CN116689017A - Catalytic cracking catalyst for resisting metal pollution and preparation method thereof - Google Patents

Catalytic cracking catalyst for resisting metal pollution and preparation method thereof Download PDF

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CN116689017A
CN116689017A CN202210183718.3A CN202210183718A CN116689017A CN 116689017 A CN116689017 A CN 116689017A CN 202210183718 A CN202210183718 A CN 202210183718A CN 116689017 A CN116689017 A CN 116689017A
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catalyst
rare earth
microspheres
microsphere
catalytic cracking
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周灵萍
沙昊
严加松
宋海涛
袁帅
张蔚琳
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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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    • 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

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Abstract

The invention belongs to the technical field of catalyst preparation, and relates to a preparation method of a catalytic cracking catalyst for resisting metal pollution, which comprises the steps of treating catalyst microspheres by organic acid and inorganic acid, then treating the catalyst microspheres by a mixed solution of rare earth salt and alkaline earth metal salt and then contacting the catalyst microspheres with ammonia water, wherein the preparation method of the catalyst microspheres comprises the steps of roasting microspheres comprising unmodified NaY molecular sieve, alumina binder, silica binder and clay at 280-380 ℃, carrying out rare earth ion exchange, treating the microspheres at the temperature of 350-450 ℃ and containing 40-60 volume percent of water vapor, and treating the microspheres by SiCl 4 The catalytic cracking catalyst prepared by the method has higher pore volume and higher specific surfaceThe product and strength are good, the nickel-vanadium pollution resistance is strong, the catalyst is used for heavy oil conversion, the activity is high, the gasoline yield is high, the total liquid yield is high, and the selectivity of dry gas and coke is good.

Description

Catalytic cracking catalyst for resisting metal pollution and preparation method thereof
Technical Field
The invention relates to a catalytic cracking catalyst resistant to metal pollution and a preparation method thereof.
Background
With the recent world's heavy and poor quality of crude oil, catalytic cracking technology (FCC) blending or total refining heavy oils and residues is particularly important. Compared with the distillate catalytic cracking raw oil, the content of harmful metals in the heavy oil or residual oil is far higher than that in the distillate. The porphyrin compound, naphthenate, inorganic salt and other harmful metals are present in the raw oil, and the harmful metals such as nickel, vanadium, iron, sodium, calcium and the like are decomposed and enriched on the balancing agent in the catalytic cracking reaction process, and the harmful metals react with the molecular sieve to destroy the lattice structure of the catalyst, weaken the acidity of the molecular sieve, and deteriorate the activity and selectivity of the catalyst, thereby influencing the distribution and quality of the product. The effective inhibition of heavy metal pollution to the catalyst is one of the key measures for improving the economic and technical benefits of the RFCC device.
CN1854255A discloses a process for preparing cracking catalyst resistant to heavy metal contamination, which comprises mixing clay, deionized water and optional additives uniformly to obtain clay slurry, mixing molecular sieve, deionized water and optional additives uniformly to obtain molecular sieve slurry, mixing binder, deionized water, alkaline earth metal compound, rare earth metal compound and optional inorganic acid uniformly to obtain binder slurry; and uniformly mixing the clay slurry, the molecular sieve slurry and the binder slurry, and drying. The cracking catalyst prepared by the method has good nickel and vanadium pollution resistance, and can still maintain high conversion rate and light oil yield when the nickel content of the catalyst is higher, however, the catalyst prepared by the method, alkaline earth metal compounds and rare earth metal compounds are mainly distributed in the catalyst, and the nickel and vanadium pollution resistance of the catalyst is limited to a certain extent.
The catalytic cracking catalyst generally contains a binder and an active component, and the active component has a great influence on the activity and coke selectivity of the catalytic cracking catalyst. One commonly used active component in the catalytic cracking catalyst is a Y-type molecular sieve, in order to improve the activity and coke selectivity of the Y-type molecular sieve for heavy oil conversion, the Y-type molecular sieve is generally subjected to ultrastable modification treatment and then mixed with a binder and pulped, and the performance of the catalyst containing the ultrastable Y-type molecular sieve in the prior art is difficult to further improve when the catalyst is used for heavy oil conversion.
CN102806096a discloses a method for preparing a rare earth-containing Y-type molecular sieve cracking catalyst, which comprises (1) mixing a NaY molecular sieve which is not subjected to ion exchange with a matrix, pulping, and spray-drying to form a catalyst precursor; (2) Performing first roasting on the catalyst precursor at a temperature of 200 ℃ to less than 400 ℃, and performing ammonium ion exchange on a product obtained after the first roasting; and (3) subjecting the product obtained after the ammonium ion exchange to at least one second calcination and at least one rare earth ion exchange, the rare earth ion exchange being performed after the second calcination; the temperature of the ammonium ion exchange is higher than that of the rare earth ion exchange; the second firing temperature is higher than the first firing temperature. However, the catalyst obtained by the method has low stability in catalytic cracking reaction activity of heavy oil, and the heavy oil conversion activity of the product after the anti-metal pollution component is introduced is low.
Disclosure of Invention
The invention aims to provide a novel preparation method of a catalytic cracking catalyst containing an ultrastable Y-type molecular sieve and resisting metal pollution.
The invention provides a preparation method of a catalytic cracking catalyst resistant to metal pollution, which comprises the following steps:
(S1): forming first microspheres comprising a Y-type molecular sieve, an alumina binder, a silica binder, and clay;
(S2): the first microspheres are contacted with inorganic acid and organic acid solution to remove non-framework aluminum of the molecular sieve, and are filtered and washed to obtain second microspheres;
(S3): the second microsphere is contacted with a mixed solution containing rare earth salt and alkaline earth metal salt, filtered, contacted with ammonia water, filtered, dried and roasted to obtain a catalytic cracking catalyst finished product.
The weight ratio of the alumina binder calculated by alumina to the silica binder calculated by silica in the first microspheres is 2-15:10-30 parts of a base;
the weight ratio of the Y-type molecular sieve in the first microsphere to the silicon oxide binder in the first microsphere is preferably 10-50:10-30.
