8.5 to 11 or from 9 to 10. And when the ammonia water is selected, assuming that the ammonia water is completely ionized, and calculating the required addition amount of the ammonia water according to the calculated hydroxyl.
In the specific embodiment of the method for preparing the high specific heat capacity matrix material, the variety of the aluminum source can be widely selected, and a water-soluble aluminum source capable of dissolving in water can be used in the present invention, for example, the aluminum salt is selected from one or more of aluminum nitrate, aluminum sulfate, aluminum phosphate and aluminum chloride, preferably one or more of aluminum nitrate, aluminum sulfate and aluminum chloride.
In the specific embodiment of the preparation method of the matrix material with high specific heat capacity, in the step (2), a manganese salt solution with a specific pH value is mixed with urea to form a mixture, and the pH value of the manganese salt solution is 3-7, preferably 5-7. The conditions for mixing urea with the manganese salt solution can be selected from a wide range, and for the present invention, in one embodiment, the mixing method in step (2) comprises: adding urea into the manganese salt solution, and stirring at room temperature for 40-60 minutes, wherein the molar ratio of urea to manganese ions is preferably 2-4. The manganese salt solution in the step (2) can be selected from water solution of water-soluble manganese salt and/or salt solution formed after manganese oxide and manganese hydroxide are contacted with acid. The kind of the manganese salt is wide in the optional range, and a water-soluble manganese salt capable of dissolving in water, such as one or more of manganese nitrate, manganese sulfate, manganese phosphate, manganese chloride, or the like, preferably one or more of manganese nitrate, manganese sulfate, manganese chloride, or the like, may be used in the present invention. The manganese salt solution can also be prepared by contacting manganese oxide, such as one or more of manganese monoxide, trimanganese tetroxide, manganomanganic oxide, manganese dioxide, and/or manganese hydroxide with an acid, such as one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, preferably one or more of hydrochloric acid, sulfuric acid, nitric acid.
In the specific implementation mode of the preparation method of the matrix material with high specific heat capacity, the product obtained in the step (1) in the step (3) is Al2O3Metering the product obtained in the step (2) with MnO2The proportion of the boron nitride to the weight of the boron nitride on a dry basis is (5-95) Al2O3：(5-95)MnO2: (0-40) BN is, for example, (20-80) Al2O3：(15-75)MnO2: (5-30) BN or (20-70) Al2O3：(15-60) MnO2：(8-25)BN。
In the specific embodiment of the method for preparing the matrix material with high specific heat capacity, the aging conditions in the step (3) are wide in optional range, and preferably, the aging conditions in the step (3) comprise: aging at 60-100 deg.C for 12-36 hr under stirring. There is no particular requirement for the manner of stirring, for example, the stirring speed may be from 50 to 300 revolutions per minute.
In a specific embodiment of the method for preparing the high specific heat capacity matrix material, the boron nitride is selected from one or more of hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), rhombohedral boron nitride (r-BN) and wurtzite boron nitride (w-BN).
In the specific implementation mode of the preparation method of the matrix material with high specific heat capacity, in the step (4), the aged product obtained in the step (3) is filtered, and optionally subjected to first washing to obtain an aged solid precipitate, and then the aged solid precipitate is contacted with a phosphorus source, and optionally subjected to second washing. Wherein said phosphorus source is P2O5The weight ratio of the material feeding amount to the dry basis of the high specific heat capacity matrix material is (0.005-0.1): 1. preferably, step (ii)(3) The product obtained in step (1), the product obtained in step (2), the boron nitride and the phosphorus source are used in amounts such that the matrix material obtained is prepared containing 5 to 94% by weight, for example 15 to 80% by weight or 19 to 74% by weight or 20 to 80% by weight, of alumina, in MnO25-94% by weight, such as 15-75% by weight or 15-70% by weight or 14-66% by weight, manganese oxide, more than 0 and not more than 40% by weight, such as 0.5-35% by weight or 5-30% by weight or 8-26% by weight, boron nitride and P2O50.5-10% by weight of phosphorus oxide. The first wash or the second wash may be washed with water, preferably the wash renders the wash solution neutral (neutral means a pH of 6.5-7.5) after washing, for example by rinsing with deionized water until the deionized water after washing is neutral. Preferably, the first and second washes are performed at least once, preferably at least the first wash is performed.
In the specific embodiment of the preparation method of the matrix material with high specific heat capacity, in the step (4), the aged solid precipitate is contacted with a phosphorus source, and the preferable process comprises the following steps of treating the obtained solid precipitate according to the proportion of the precipitate (dry basis): h2O is 1: (2-5) mixing the mixture with water according to the weight ratio, pulping, adding a phosphorus source into the slurry, carrying out contact treatment (for example, stirring) at room temperature to 90 ℃ for 0.2-5 hours, preferably 0.5-3 hours, optionally filtering, and optionally carrying out secondary washing; alternatively, the aged solid precipitate can be directly mixed with phosphorus source in proportion and ground uniformly. Wherein with P2O5The weight ratio of the phosphorus source to the aged solid precipitate on a dry basis may be 0.005-0.1: 0.9-0.995.
In one embodiment of the method for preparing the high specific heat capacity matrix material, the phosphorus source comprises a phosphorus-containing compound, and the phosphorus-containing compound can be one or more of ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate or phosphoric acid.