The weight ratio of clay in dry basis to silica binder in silica in the first microspheres is preferably 10-80:10-30.
In step (S2), the first microspheres are contacted with an inorganic acid and an organic acid solution, preferably at a temperature of 25-70 ℃; the inorganic acid may be contacted with the inorganic acid solution and the organic acid solution sequentially, or may be contacted with a solution containing both the inorganic acid and the organic acid, wherein the molar concentration of the inorganic acid in the solution containing the inorganic acid (the inorganic acid solution or the solution containing both the inorganic acid and the organic acid) is preferably 0.01mol/L to 0.15mol/L, and the weight ratio of the solution containing the inorganic acid to the first microspheres on a dry basis is 6 to 12:1, a step of; the weight ratio of the organic acid to the first microspheres on a dry basis is 0.02-0.10:1.
In the step (S3), in one mode, the second microsphere is contacted with a solution containing rare earth salt and alkaline earth metal salt for 5-30 minutes at room temperature, then filtered, then contacted with ammonia water for 5-30 minutes, filtered, dried and roasted to obtain a catalytic cracking catalyst finished product.
The rare earth of the invention is, for example, la, ce, pr, nd or a misch metal comprising one or more of the above rare earth elements.
One or more of the alkaline earth metals, e.g., be, mg, ca, sr, ba, preferably Mg and/or Ca, more preferably Mg;
the rare earth salt in the step (S3) is preferably lanthanum nitrate and/or lanthanum chloride, and the alkaline earth metal salt is preferably magnesium nitrate and/or magnesium chloride.
Preferably, in the step (S3), the concentration of the rare earth salt in the solution containing the rare earth salt and the alkaline earth metal salt is RE 2 O 3 The concentration of the alkaline earth metal salt is calculated as 60-150 g/L, and the concentration of the alkaline earth metal salt is calculated as 30-80 g/L of alkaline earth metal oxide.
The concentration of the ammonia water is NH 3 Preferably the meter is 5About 15 wt.%.
The weight ratio of the mixed solution containing the rare earth salt and the alkaline earth metal salt to the second microsphere is preferably 3-6: 1.
preferably, with RE 2 O 3 And (3) the rare earth content in the finished catalytic cracking catalyst obtained in the step (S3) is 0.2-1 wt% higher than that of the second microspheres.
RE is used in the finished catalytic cracking catalyst product obtained in the step (S3) 2 O 3 The rare earth content is preferably 1 to 6% by weight, for example 1.2 to 5.8% by weight.
The catalyst preparation method provided by the invention can improve the metal pollution resistance effect of the metal pollution resistance catalyst, and the catalytic cracking catalyst has higher heavy oil conversion activity under the condition of metal pollution. Preferably, the preparation method of the catalytic cracking catalyst provided by the invention can be used for preparing the catalytic cracking catalyst with larger specific surface area, higher pore volume, better strength (good wear resistance), higher gasoline yield, higher total liquid yield, better coke selectivity and stronger heavy oil conversion capability. The preparation method of the catalytic cracking catalyst can obtain the catalytic cracking catalyst with the sodium oxide content lower than 0.15 weight percent, and the preparation process effectively solves the ammonia nitrogen pollution problem to be solved in the production of the catalytic cracking catalyst.
Detailed Description
The invention provides a preparation method of a catalytic cracking catalyst resistant to metal pollution, which preferably comprises the following steps:
(1) Mixing unmodified NaY molecular sieve with alumina binder, silica binder (also called silicon binder in the invention), clay and water, pulping, spray drying, forming, and roasting at 280-380 ℃ for preferably 1-4 hours to obtain catalyst microsphere A; the alumina binder is alumina sol;
(2) Making the catalyst microsphere A contact with rare earth solution to make ion exchange reaction, filtering and washing so as to obtain rare earth-containing catalyst microsphere B with reduced sodium oxide content; wherein the rare earth solution is also called rare earth salt solution;
(3) Subjecting the catalyst microspheres B to modification treatment, and optionally drying to obtain catalyst microspheres C containing molecular sieves with reduced unit cell constants, wherein the modification treatment is to bake the catalyst microspheres B for 4-6 hours at the temperature of 350-450 ℃ in an atmosphere containing 40-60% by volume of water vapor (also called as 40-60% by volume of water vapor atmosphere or 40-60% by volume of water vapor); the unit cell constant of the molecular sieve in the catalyst microsphere C containing the molecular sieve with reduced unit cell constant is preferably 24.61nm-24.64nm; wherein the water content of the catalyst microspheres C preferably does not exceed 1 wt.%;
(4) Allowing the catalyst microsphere C to react with SiCl 4 The gas is contacted and reacted at the temperature of 250-450 ℃, wherein SiCl 4 : weight ratio of catalyst microsphere C on a dry basis = 0.03-0.2: 1, reacting for 10 minutes to 5 hours, washing and filtering to obtain a catalyst microsphere D; if the water content of the catalyst microsphere C obtained by the modification treatment in the step (3) is not more than 1 weight percent, the catalyst microsphere C can be directly contacted with silicon tetrachloride for carrying out the reaction, and if the water content of the catalyst microsphere C is more than 1 weight percent, the catalyst microsphere C is preferably dried to ensure that the water content of the catalyst microsphere C is less than 1 weight percent and then is contacted with the silicon tetrachloride for carrying out the reaction;
(5) Contacting the catalyst microsphere D with an inorganic acid and an organic acid solution at a temperature of 25-70 ℃ for at least 60 minutes, such as 60-120 minutes, filtering, washing and drying to obtain a catalyst microsphere E;
(6) Contacting the catalyst microsphere E with a mixed solution containing rare earth salt and alkaline earth metal salt, filtering, then contacting with ammonia water, filtering, drying and roasting; preferably, the catalyst microspheres E are added into a mixed solution containing rare earth salt and alkaline earth metal salt at room temperature, stirred for preferably 5-30 minutes, filtered, and then added into NH 3 Stirring in 10-15 wt% ammonia water for 5-30 min, filtering, drying and roasting to obtain the catalyst product F. Wherein the mixed solution of rare earth salt and alkaline earth metal salt is preferably lanthanum nitrate and/or lanthanum chloride, and the alkaline earth metal salt is magnesium nitrate and/or magnesium chlorideMagnesium chloride. The temperature of the room temperature is preferably 10 to 30 ℃. The preferred preparation method can prepare the catalytic cracking catalyst with larger specific surface area, higher pore volume, better strength (good wear resistance), higher gasoline yield, better coke selectivity and stronger heavy oil conversion capability. The sodium oxide content of the obtained catalytic cracking catalyst can be lower than 0.15 weight percent, so that the ammonia nitrogen pollution problem to be solved in the production of the catalytic cracking catalyst is effectively solved. The catalytic cracking catalyst obtained by the preparation method of the preferred catalytic cracking catalyst has higher activity stability under the condition of metal pollution, higher heavy oil conversion activity for heavy oil catalytic cracking reaction, higher gasoline yield and lower coke selectivity and dry gas selectivity.
In the preparation method of the catalytic cracking catalyst, in the step (1), an unmodified NaY molecular sieve is mixed with an alumina binder, a silica binder, clay and water, wherein the weight ratio of the alumina binder to the unmodified NaY molecular sieve on a dry basis is 2-15:10-50, and the weight ratio of the silica binder to the unmodified NaY molecular sieve on a dry basis is 10-30:10-50, and the weight ratio of the clay to the unmodified NaY molecular sieve on a dry basis is 10-80:10-50.
In the preparation method of the catalytic cracking catalyst, in the step (1), unmodified NaY molecular sieve is mixed with alumina binder, silica binder, clay and water, and pulped to form slurry, and the process can be operated under the condition of no heating, temperature rising and aging. The mixing and beating processes are not heated, so that the slurry viscosity is high and the slurry cannot be conveyed due to heating, the solid content of the slurry is improved, the production efficiency is improved, the energy consumption is reduced, and the production cost is reduced.
In one embodiment, the mixing and beating is performed by mixing the unmodified NaY molecular sieve, the alumina sol and silica sol binder, clay and water at ambient temperature, e.g., room temperature (10-30 c), and then stirring for more than 30 minutes, e.g., 30-180 minutes or 30-60 minutes, without the need for elevated temperature aging.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the unmodified NaY molecular sieve is used for being mixed with an aluminum binder such as aluminum sol and a silicon oxide binder such as silica sol binder, clay and water, and pulping, and the mixing and pulping methods have no special requirements compared with the existing preparation methods of the catalytic cracking catalyst. For example, clay such as kaolin and/or other clay may be slurried with an aluminum sol and a silica sol to form a matrix slurry, and then the matrix slurry is slurried with an unmodified NaY molecular sieve or an unmodified NaY molecular sieve slurry to form a catalyst colloid. The solids content of the catalyst colloid is preferably 28 to 40% by weight.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the content of the unmodified NaY-type molecular sieve in the catalyst microsphere A is 10-50 wt%, preferably 15-45 wt% or 20-50 wt%, for example 25-40 wt%, based on dry basis.
In the preparation method of the catalytic cracking catalyst provided by the invention, the unmodified NaY molecular sieve is preferably a hydrothermally synthesized NaY molecular sieve which is only washed by water such as industrial water and the pH value of a filter cake of the NaY molecular sieve is determined to be 7-9, preferably 7.0-8.0 after washing. The hydrothermally synthesized NaY molecular sieves can be synthesized commercially or with reference to the prior art, for example, with reference to the methods provided in the claims or examples of U.S. patent No. 3639099, US 3671191. Such industrial waters are well known to those skilled in the art.
According to the method for preparing a catalytic cracking catalyst provided by the present invention, preferably, the clay content in the catalyst microsphere a provided by the present invention is 20 to 55 wt%, for example, 30 to 50 wt% or 40 to 50 wt% on a dry basis. The clay is selected from one or more of clay used as cracking catalyst component, such as one or more of kaolin, halloysite, montmorillonite, kieselguhr, attapulgite, saponite, rectorite, sepiolite, hydrotalcite and bentonite. Such clays are well known to those of ordinary skill in the art.
According to the preparation method of the catalytic cracking catalyst provided by the invention, the alumina binder is alumina sol, preferably, the catalyst microsphere A contains 2-15 wt%, such as 2-10 wt%, preferably 3-5 wt%, of alumina sol calculated by alumina.
The silica binder, for example silica sol, is present in the catalyst microspheres A in an amount of 10 to 30 wt%, preferably 10 to 25 wt% or 20 to 25 wt%, based on silica.
Preferably, the catalyst microspheres a contain 10 to 50 wt% of an unmodified NaY-type molecular sieve on a dry basis, 2 to 15 wt% of an alumina binder on an alumina basis, 10 to 30 wt% of a silica binder on a silica basis, and 10 to 80 wt% of clay on a dry basis. For example, the catalyst microsphere a contains: 20-50 wt% of unmodified NaY-type molecular sieve based on dry basis, 20-55 wt% of clay based on dry basis, 3-5 wt% of alumina sol based on alumina, and 10-25 wt% of silica sol based on silica.
According to the preparation method of the catalytic cracking catalyst provided by the invention, other molecular sieves except the unmodified NaY type molecular sieve can be added in the mixing and pulping process, and the content of the other molecular sieves in the catalyst microsphere A can be 0-40 wt%, for example, 0-30 wt% or 1-20 wt% on a dry basis based on the weight of the catalyst microsphere A. The other molecular sieve is selected from molecular sieves used in catalytic cracking catalysts, such as one or more of zeolite having MFI structure, beta zeolite, non-zeolite molecular sieves. The MFI structure zeolite is one or more of ZRP, HZSM-5 and ZSP zeolite, the beta zeolite is H beta zeolite, and the non-zeolite molecular sieve is one or more of aluminum phosphate molecular sieve (AlPO molecular sieve) or silicon aluminum phosphorus molecular sieve (SAPO molecular sieve).