In the specific implementation mode of the preparation method of the matrix material with high specific heat capacity, the optional range of the drying condition and the roasting condition in the step (4) is wide. The drying and roasting methods can be carried out according to the prior art, and the invention has no special requirement for the method. For example, the drying conditions in step (4) include: drying at 100-150 deg.C for 6-24 hr; the roasting conditions in the step (4) comprise: calcining at 550-800 deg.C, such as 550-750 deg.C, for 4-8 h.
According to the catalytic cracking catalyst provided by the invention, the cracking active component contains a first molecular sieve, and the first molecular sieve is a Y-type molecular sieve. The type of the Y-type molecular sieve may be selected conventionally in the art, and for example, may be one or more of a rare earth-containing Y-type molecular sieve (e.g., REHY molecular sieve), a phosphorus-and rare earth-containing Y-type molecular sieve (e.g., DOSY molecular sieve), an ultrastable Y-type molecular sieve (e.g., DASY molecular sieve), a phosphorus-and/or rare earth-containing ultrastable Y-type molecular sieve, and the like. For example, the Y-type molecular sieve is one or more of REY molecular sieve, REHY molecular sieve, DASY molecular sieve, RE-DASY molecular sieve, USY molecular sieve, RE-USY molecular sieve, PSRY molecular sieve, HSY molecular sieve and SOY molecular sieve, and optionally, the cracking active component can also contain a second molecular sieve, wherein the second molecular sieve is one or more of faujasite, Beta zeolite, MFI structure molecular sieve (such as ZRP-1 molecular sieve) and mordenite besides the Y molecular sieve. Wherein the content of the Y-type molecular sieve is more than 75 wt%, preferably more than 90 wt%, and more preferably more than 95 wt% based on the total weight of the cracking active component; the content of the second molecular sieve may be 25 wt% or less, preferably 10 wt% or less, more preferably 5 wt% or less.
According to the catalytic cracking catalyst provided by the invention, the clay can be various clays which can be used in the catalytic cracking catalyst, for example, one or more selected from kaolin, halloysite, montmorillonite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite can be selected.
According to the catalytic cracking catalyst provided by the invention, the binder can be various existing binders capable of being used in the catalytic cracking catalyst, and for example, the binder can be selected from one or more of silica sol, aluminum sol and boehmite.
In the catalytic cracking catalyst provided by the inventionMay contain added rare earths. The added rare earth may be formed by additionally adding rare earth chloride during the preparation of the catalytic cracking catalyst. In the catalytic cracking catalyst, the added rare earth is usually in the form of a rare earth oxide (RE)2O3) Exist in the form of (1). The added rare earth may be present in an amount of 0 to 3 wt.%, preferably 0.5 to 2 wt.%, calculated as rare earth oxide, based on the dry weight of the catalytic cracking catalyst. Wherein, the rare earth element in the additional rare earth refers to various conventional rare earth elements involved in the field of catalytic cracking catalysts, and for example, one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium and europium can be used.
The preparation method of the catalytic cracking catalyst provided by the invention comprises the steps of mixing and pulping the cracking active component, the high specific heat capacity matrix material, the clay and the binder, and then sequentially carrying out spray drying, washing, filtering and drying. In addition, when the catalytic cracking catalyst also contains added rare earth, the preparation method of the catalytic cracking catalyst provided by the invention also comprises the steps of mixing and pulping the rare earth chloride, the cracking active component, the mesoporous active silicoaluminophosphate material, the clay and the binder, and then sequentially carrying out spray drying, washing, filtering and drying.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the cracking active component, the high specific heat capacity matrix material, the clay and the binder and the optional rare earth chloride are mixed and pulped, and then spray drying, washing, filtering and drying are carried out, and the implementation methods of the working procedures can be implemented by adopting the conventional methods, and the specific implementation methods of the working procedures are fully described in CN1916166A, CN1362472A, CN1132898C, CN1727442A, CN1098130A and CN1727445A, which are also incorporated into the invention by reference. In addition, generally, the preparation method of the catalytic cracking catalyst after the spray drying and before the washing generally further includes a step of calcining the spray-dried product. The calcination conditions generally include that the calcination temperature may be 500 to 700 ℃ and the calcination time may be 1 to 4 hours.
In addition, the invention also provides the application of the catalytic cracking catalyst in the catalytic cracking of heavy oil.
The invention provides a method for applying the catalytic cracking catalyst in heavy oil catalytic cracking, which comprises the step of carrying out contact reaction on the catalytic cracking catalyst and heavy oil, such as one or more of vacuum residue, vacuum gas oil, atmospheric residue, atmospheric gas oil and deasphalted oil. Reaction conditions of the contact reaction include: the reaction temperature is 480-530 deg.C, such as 490-520 deg.C, the ratio of the reagents to the oil (by weight) is 3-10, such as 4-8, and the reaction time is 0.5-15 seconds, preferably 1-5 seconds.
The present invention will be described in detail below by way of examples.