According to the preparation method of the catalytic cracking catalyst provided by the invention, in the step (1), the spray drying method is not particularly required, and can be performed according to the spray drying method in the existing preparation process of the catalytic cracking catalyst.
In the preparation method of the catalytic cracking catalyst, in the step (1), the catalyst microspheres are obtained by spray drying and molding, and then the catalyst microspheres are roasted at the roasting temperature of 280-380 ℃, preferably 300-350 ℃; the calcination time is 1 to 4 hours, for example 1 hour, 2 hours, 3 hours or 4 hours.
In the preparation method of the catalytic cracking catalyst, in the step (2), the catalyst microsphere A is contacted with the rare earth solution to carry out ion exchange reaction, wherein the temperature of the ion exchange reaction can be 20-60 ℃, preferably 25-45 ℃, and the exchange time can be more than 60 minutes, preferably 60-120 minutes. The rare earth salt solution (rare earth solution for short) is an aqueous solution of rare earth salt, and the rare earth salt is preferably rare earth chloride and/or rare earth nitrate. In one embodiment, the concentration of the rare earth salt solution is RE 2 O 3 200-350g/L, and the weight ratio of the rare earth salt solution to the catalyst microsphere A is 0.03-0.3.
Preferably, the ion exchange results in a catalyst microsphere B having a rare earth content of RE 2 O 3 1-5 wt%.
In the preparation method of the catalytic cracking catalyst provided by the invention, in the step (3), the temperature of modifying the catalyst microsphere B (the modifying treatment is called moderating hydrothermal superstable modifying treatment) or the roasting temperature is 350-450 ℃, preferably 370-420 ℃.
In the preparation method of the catalytic cracking catalyst provided by the invention, the modification treatment atmosphere condition in the step (3) is an atmosphere containing 40-60% by volume of water vapor, preferably an atmosphere containing 45-55% by volume of water vapor.
In the preparation method of the catalytic cracking catalyst provided by the invention, the modification treatment time or the roasting time in the step (3) is 4-6 hours, preferably 5-6 hours.
In the preparation method of the catalytic cracking catalyst provided by the invention, the catalyst microsphere C and SiCl in the step (4) are prepared 4 The reaction temperature of the gas contact reaction is 250 to 450 ℃, preferably 280 to 420 ℃.
In the preparation method of the catalytic cracking catalyst provided by the invention, the catalyst microsphere C and SiCl in the step (4) are prepared 4 Reaction time of gas contact reactionFrom 10 minutes to 5 hours, for example from 0.2 to 2 hours, preferably from 0.5 to 2 hours.
In the preparation method of the catalytic cracking catalyst provided by the invention, the catalyst microsphere C and SiCl in the step (4) are prepared 4 Weight ratio of SiCl to reaction material for gas contact reaction 4 : the weight ratio of the catalyst microsphere C is 0.03-0.2: 1, preferably 0.05 to 0.15:1.
according to the preparation method of the catalytic cracking catalyst, in the step (5), the catalyst microspheres D are contacted with the acid solution for acid treatment modification, wherein the acid is organic acid and inorganic acid, and preferably, the catalyst microspheres D are contacted with the inorganic acid and the organic acid solution at the temperature of 25-70 ℃ for at least 60 minutes, so that the catalyst microspheres D have a better effect of increasing the pore volume. In one embodiment, the treatment with the mineral acid is followed by the treatment with the mineral acid and the organic acid, preferably at a temperature of 25-70 ℃, and for a time of at least 60 minutes each. The inorganic acid is preferably an inorganic acid with a medium strength or more, and the molar concentration of the inorganic acid with a medium strength or more in the acid solution is preferably 0.01mol/L to 0.15mol/L (M). The molar concentration of the organic acid in the acid solution is preferably 0.004-0.1mol/L, for example 0.01-0.05mol/L, and the weight ratio of water to the catalyst microspheres D (dry basis) is preferably 5-15:1.
In one embodiment, in step (5), the catalyst microspheres D obtained in step (4) are first mixed with an inorganic acid solution of medium strength or higher, contacted at 25-70 ℃, preferably 40-60 ℃, for at least 60 minutes, e.g., 60-120 minutes, then added with an organic acid, contacted at 25-70 ℃, preferably 40-60 ℃, for at least 60 minutes, e.g., 60-120 minutes, filtered, washed and dried to obtain catalyst microspheres E. Wherein preferably, the weight ratio of the inorganic acid solution with medium strength to the catalyst microsphere D on a dry basis is 6-12: the inorganic acid solution with more than medium strength is an aqueous solution of the inorganic acid with more than medium strength, wherein the molar concentration of the inorganic acid with more than medium strength is 0.01M-0.15M. The weight ratio of the organic acid to the catalyst microsphere D on a dry basis is 0.02-0.10:1.
the inorganic acid with medium strength or above is one or more of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid; the organic acid is one or more of formic acid, acetic acid, citric acid, oxalic acid and tartaric acid.
In the preparation method of the catalytic cracking catalyst provided by the invention, the mixed solution containing the rare earth salt and the alkaline earth metal salt in the step (6), wherein the rare earth salt can be lanthanum nitrate and/or lanthanum chloride, and the alkaline earth metal salt is magnesium nitrate and/or magnesium chloride; the ammonia water in the step (6) is ammonia water solution, the temperature of the catalyst microsphere E contacted with the mixed solution containing rare earth salt and alkaline earth metal salt is room temperature, the temperature of the catalyst microsphere E contacted with the ammonia water is room temperature, and the room temperature is 10-30 ℃.
The following examples further illustrate the invention but are not intended to limit it.
Examples and comparative examples, unmodified NaY molecular sieves (also referred to as NaY zeolite) were provided by ziluta corporation, a chinese petrochemical catalyst, with a sodium oxide content of 13.5 wt%, a framework silica to alumina ratio (SiO 2 /Al 2 O 3 Molar ratio) =4.6, unit cell constant of 2.470nm, relative crystallinity of 90%, which is the pH of the filter cake of the as-synthesized NaY molecular sieve after washing with industrial water, of 7.6; magnesium chloride, magnesium nitrate, lanthanum chloride and lanthanum nitrate are chemical pure reagents produced by Beijing chemical factory, and rare earth chloride and rare earth nitrate (respectively recorded as RECl) 3 And RE (NO) 3 ) 3 Mixed rare earth, wherein La 2 O 3 The content of Ce is 33.6 wt.% 2 O 3 The content of the rare earth alloy is 66.4 weight percent) which is an industrial product produced by rare earth alloy company of coated steel. The kaolin is special for cracking catalyst produced by Suzhou China kaolin company, and has 76 weight percent of solid content; the alumina sol is provided by Qilu division of China petrochemical catalyst, wherein the alumina content is 21 weight percent; silica sol is provided by Qilu division of China petrochemical catalyst, wherein the content of silica is 25 weight percent, and the pH value is 2.5.
The analysis method comprises the following steps: in each of the comparative examples and examples, the element content of the catalyst was measured by X-ray fluorescence spectrometry; the unit cell constant and the relative crystallinity of the zeolite in the catalyst are measured by an X-ray powder diffraction (XRD) method by using RIPP145-90 and RIPP146-90 standard methods (see, e.g., petrochemical analysis method (RIPP test method) Yang Cuiding, published by scientific Press, 1990). The specific surface area of the catalyst was measured according to GB/T5816-1995 method using an Autosorb-1 nitrogen adsorption/desorption apparatus from America Kang Da company, and the sample was degassed at 300℃for 6 hours before the test. The total pore volume of the catalyst was measured according to the RIPP151-90 standard method (see petrochemical analysis methods (RIPP test methods), yang Cuiding et al, scientific Press, 1990). The attrition index of the catalyst (used to characterize attrition resistance, the smaller the attrition index, the better the attrition resistance) was measured according to the RIPP29-90 standard method (see petrochemical analytical methods (RIPP test methods), yang Cuiding et al, scientific press, 1990).
The chemical reagents used in the comparative examples and examples are not particularly noted and are chemically pure in specification.
Example 1
(1) 150Kg of deionized water is added into a catalyst gelling kettle, and then the gelling raw materials are added in sequence under stirring: 52.1Kg of kaolin (76% by weight solids, from Kaolin Co., st. Johnson), 21Kg of alumina sol (21.5% alumina), 86.4Kg of silica Sol (SiO) 2 25 wt.% of ziluta, a product of chinese petrochemical catalyst, pH 2.5), for 30 minutes. Then, 24.3Kg (based on NaY dry basis) of unmodified NaY molecular sieve slurry (53 wt% concentration, qilu division Co., ltd.) was added thereto and stirred for 60 minutes. Then spray drying and forming are carried out, and roasting is carried out for 2 hours in a roasting furnace at 310 ℃ to obtain a catalyst microsphere A1;
(2) Adding the prepared catalyst microsphere A1 into 900L of decationizing water solution, stirring to mix uniformly, adding 7.36L of RE (NO) 3 ) 3 Solution (rare earth solution concentration with RE) 2 O 3 330 g/L), stirring, heating to 30 ℃ and maintaining for 1h, then filtering, washing, and drying a filter cake at 120 ℃ to obtain rare earth-containing catalyst microspheres B1 with reduced sodium oxide content;
(3) Roasting the catalyst microsphere B1 at the temperature of 410 ℃ for 6 hours in an atmosphere containing 45 volume percent of water vapor, and then drying to ensure that the water content is lower than 1 weight percent to obtain a catalyst microsphere C1 containing a molecular sieve with reduced unit cell constant;
(4) According to SiCl 4 : catalyst microsphere C1 (dry basis) =0.05: 1 weight ratio, siCl vaporized by heating is introduced 4 Reacting gas at 400 ℃ for 30Min to obtain a catalyst microsphere D1;
(5) The catalyst microsphere D1 is contacted with an acid solution for acid treatment modification. Catalyst microsphere D1 was added to a 0.08M hydrochloric acid solution at a weight ratio of 0.08M hydrochloric acid solution to catalyst microsphere on a dry basis of 10:1, stirring at 50 ℃ for 75 minutes, then adding citric acid, wherein the weight ratio of citric acid to catalyst on a dry basis is 0.02:1, stirring for 70 minutes at 50 ℃, filtering and washing to obtain the catalyst microsphere E1.
(6) At 25 ℃, 10Kg of catalyst microsphere E1 is taken and added into 25L of catalyst microsphere containing LaCl 3 (concentration in La) 2 O 3 120 g/L) and MgCl 2 The mixture solution (with the concentration of 55g/L calculated as MgO) was stirred for 5 minutes, filtered, then added into 22 liters of 11 wt% ammonia water, stirred for 5 minutes, filtered, dried, and calcined at 550 ℃ for 2 hours to obtain a catalyst finished product SCAT-1, and the performance analysis results are shown in Table 1.