The raw materials used in the following preparations, comparative preparations, examples and comparative examples are as follows:
the hydrochloric acid is produced by a Beijing chemical plant, is chemically pure and has the concentration of 36 weight percent;
sodium water glass is commercially available, SiO2The concentration is 26.0 weight percent, and the modulus is 3.2;
kaolin, a product of Suzhou Kaolin corporation, has a solids content of 74.0 wt%;
the pseudoboehmite is an industrial product of Shandong aluminum factories, and the solid content is 62.0 percent by weight;
the aluminum sol is Al, a product of Chinese petrochemical catalyst Qilu division2O3The content was 21.5 wt%;
DASY molecular sieve (solid content 92.0 wt%, RE)2O3The content was 1.8% by weight, Na2O content of 1.0 wt%, crystallinity of 60%), ZRP-1 molecular sieve (solid content of 97.8 wt%, Na)21.1 percent of O content by weight and 70 percent of crystallinity) and REHY molecular sieve (solid content of 88.0 percent by weight and RE2O3The content was 5.0% by weight, Na20.9 wt% of O, 65 wt% of crystallinity), Beta molecular sieve (95.2 wt% of solid content, Na)2O content of 1.2 wt%, crystallinity of 60%), DOSY molecular sieve (solid content of 93.5 wt%, RE)2O3The content was 8.0% by weight, Na20.8 wt% of O, 80% of crystallinity) and HSY molecular sieve(solids content 91.5 wt.%, RE)2O3The content was 10.5% by weight, Na20.9% by weight of O, 85% crystallinity), HRY molecular sieve (91% by weight of solid content, RE)2O3The content was 6.5% by weight, Na21.1% by weight of O and 70% by weight of crystallinity) are all produced by the Chinese petrochemical catalyst Qilu division;
the rare earth chloride is purchased from high-tech Steel-coated rare earth GmbH, wherein the rare earth elements are La and Ce.
The invention is further illustrated by the following examples, which are not intended to be limiting thereof.
In the present invention, the catalyst-to-oil ratio refers to the mass ratio of the catalyst to the feedstock oil.
In the present invention, ppm is ppm by weight unless otherwise specified.
BN used is hexagonal boron nitride.
In each of examples and comparative examples, Al in the sample2O3、MnO2The content of B, N, Fe was measured by X-ray fluorescence (see "analytical methods in petrochemical industry (RIPP), eds of Yangroi, published by scientific Press, 1990). The sample phase was determined by X-ray diffraction. The specific surface area, the pore volume and the average pore diameter of the sample are measured by a low-temperature nitrogen adsorption-desorption method and calculated by a BJH method to obtain the pore diameter distribution.
Preparation example 1
This example illustrates the preparation of a high specific heat capacity matrix material provided by the present invention.
The concentration of 350gAl2O3Al of/L2(SO4)3Solution with CO3 2-Ammonium carbonate solution with a concentration of 0.10mol/L was mixed to a gel at 20 ℃ and the resulting gel pH was 7.5 to give slurry a. To a concentration of 145gMnO2MnCl of/L2Hydrochloric acid (concentration 36 wt%) was added to the solution, and the pH was controlled to 3.5, then urea was added to the solution at a molar ratio of urea to manganese ions of 2, and the mixture was stirred at room temperature for 30 minutes to obtain solution B. Adding the solution B into the slurry A, stirring and aging at 80 ℃ for 24h, cooling the system to room temperature, filtering, and removingWashing with ionized water until the washed water is neutral to obtain an aged solid precipitate, and then washing with the aged solid precipitate (dry basis): h2O is 1: 2, mixing the obtained aged solid precipitate with water, pulping, and adding water according to the weight ratio of P2O5: high specific heat capacity matrix material dry basis 0.01: 1, stirring for 2 hours at 50 ℃, drying for 12 hours at 120 ℃ to obtain a matrix material precursor, roasting for 6 hours at 550 ℃, and cooling to room temperature along with the furnace to obtain the high specific heat capacity matrix material, which is marked as AM-1. The formulation, preparation parameters, specific heat capacity, specific surface area, pore volume and average pore diameter of AM-1 are listed in Table 1.
In an X-ray diffraction spectrum of AM-1, diffraction peaks are provided at 2 theta angles of 18 +/-0.5 degrees, 37 +/-0.5 degrees, 48 +/-0.5 degrees, 59 +/-0.5 degrees and 66 +/-0.5 degrees, wherein the intensity ratio of characteristic peaks at the 2 theta angles of 18 +/-0.5 degrees and the 2 theta angles of 37 +/-0.5 degrees is 1: 4.1; the elemental analysis weight chemical composition of the composition is 28.9 percent MnO2、70.2％Al2O3、 0.9％P2O5(ii) a Specific heat capacity of 1.33J/(g.K), specific surface area of 308m2Per g, pore volume 0.59cm3G, average pore diameter 7.7 nm.
Preparation examples 2 to 4
Examples 2-4 are provided to illustrate the preparation of high specific heat capacity matrix materials provided by the present invention.
High specific heat capacity matrix materials AM-2 to AM-4 were prepared according to the method of example 1, except for the raw material ratio, preparation condition parameters, in which solution B and boron nitride were added to slurry a, followed by the aging. The raw material ratios, preparation condition parameters, elemental composition, specific heat capacity, specific surface area, pore volume and average pore diameter of the product are listed in table 1.