Example 2
(1) 154Kg of deionized water is added into a catalyst gelling kettle, and then the gelling raw materials are added in sequence under stirring: 59.3Kg of kaolin (76% by weight solids available from Kaolin Co., st.) 16.8Kg of alumina sol (21.5% by weight alumina), 79.2Kg of silica Sol (SiO) 2 The content was 25% by weight, which was supplied by ziluta corporation, chinese petrochemical catalyst, and stirred for 30 minutes. Then, 22.5Kg (based on dry NaY) of unmodified NaY molecular sieve slurry (53 wt% strength, available from Qilu Co., ltd.) was added thereto and stirred for 60 minutes. Then spray drying and shaping, and bakingRoasting in a roasting furnace at 350 ℃ for 1 hour to obtain a catalyst microsphere A2;
(2) Adding the prepared catalyst microsphere A2 into 900L of decationizing water solution, stirring to mix uniformly, adding 6.1L of RE (NO) 3 ) 3 Solution (rare earth solution concentration with RE) 2 O 3 330 g/L), stirring, heating to 40 ℃ and maintaining for 1h, then filtering, washing, and drying a filter cake at 120 ℃ to obtain rare earth-containing catalyst microspheres B2 with reduced sodium oxide content;
(3) Roasting the catalyst microsphere B2 at the temperature of 350 ℃ in an atmosphere containing 55% by volume of water vapor for 6 hours, and then drying to ensure that the water content is lower than 1% by weight to obtain a catalyst microsphere C2 containing a molecular sieve with a reduced unit cell constant;
(4) According to SiCl 4 : catalyst microsphere C2 (dry basis) =0.08: 1 weight ratio, siCl vaporized by heating is introduced 4 Reacting the gas at 300 ℃ for 2 hours, washing with 900L of decationized water, filtering, and drying a filter cake at 120 ℃ for 5 hours to obtain a catalyst microsphere D2;
(5) The catalyst microsphere D2 is contacted with an acid solution for acid treatment modification. Firstly, adding the catalyst microspheres D2 into a sulfuric acid solution with the molar concentration of 0.05M, wherein the weight ratio of the sulfuric acid solution with the molar concentration of 0.05M to the catalyst microspheres D2 on a dry basis is 8:1, stirring for 90 minutes at 60 ℃, then heating to 85 ℃ and adding tartaric acid, wherein the weight ratio of tartaric acid to the catalyst on a dry basis is 0.025:1, stirring for 80 minutes at 85 ℃, filtering and washing to obtain the catalyst microsphere E2.
(6) 10Kg of catalyst microspheres E2 were added to 30L of a catalyst containing La (NO) 3 ) 3 (concentration in La) 2 O 3 Calculated as 100 g/L) and Mg (NO 3 ) 2 The mixture solution (with the concentration of 45g/L calculated by MgO) is stirred for 5 minutes and then filtered, and then added into 30L of 11% ammonia water by weight, stirred for 5 minutes, filtered, dried and roasted at 550 ℃ for 2 hours to obtain a catalyst finished product SCAT-2, and the performance analysis results are shown in Table 1.
Example 3
(1) In promoting171Kg of deionized water is added into a gelatinizing kettle of the gelatinizing agent, and then, the gelatinizing raw materials are sequentially added under stirring: 52.2Kg of kaolin (76% by weight solids, from Kaolin Co., st. Johnson), 16.8Kg of alumina sol (21.5% by weight alumina), 82.8Kg of silica Sol (SiO) 2 The content was 25% by weight, which was supplied by ziluta corporation, chinese petrochemical catalyst, and stirred for 30 minutes. Then 26.1Kg (based on NaY dry basis) of unmodified NaY molecular sieve slurry (53 wt% strength, available from zilut division, chinese petrochemical catalyst co.) was added and stirred rapidly for 60 minutes. Then spray drying and forming are carried out, and roasting is carried out for 3 hours in a roasting furnace at 300 ℃ to obtain catalyst microspheres A3;
(2) Adding the prepared catalyst microsphere A3 into 900L of decationizing water solution, stirring to mix uniformly, adding 9.3L of RE (NO) 3 ) 3 Solution (rare earth solution concentration with RE) 2 O 3 330 g/L), stirring, heating to 35 ℃ and keeping for 1h, then filtering, washing, and drying a filter cake at 120 ℃ to obtain rare earth-containing catalyst microspheres B3 with reduced sodium oxide content;
(3) Roasting the catalyst microsphere B3 at 390 ℃ for 5 hours in an atmosphere containing 50 volume percent of water vapor, and then drying to ensure that the water content is lower than 1 weight percent to obtain a catalyst microsphere C3 containing a molecular sieve with reduced unit cell constant;
(4) According to SiCl 4 : catalyst microsphere C3 (dry basis) =0.10: 1 weight ratio, siCl vaporized by heating is introduced 4 Reacting the gas at 350 ℃ for 1h, washing with 900L of decationized water, filtering, and drying the filter cake at 120 ℃ for 5h to obtain a catalyst microsphere D3;
(5) And (3) contacting the catalyst microsphere D3 with an acid solution for acid treatment modification. Firstly, adding the catalyst microsphere D3 into a nitric acid solution with the molar concentration of 0.07M, contacting for 90 minutes at the temperature of 45 ℃, then adding oxalic acid, contacting for 80 minutes at the temperature of 45 ℃, and obtaining the catalyst microsphere E3 through filtration, washing and drying; wherein the weight ratio of oxalic acid to catalyst on a dry basis is 0.05:1, a weight ratio of nitric acid solution with a molar concentration of 0.07M to the catalyst microspheres D3 on a dry basis of 12:1.
(6) The catalyst microsphere E1 was added to a solution containing 35L LaCl at 25℃ 3 (concentration in La) 2 O 3 75 g/L) and MgCl 2 The mixture solution (35 g/L in terms of MgO) was stirred for 5 minutes and then filtered, and then added to 35L of 8% ammonia water by weight, stirred for 5 minutes, filtered, dried, and calcined at 550℃for 2 hours to give a catalyst finished product SCAT-3, the results of which are shown in Table 1.
Comparative example 1
2000Kg (dry basis) of skeleton SiO 2 /Al 2 O 3 NaY-type zeolite (sodium oxide content 13.5 wt%, product of Mitsui catalyst Oldham Co.) of 4.6 was added to the catalyst containing 20m 3 Adding 581L RECl after stirring uniformly in a primary water exchange tank at 25deg.C 3 Solution (RECl) 3 Rare earth concentration in solution as RE 2 O 3 330 g/L), continuously stirring for 60 minutes, filtering, washing, and sending the filter cake into a flash evaporation drying furnace for drying; then, the mixture is sent into a roasting furnace to be roasted for 6 hours under the atmosphere of 60 percent of water vapor and 40 percent of air by volume at the temperature of 400 ℃; then roasting for 2.5 hours at 500 ℃ in dry air atmosphere (the water vapor content is lower than 1% by volume) to make the water content lower than 1% by weight, and then directly feeding the materials into a continuous gas-phase hyperstable reactor for gas-phase hyperstable reaction. The gas phase ultrastable reaction process of molecular sieve in continuous gas phase ultrastable reactor and its subsequent tail gas absorption process are carried out according to the method of example 1 disclosed in CN103787352A patent, and the process conditions are SiCl 4 : weight ratio of Y zeolite = 0.38:1, the molecular sieve feed rate was 800 kg/hr and the reaction temperature was 420 ℃. Separating the molecular sieve material after the gas phase ultrastable reaction by a gas-solid separator, and then sending the molecular sieve material into a secondary exchange tank, wherein 20m of molecular sieve material is added in the secondary exchange tank in advance 3 Adding molecular sieve material weight of 2000Kg (dry basis weight) into secondary exchange tank, stirring uniformly, then adding 10 wt% hydrochloric acid 0.65m 3 Heating to 90 ℃, stirring for 70 minutes, then adding 125Kg of citric acid, stirring for 60 minutes at 90 ℃, Filtering, washing and drying to obtain the modified Y-type molecular sieve which is marked as DZ-1.
11.62 Kg of an alumina sol having an alumina content of 21.5% by weight was added to 69.5 Kg of decationized water, stirring was started, 27.63 Kg of kaolin having a solid content of 76% by weight was added to disperse for 60 minutes, and then 46Kg of a silica sol (SiO 2 The content was 25% by weight, which was supplied by ziluta corporation, chinese petrochemical catalyst, and stirred for 30 minutes. Then 15 kg (dry basis) of ground DZ1 molecular sieve is added, and after rapid stirring for 60 minutes, spray drying, roasting and washing treatment are carried out, and the catalyst is obtained after drying and is marked as DC1. Wherein the obtained DC1 catalyst contains 30 weight percent of DZ1 molecular sieve, 42 weight percent of kaolin, 23 weight percent of silica sol binder and 5 weight percent of alumina sol based on dry basis.
Comparative example 2
2000Kg (dry basis) of skeleton SiO 2 /Al 2 O 3 NaY-type zeolite (sodium oxide content 13.5 wt%, product of Mitsui catalyst Oldham Co.) of 4.6 was added to the catalyst containing 20m 3 In a primary exchange tank of the decationized water, stirring uniformly at 90 ℃, then adding 685L RECl 3 Solution (RECl) 3 Rare earth concentration in solution as RE 2 O 3 330 g/L), stirring for 60 minutes; filtering, washing, and delivering the filter cake into a flash evaporation drying furnace for drying; then, the mixture is sent into a roasting furnace to be roasted for 6 hours under the atmosphere of 70 percent of water vapor at the temperature (atmosphere temperature) of 440 ℃; then, the molecular sieve material enters a roasting furnace to be roasted and dried, wherein the roasting temperature is 500 ℃, the atmosphere is a dry air atmosphere, and the roasting time is 2 hours, so that the water content is lower than 1 weight percent; then, the Y-type molecular sieve material with the unit cell constant reduced is directly sent into a continuous gas-phase ultrastable reactor for gas-phase ultrastable reaction. The gas phase ultrastable reaction process of the molecular sieve in the continuous gas phase ultrastable reactor and the subsequent tail gas absorption process thereof are carried out according to the method of example 1 disclosed in the patent CN103787352A, and the process conditions are as follows: siCl 4 : weight ratio of Y zeolite = 0.30:1, molecular sieve feed rate was 800 kg/hr and reaction temperature was 470 ℃. Separating the molecular sieve material after the gas phase ultrastable reaction by a gas-solid separator, and then delivering the molecular sieve material into a secondary cross sectionIn the tank replacement, 20m of the secondary tank is added in advance 3 Adding molecular sieve material weight of 2000Kg (dry basis weight) into secondary exchange tank, stirring, adding sulfuric acid solution with concentration of 7 wt% 0.85m 3 Heating to 85 ℃, stirring for 80 minutes, then adding 65Kg of citric acid and 55Kg of tartaric acid, continuously stirring for 80 minutes at 85 ℃, filtering, washing and drying to obtain a modified Y-type molecular sieve product which is marked as DZ-2.
Referring to the preparation method of comparative example 1, the catalyst slurry was prepared by beating DZ2 molecular sieve, kaolin, water, silica sol binder and alumina sol, spray-drying, calcining, washing and drying to prepare a microsphere catalyst, and the prepared catalytic cracking catalyst was designated as DC2. Wherein the obtained DC2 catalyst contains 30 weight percent of DZ2 molecular sieve, 42 weight percent of kaolin, 23 weight percent of silica sol binder and 5 weight percent of alumina sol based on dry basis.
Comparative example 3
The catalyst was prepared according to the method of example 1 of patent application CN1854255A, product designated DC3.
Comparative example 4
A catalyst was prepared according to the method of example 1, except that after the catalyst was spray-dried and molded, the catalyst microspheres were calcined in a calciner at 500℃for 1 hour to obtain catalyst DC4.
Comparative example 5
Catalyst of comparative example 1 step (6) of reference example 1 rare earth oxide and magnesium oxide were introduced to obtain catalyst DC5
Examples 4 to 6
Examples 4 to 6 are for explaining the heavy metal contamination method of the catalyst and the catalytic cracking performance of the catalytic cracking catalyst of the present invention.