Preparation example 5
At 25 ℃ and room temperature, the concentration of 350gAl2O3Al (NO)/L3)3Solution with CO3 2-The concentration of ammonium carbonate and OH is 0.1mol/L-A solution of 0.15mol/L aqueous ammonia was mixed, stirred for 1 hour, and the pH was controlled to 10.5 to obtain slurry A. Adding Mn3O4Mixing with hydrochloric acid and water to obtain MnO with a concentration of 87.5g2L of chlorineDissolving a manganese solution, controlling the pH value to be 6, then adding urea into the solution, wherein the molar concentration ratio of the urea to manganese ions is 3, and stirring for 40 minutes at room temperature to obtain a solution B. Adding the solution B and 145.6gBN (solid content is 80 weight percent) into the slurry A, aging for 24h under stirring at 60 ℃, cooling the system to room temperature, washing with deionized water until the washed water is neutral, filtering, and mixing the obtained aged solid precipitate with the aged solid precipitate (dry basis): h2O is 1: 4 is mixed with water and beaten according to the weight ratio of P2O5: dry basis of high specific heat capacity material is 0.05: 1, reacting at 50 ℃ for 2 hours, drying at 120 ℃ for 12 hours to obtain a matrix material precursor, roasting at 650 ℃ for 4 hours, and cooling to room temperature along with the furnace to obtain the matrix material, namely AM-5. The formulation, preparation parameters, specific heat capacity, specific surface area, pore volume and average pore diameter of AM-5 are listed in Table 1.
AM-5 elemental analytical chemical composition in weight percent 15.6% MnO2、59.4％Al2O3、 19.5％BN、5.5％P2O5(ii) a Specific heat capacity of 1.45J/(g.K), specific surface area of 380m2G, pore volume 1.12cm3G, average pore diameter 11.8 nm.
Preparation example 6
Preparation example 6 is used to illustrate the preparation process of the mesoporous matrix material with high specific heat capacity provided by the present invention.
The matrix material AM-6 was prepared according to the method of preparation example 5, except that the formulation, preparation parameters, elemental composition, specific surface area, pore volume and average pore diameter were as listed in table 1. CO in alkali solution3 2-The concentration is 0.15mol/L and OH-The concentration was 0.25 mol/L.
XRD spectra of AM-2 to AM-6 are similar to those of AM-1, and diffraction peaks are provided at 2 theta angles of 18 +/-0.5 degrees, 37 +/-0.5 degrees, 48 +/-0.5 degrees, 59 +/-0.5 degrees and 66 +/-0.5 degrees.
Comparative preparation example 1
Deionized water is used for respectively preparing 350gAl2O3Al (NO)/L3)3Solution and concentration of 145gMnO2The manganese nitrate solution is mixed evenlyAnd (6) homogenizing to obtain a solution A. And preparing an ammonium bicarbonate solution, controlling the pH to be 10.0, and marking as a solution B. And mixing the solution A and the solution B under continuous stirring to obtain mother liquor C, wherein the PH value of the mother liquor C is controlled to be 8-9 by controlling the adding amount of the solution B in the mixing process. After mixing, aging at 180 ℃ for 20h, cooling the system to room temperature, washing the system to be neutral by deionized water to obtain an aged solid precipitate, and then aging the aged solid precipitate (dry basis): h2O is 1: 3, mixing the obtained aged solid precipitate with water, pulping, and adding water according to the weight ratio of P2O5: the resulting matrix material was 0.01: 1, adding phosphoric acid, stirring for 2 hours at 50 ℃, drying for 12 hours at 120 ℃ to obtain a manganese-aluminum matrix precursor, roasting for 4 hours at 1000 ℃, and cooling to room temperature along with a furnace to obtain a matrix material, which is marked as DAM-1.
An X-ray diffraction spectrum of DAM-1, wherein characteristic peaks are present at an angle of 2 theta of 18 + -0.5 DEG and an angle of 2 theta of 37 + -0.5 DEG at an intensity ratio of 1: 1.5; the elemental analytical chemical composition of DAM-1 was 30.2 wt.% MnO268.9% by weight of Al2O3、0.9％P2O5(ii) a Specific heat capacity of 0.58J/(g.K), specific surface area of 284m2G, pore volume 0.41cm3G, average pore diameter 5.8 nm.
Comparative preparation example 2
The concentration of 350gAl2O3Al of/L2(SO4)3The solution was mixed with ammonium carbonate to give a gel, and the pH was controlled to 10.0 to give slurry A. The concentration of 209.7gMnO2MnSO of/L4The solution was added to slurry A and stirred at room temperature for 30 minutes to give slurry B. Adding the solution B and 95.4g of boron nitride (with the solid content of 80 weight percent) into the slurry A, aging for 24h at the temperature of 80 ℃, respectively washing the mixture with deionized water until the mixture is neutral after the temperature of the system is reduced to room temperature to obtain an aged solid precipitate, and then mixing the aged solid precipitate (dry basis): h2O is 1: 4, mixing the obtained aged solid precipitate with water, pulping, and adding water according to the weight ratio of P2O5: the resulting matrix material was 0.03 dry basis: 1, stirring at 50 deg.C for 2 hr, drying at 120 deg.C for 12 hr to obtain manganese-aluminum matrix precursor, and calcining at 900 deg.CAnd cooling the mixture to room temperature along with the furnace for 6 hours to obtain a matrix material which is marked as DAM-2.
The elemental analytical chemical composition of DAM-2 was 33.3 wt.% MnO254.7% by weight of Al2O39.1% by weight of BN and 2.9% by weight of P2O5(ii) a Specific heat capacity of 0.89J/(g.K), specific surface area of 249m2G, pore volume 0.35cm3G, average pore diameter 5.6 nm.
TABLE 1
Figure BDA0002700459190000121
Figure BDA0002700459190000131
In I1/I2 in Table 1, I1 is the intensity of the peak at an angle of 18. + -. 0.5 ℃ in terms of 2. theta. in the XRD spectrum, I2 is the intensity of the peak at an angle of 37. + -. 0.5 ℃ in terms of 2. theta.
Example 1
This example serves to illustrate the catalytic cracking catalyst and the process for its preparation according to the invention.
Mixing 25 parts by weight of pseudo-boehmite on a dry basis with deionized water, pulping (the solid content of the pulp is 15 wt%), adding hydrochloric acid into the obtained pulp, and peptizing, wherein the acid-aluminum ratio (weight) is 0.20: 1, then raising the temperature to 65 ℃ and acidifying for 1 hour, then respectively adding 30 parts by weight of a slurry of kaolin (solid content of 25 wt%) on a dry basis, 6 parts by weight of an aluminum sol on a dry basis and 12 parts by weight of a slurry of the high specific heat capacity matrix material AM-1 (solid content of 18 wt%) prepared in preparation example 1 on a dry basis, stirring for 20 minutes, then adding 27 parts by weight of the HRY molecular sieve slurry (solid content of 35 wt%) on a dry basis thereto, continuing stirring and spray-drying to prepare the microspherical catalyst. The microspherical catalyst is then calcined at 500 deg.C for 1 hour and then calcined at 60 deg.C with (NH)4)2SO4Liquid wash (wherein, (NH)4)2SO4: microspherical catalyst: h2O ═ 0.05: 1: 10) to Na2Content of OLess than 0.25 wt%, leaching with deionized water, filtering, and drying at 110 ℃ to obtain a catalytic cracking catalyst C1, wherein the catalytic cracking catalyst C1 contains 12 wt% of high specific heat capacity matrix material, 27 wt% of HRY molecular sieve, 30 wt% of kaolin, 31 wt% of Al based on the total weight of the catalytic cracking catalyst C12O3And (3) a binder.
Comparative example 1
This comparative example serves to illustrate a reference catalytic cracking catalyst and a method for its preparation.
A catalytic cracking catalyst was prepared by following the procedure of example 1 except that the high specific heat capacity matrix material AM-1 prepared in preparation example 1 was replaced with the same parts by weight of the matrix material DAM-1 prepared in comparative preparation example 1 to obtain a reference catalytic cracking catalyst CB1, wherein the reference catalytic cracking catalyst CB1 contained 12% by weight of the reference matrix material, 27% by weight of HRY molecular sieve, 30% by weight of kaolin, 31% by weight of Al, based on the total weight of the reference catalytic cracking catalyst CB12O3And (3) a binder.
Comparative example 2
This comparative example serves to illustrate a reference catalytic cracking catalyst and a method for its preparation.
A catalytic cracking catalyst was prepared by following the procedure of example 1 except that the high specific heat capacity matrix material AM-1 prepared in preparation example 1 was replaced with the same parts by weight of the matrix material DAM-2 prepared in comparative preparation example 1 to obtain a reference catalytic cracking catalyst CB2, wherein the reference catalytic cracking catalyst CB2 contained 12% by weight of the reference matrix material, 27% by weight of HRY molecular sieve, 30% by weight of kaolin, 31% by weight of Al, based on the total weight of the reference catalytic cracking catalyst CB22O3And (3) a binder.
Comparative example 3
This comparative example serves to illustrate a reference catalytic cracking catalyst and a method for its preparation.
A catalytic cracking catalyst was prepared by following the procedure of example 1 except that high specific heat was not addedThe host material AM-1 with high specific heat capacity is replaced by kaolin with the same dry weight to obtain a reference catalytic cracking catalyst CB3, wherein the reference catalytic cracking catalyst CB3 contains 27 wt% of HRY molecular sieve, 42 wt% of kaolin and 31 wt% of Al based on the total weight of the reference catalytic cracking catalyst CB32O3And (3) a binder.
Example 2
This example serves to illustrate the catalytic cracking catalyst and the process for its preparation according to the invention.
27 parts by weight of kaolin and deionized water on a dry basis are mixed and pulped (the solid content of the slurry is 40 wt%), 20 parts by weight of pseudo-boehmite on a dry basis are added, hydrochloric acid is added into the obtained slurry for peptization, and the acid-aluminum ratio (weight) is 0.20: 1, then the temperature was raised to 65 ℃ and acidified for 1 hour, then 8 parts by weight on a dry basis of an aluminum sol, 20 parts by weight on a dry basis of a slurry of the high specific heat capacity matrix material AM-2 prepared in preparation example 2 (solid content of 20 wt%), respectively, was added and stirred for 20 minutes, and thereafter, a mixed slurry of 20 parts by weight on a dry basis of the HSY molecular sieve, 5 parts by weight on a dry basis of the ZRP-1 molecular sieve (solid content of 35 wt%) was further added thereto, followed by stirring for 30 minutes and spray-drying to prepare a microspherical catalyst. The microspherical catalyst is then calcined at 500 deg.C for 1 hour and then calcined at 60 deg.C with (NH)4)2SO4Solution washing (wherein, (NH)4)2SO4: microspherical catalyst: h2O ═ 0.05: 1: 10) to Na2O content is less than 0.25 wt%, then the catalyst is rinsed by deionized water and filtered, and then the catalyst is dried at 110 ℃ to obtain a catalytic cracking catalyst C2, wherein the catalytic cracking catalyst C2 contains 20 wt% of high specific heat capacity matrix material, 20 wt% of HSY molecular sieve, 5 wt% of ZRP-1 molecular sieve, 27 wt% of kaolin, 28 wt% of Al based on the total weight of the catalytic cracking catalyst C22O3And (3) a binder.
Example 3
This example serves to illustrate the catalytic cracking catalyst and the process for its preparation according to the invention.
Mixing 28 parts by weight of kaolin and deionized water on a dry basis for pulping, adding 15 parts by weight of pseudo-boehmite on a dry basis, adding hydrochloric acid into the obtained slurry for peptization, wherein the acid-aluminum ratio (weight) is 0.20: 1, then raising the temperature to 65 ℃ for acidification for 1 hour, then adding 10 parts by weight on a dry basis of a slurry of the high specific heat capacity matrix material AM-3 prepared in preparation example 3 (solid content of 25 wt%) and 5 parts by weight on a dry basis of an aluminum sol, respectively, stirring for 20 minutes, then adding 15 parts by weight on a dry basis of a mixed slurry of the DASY molecular sieve and 5 parts by weight on a dry basis of the Beta molecular sieve (solid content of 35 wt%) and 2 parts by weight of a rare earth chloride solution in terms of a rare earth oxide, continuing stirring, and spray-drying to prepare the microspherical catalyst. The microspherical catalyst is then calcined at 500 deg.C for 1 hour and then calcined at 60 deg.C with (NH)4)2SO4Solution wash (where, (NH)4)2SO4: microspherical catalyst: h2O ═ 0.05: 1: 10) to Na2The O content is less than 0.25 wt%, then the catalyst is rinsed by deionized water and filtered, and then the catalyst is dried at 110 ℃ to obtain a catalytic cracking catalyst C3, wherein the catalytic cracking catalyst C3 contains 10 wt% of high specific heat capacity matrix material, 15 wt% of DASY molecular sieve, 5 wt% of Beta molecular sieve, 28 wt% of kaolin, and 20 wt% of Al based on the total weight of the catalytic cracking catalyst C32O3Binder, 2 wt% rare earth oxide.
Example 4
This example serves to illustrate the catalytic cracking catalyst and the process for its preparation according to the invention.
39 parts by weight of kaolin on a dry basis was mixed with 18 parts by weight of alumina sol on a dry basis and 15 parts by weight of the slurry (solid content: 20% by weight) of the high specific heat capacity matrix material AM-4 prepared in preparation example 4 on a dry basis, and the mixture was beaten, stirred for 120 minutes, and then 28 parts by weight of the DOSY molecular sieve slurry (solid content: 35% by weight) on a dry basis was added thereto, and stirring was continuedThen spray drying to prepare the microsphere catalyst. The microspherical catalyst is then calcined at 500 deg.C for 1 hour and then calcined at 60 deg.C with (NH)4)2SO4Solution washing (wherein, (NH)4)2SO4: microspherical catalyst: h2O ═ 0.05: 1: 10) to Na2The O content is less than 0.25 wt%, then the catalyst is rinsed by deionized water and filtered, and then the catalyst is dried at 110 ℃ to obtain a catalytic cracking catalyst C4, wherein the catalytic cracking catalyst C4 contains 15 wt% of high specific heat capacity matrix material, 28 wt% of DOSY molecular sieve, 39 wt% of kaolin, 18 wt% of Al based on the total weight of the catalytic cracking catalyst C42O3And (3) a binder.
Example 5
This example serves to illustrate the catalytic cracking catalyst and the process for its preparation according to the invention.
(1) Preparing silica sol:
1.7L of hydrochloric acid was diluted with 8.0kg of decationized water, 7.7kg of sodium water glass was diluted with 8.0kg of decationized water, and the diluted sodium water glass was slowly added to the above diluted hydrochloric acid solution with stirring to obtain a silica sol of 7.8% SiO2 and pH 2.8.
(2) Preparing a catalytic cracking catalyst:
adding 20 parts by weight of kaolin into 15 parts by weight of the silica sol on a dry basis, stirring for 1h, adding 40 parts by weight of slurry (with the solid content of 18 wt%) of the high specific heat capacity matrix material AM-5 prepared in preparation example 5 on a dry basis, mixing and pulping, adding 25 parts by weight of DASY molecular sieve slurry (with the solid content of 30 wt%) on a dry basis, continuously stirring, and performing spray drying to prepare the microspherical catalyst. The microspherical catalyst was then incubated at 60 deg.C with (NH)4)2SO4Solution washing (wherein, (NH)4)2SO4: microspherical catalyst: h2O ═ 0.05: 1: 10) to Na2O content less than 0.25 wt%, washing with deionized water, filtering, and stoving at 110 deg.c to obtain catalytic cracking catalyst C5, which may be further processedThe total weight of the catalytic cracking catalyst C5 is as reference, the catalytic cracking catalyst C5 contains 40 wt% of high specific heat capacity matrix material, 25 wt% of DASY molecular sieve, 20 wt% of kaolin, 15 wt% of SiO2And (3) a binder.
Example 6
This example serves to illustrate the catalytic cracking catalyst and the process for its preparation according to the invention.
10 parts by weight of kaolin on a dry basis, 17 parts by weight of alumina sol on a dry basis and 45 parts by weight of slurry (solid content of 20 wt%) of the high specific heat capacity matrix material AM-6 prepared in preparation example 6 on a dry basis were mixed and beaten, stirred for 120 minutes, and then 28 parts by weight of the HSY molecular sieve slurry (solid content of 35 wt%) on a dry basis was added thereto, and after further stirring, spray-drying was carried out to prepare a microspherical catalyst. The microspherical catalyst is then calcined at 500 deg.C for 1 hour and then calcined at 60 deg.C with (NH)4)2SO4Solution washing (wherein, (NH)4)2SO4: microspherical catalyst: h2O ═ 0.05: 1: 10) to Na2The O content is less than 0.25 weight percent, then the catalyst is rinsed by deionized water and filtered, and then the catalyst is dried at 110 ℃ to obtain a catalytic cracking catalyst C6, wherein the catalytic cracking catalyst C6 contains 45 weight percent of high specific heat capacity matrix material, 28 weight percent of HSY molecular sieve, 10 weight percent of kaolin, and 17 weight percent of Al based on the total weight of the catalytic cracking catalyst C62O3And (3) a binder.
Examples 7 to 12
Examples 10-18 are provided to illustrate the testing of the performance of the catalytic cracking catalysts provided by the present invention.
The prepared catalytic cracking catalysts C1-C9 are respectively dipped with 4000ppm of polluted iron, 4000ppm of nickel and 4000ppm of vanadium by a Mitchell method, namely vanadium naphthenate is taken as a vanadium source, nickel naphthenate is taken as a nickel source, iron naphthenate is taken as an iron source, and methylbenzene is taken as a solvent to prepare a metal-containing solution, and the catalysts are dipped in the metal-containing solution, then are dried, and are roasted at about 600 ℃ to remove organic matters. Aging at 800 deg.C under 100% water vapor conditionAnd (3) carrying out cracking performance evaluation on a small fixed fluidized bed for 6 hours, carrying out five reaction-regeneration cycles in the evaluation process of each sample, namely continuously carrying out five raw oil reactions and regeneration processes under the condition that the same catalyst is not discharged, and taking the result of the last reaction as the evaluation result of the cracking performance of the catalyst. The evaluation conditions of the heavy oil micro-reaction are as follows: the agent-oil ratio is 5 (weight ratio), the sample loading is 9g, the reaction temperature is 520 ℃, and the WHSV is 8h-1The oil feeding time is 70 seconds, the regeneration temperature is 720 ℃, and the raw oil is vacuum gas oil. The properties of the feed oil are shown in Table 2. The evaluation results are shown in Table 3.
Comparative examples 4 to 6
The above-prepared catalytic cracking reference agents CB1-CB3 were subjected to performance tests in the same manner as in examples 7 to 12, and the evaluation results are shown in Table 3.
TABLE 2
Figure BDA0002700459190000171
TABLE 3
Figure BDA0002700459190000181
w% means weight%
In the invention, the conversion rate is gasoline yield, liquefied gas yield, dry gas yield and coke yield,
total liquid yield (also called total liquid product yield) is gasoline yield, diesel oil yield and liquefied gas yield,
coke selectivity is the coke yield/conversion, dry gas selectivity is the dry gas yield/conversion.
As can be seen from the results in table 3, compared with the catalyst containing the same zeolite but not containing the matrix material with high specific heat capacity, the catalyst provided by the present invention has a lower attrition index, and the catalyst provided by the present invention has excellent metal contamination resistance, and under the condition of metal contamination, the heavy oil conversion capability is greatly improved, the product distribution is obviously improved, and especially, the selectivity of dry gas and coke can be obviously improved. Compared with the catalyst which has the same content of each component and adopts the matrix material different from the matrix material, the catalyst provided by the invention has the advantages of reduced abrasion index, obviously reduced dry gas selectivity, reduced coke yield, obviously improved total liquid yield and obviously improved light oil yield (gasoline and liquefied gas yield). Therefore, the catalytic cracking catalyst provided by the invention has excellent metal pollution resistance.

Claims (24)

1. An attrition resistant catalytic cracking catalyst comprising, based on the total weight of the catalytic cracking catalyst, from 1 to 60 weight percent of a cracking active component comprising a first molecular sieve and optionally a second molecular sieve, from 1 to 50 weight percent of a high specific heat capacity matrix material, from 1 to 70 weight percent of a clay, and from 1 to 70 weight percent of a binder; the first molecular sieve is a Y-type molecular sieve; the high specific heat capacity matrix material contains 5-94.5 wt% of alumina in MnO25-94.5% by weight, calculated as P, of manganese oxide2O50.5-10 wt% of phosphorus oxide, wherein the specific heat capacity of the high specific heat capacity matrix material at the temperature of 1000K is 1.3-2.0J/(g.K).
2. The catalytic cracking catalyst of claim 1, wherein the catalytic cracking catalyst comprises 5 to 45 wt% of the high specific heat capacity base material, 10 to 50 wt% of the cracking active component, 10 to 60 wt% of the clay, and 10 to 60 wt% of the binder, based on the total weight of the catalytic cracking catalyst.
3. The catalytic cracking catalyst of claim 1, wherein the high specific heat capacity matrix material contains 0-40 wt% or 4-26 wt% boron nitride on a dry basis.
4. The catalytic cracking catalyst of claim 1, wherein the high specific heat capacity matrix material has a specific surface area of 300 to 500m2·g-1Or 330-400m2·g-1。
5. The catalytic cracking catalyst of claim 1, wherein the high specific heat capacity matrix material has a pore volume of 0.5 to 1.5cm3(ii)/g; the average pore diameter of the high specific heat capacity matrix material is 3-20nm or 9-13 nm.
6. The catalytic cracking catalyst of claim 1, wherein the high specific heat capacity matrix material has an XRD pattern with peaks at 18 ± 0.5 ° 2 theta and 37 ± 0.5 ° 2 theta at an intensity ratio of 1: (3-10).
7. The catalytic cracking catalyst of any one of claims 1 to 6, wherein the Y-type molecular sieve is one or more of REY molecular sieve, REHY molecular sieve, DASY molecular sieve, USY molecular sieve, RE-DASY molecular sieve, RE-USY molecular sieve, PSRY molecular sieve, HSY molecular sieve and SOY molecular sieve.
8. The catalytic cracking catalyst of claim 19 wherein the second molecular sieve is one or more of faujasite, zeolite Beta, MFI structure molecular sieve and mordenite other than zeolite Y.
9. The catalytic cracking catalyst of claim 20, wherein the Y-type molecular sieve content is 75 wt% or more and the second molecular sieve content is 25 wt% or less, based on the total weight of the cracking active components.
10. A process for preparing a catalytic cracking catalyst as claimed in any one of claims 1 to 9, which comprises mixing the cracking active component, the high specific heat capacity matrix material, clay and binder, beating, spray drying, washing, filtering and drying.
11. The method for preparing a catalytic cracking catalyst according to claim 10, wherein the method for preparing the high specific heat capacity matrix material comprises the steps of:
(1) mixing an aluminum source and alkali into glue to obtain an aluminum-containing colloid, wherein the pH value of the aluminum-containing colloid is 7-11;
(2) mixing a manganese salt solution with the pH value of 3-7 with urea to obtain a manganese source solution;
(3) forming a mixture of an aluminum-containing colloid, a manganese source solution and optionally boron nitride, and aging;
(4) the aged solid precipitate is contacted with a source of phosphorus, optionally washed and/or dried and/or calcined.
12. The method of preparing a catalytic cracking catalyst of claim 11, wherein the mixing the aluminum source and the alkali into the gel comprises: mixing the aluminum source solution and the alkali solution to form colloid with the temperature of room temperature to 85 ℃ and the pH value of 7-11.
13. The catalytic cracking catalyst as claimed in claim 11, wherein the concentration of alumina in the aluminum source solution is 150 to 350gAl2O3and/L, wherein the concentration of the alkali in the alkali solution is 0.1-1 mol/L.
14. The method for preparing a catalytic cracking catalyst according to claim 11, wherein the aluminum source is one or more selected from the group consisting of aluminum nitrate, aluminum sulfate, aluminum phosphate, aluminum chloride, and the like; the alkali is one or more of carbonate dissolved in water, bicarbonate dissolved in water and hydroxide dissolved in water.
15. The catalytic cracking catalyst preparation method of claim 11, wherein the alkali solution is selected from the group consisting of CO-containing solutions3 2-、HCO3 -Or OH-An alkaline aqueous solution of one or more of (a) and (b), the solution of the base being CO3 2-Has a concentration of 0-0.6mol/L, OH-The concentration of (A) is 0-0.5mol/L, HCO3 -The concentration of (b) is 0 to 1 mol/L.
16. The process for preparing a catalytic cracking catalyst according to claim 11, wherein in the step (2), the molar ratio of urea to manganese ions is 1 to 5, for example, 2 to 4, and the manganese salt solution isThe concentration of medium manganese salt is MnO2The amount can be 50-500 g.L-1。
17. The catalytic cracking catalyst as claimed in claim 11, wherein the step (2) comprises adding urea to the manganese salt solution, and stirring at room temperature for 30-60 minutes to obtain the manganese source solution.
18. The process for preparing a catalytic cracking catalyst according to claim 11, wherein the aging temperature in the step (3) is from room temperature to 120 ℃ and the aging time is from 4 to 72 hours.
19. The process for preparing a catalytic cracking catalyst according to claim 11, wherein the aging temperature is 60 to 100 ℃ and the aging time is 12 to 36 hours, and stirring and aging are carried out.
20. The process for preparing a catalytic cracking catalyst according to claim 11, wherein the aging solid precipitate is contacted with a phosphorus source by the process comprising: mixing the aged solid precipitate with water according to the dry basis of the aged solid precipitate: water 1: (2-5), mixing and pulping, mixing the phosphorus source and the slurry at the temperature of room temperature to 90 ℃, and then stirring or standing for 0.2-5 hours.
21. The method of preparing a catalytic cracking catalyst according to claim 11, wherein the manganese salt is selected from one or more of manganese nitrate, manganese sulfate, manganese phosphate, manganese chloride, or the like, the boron nitride is selected from at least one of hexagonal boron nitride (h-BN), cubic boron nitride (c-BN), rhombohedral boron nitride (r-BN), and wurtzite boron nitride (w-BN), and the phosphorus source is selected from one or more of ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate, or phosphoric acid.
22. The process for preparing a catalytic cracking catalyst according to claim 11, wherein the calcination in the step (4) is carried out at a calcination temperature of 500 to 900 ℃ for 4 to 8 hours.
23. A catalytic cracking catalyst prepared by the process of any one of claims 10 to 22.
24. Use of the catalytic cracking catalyst of any one of claims 1 to 9 or 23 in catalytic cracking of heavy oil.
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