The SCAT-1, SCAT-2 and SCAT-3 catalysts are firstly subjected to cyclic pollution (for depositing Ni and V) on a cyclic aging device, the Ni and V contents of the catalysts after cyclic pollution are shown in a table 3, and the cyclic pollution step comprises the following steps: after introducing heavy metals (Ni and V) into the catalyst by Michael impregnation, the catalyst after introducing heavy metals is then loaded into a D-100 apparatus (small fixed fluidized bed) and treated on the D-100 apparatus as follows:
(a) Heating to 600 ℃ at a heating rate of 20 ℃/min under nitrogen atmosphere;
(b) Heating to 780 ℃ at a heating rate of 1.5 ℃/min, keeping the temperature at 780 ℃, and changing the treatment atmosphere in the constant temperature process according to the following steps:
(i) Treating for 10 minutes in an atmosphere containing 40% by volume of nitrogen (wherein the nitrogen contains 5% by volume of propylene) and 60% by volume of water vapor;
(ii) Treating for 10 minutes in an atmosphere containing 40% by volume of nitrogen (pure nitrogen, no propylene) and 60% by volume of water vapor;
(iii) To contain 40% by volume of air (4000. Mu. Mol/mol SO) 2 ) An atmosphere treatment of 60% by volume of water vapor for 10 minutes;
(iv) treating for 10 minutes in an atmosphere containing 40% by volume of nitrogen and 60% by volume of water vapor; then repeating the circulating steps (i) - (iv) for one time according to the sequence, and then repeating the step (i) to finish the circulating pollution step;
then an aging step of aging the catalyst mixture after the cyclic contamination at 788 ℃ in an atmosphere containing 80% by volume of water vapor and 20% by volume of air for 8 hours;
the catalytic performance of the catalyst after cyclic contamination-aging was then examined on an ACE unit, wherein the feed oil was brought into contact with the catalyst mixture at the bottom of the reactor, wherein the catalyst loading was 9g, the reaction temperature 500℃and the weight hourly space velocity was 16h －1 The ratio of agent to oil (weight ratio) was 5, the raw material properties of the ace experiment are shown in table 2, and the evaluation results are shown in table 3.
Wherein conversion = 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
Dry gas selectivity = dry gas yield/conversion
Comparative examples 6 to 10
Comparative examples 6 to 10 illustrate the reactivity of the catalytic cracking catalysts prepared by the methods provided in comparative examples 1 to 5.
The DC 1-DC 5 catalysts are firstly subjected to cyclic pollution (for depositing Ni and V) on a cyclic aging device, the Ni and V contents of the catalysts after cyclic pollution are shown in a table 3, and the cyclic pollution step is shown in an example 4. Then an aging step of aging the catalyst mixture after the cyclic contamination at 788 ℃ in an atmosphere containing 80% by volume of water vapor and 20% by volume of air for 8 hours;
the catalytic performance of the catalyst after cyclic contamination-aging was then examined on an ACE unit, wherein the feed oil was brought into contact with the catalyst mixture at the bottom of the reactor, wherein the catalyst loading was 9g, the reaction temperature 500℃and the weight hourly space velocity was 16h －1 The ratio of agent to oil (weight ratio) was 5, the raw material properties of the ace experiment are shown in table 2, and the evaluation results are shown in table 3.
TABLE 1
As shown in the results of Table 1, the catalytic cracking catalyst provided by the invention has larger pore volume and specific surface area, better strength, low sodium oxide content in the catalyst and high relative crystallinity of the molecular sieve in the catalyst.
Table 2 ACE evaluation of raw oil properties
TABLE 3 Table 3
As can be seen from Table 3, the catalytic cracking catalyst provided by the invention has obviously lower coke selectivity after Ni and V pollution and aging, has low dry gas selectivity, higher total liquid product yield and gasoline yield, and higher heavy oil conversion activity, and shows that the catalytic cracking catalyst provided by the invention has excellent Ni and V pollution resistance.

Claims (11)

1. A preparation method of a catalytic cracking catalyst resistant to metal pollution comprises the following steps:
(S1): forming first microspheres comprising an ultrastable Y-type molecular sieve, an alumina binder, a silica binder and clay;
(S2): the first microspheres are contacted with inorganic acid and organic acid solution to remove non-framework aluminum in the molecular sieve, and the second microspheres are obtained by filtering and washing;
(S3): the second microsphere is contacted with a mixed solution containing rare earth salt and alkaline earth metal salt, filtered, contacted with ammonia water, filtered, dried and roasted to obtain a catalytic cracking catalyst finished product.
2. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the weight ratio of alumina binder in terms of alumina to silica binder in terms of silica in the first microspheres is 2 to 15:10-30 parts of a base;
The weight ratio of the ultrastable Y-type molecular sieve in the first microsphere based on dry basis to the silicon oxide binder based on silicon oxide is preferably 10-50:10-30 parts of a base;
the weight ratio of clay in dry basis to silica binder in silica in the first microspheres is preferably 10-80:10-30 parts of a base;
in the step (S2), the first microspheres are contacted with an inorganic acid and an organic acid solution, preferably at a temperature of 25-70 ℃, and may be contacted with the inorganic acid solution and the organic acid solution sequentially, or may be contacted with a solution containing both the inorganic acid and the organic acid, wherein the molar concentration of the inorganic acid in the solution containing the inorganic acid is preferably 0.01mol/L to 0.15mol/L, and the weight ratio of the solution containing the inorganic acid to the first microspheres on a dry basis is 6-12:1, a step of; the weight ratio of the organic acid to the first microspheres on a dry basis is 0.02-0.10:1, a step of;
in the step (S3), in one mode, the second microspheres are contacted with a solution containing rare earth salt and alkaline earth metal salt at room temperature for preferably 5-30 minutes, then filtered, then contacted with ammonia water for preferably 5-30 minutes, filtered, dried and roasted to obtain a catalytic cracking catalyst finished product;
in step (S3), the rare earth is, for example, la, ce, pr, nd or a mixed rare earth including one or more of the above rare earth elements.
One or more of the alkaline earth metals, e.g., be, mg, ca, sr, ba, preferably Mg and/or Ca, more preferably Mg;
the rare earth salt in the step (S3) is preferably lanthanum nitrate and/or lanthanum chloride, and the alkaline earth metal salt is preferably magnesium nitrate and/or magnesium chloride;
preferably, the concentration of the rare earth salt in the solution containing the rare earth salt and the alkaline earth metal salt is RE 2 O 3 The concentration of the alkaline earth metal salt is calculated as 60-150 g/L, and the concentration of the alkaline earth metal salt is calculated as 30-80 g/L of alkaline earth metal oxide;
the concentration of the ammonia water is NH 3 Preferably 5 to 15% by weight;
the weight ratio of the mixed solution containing the rare earth salt and the alkaline earth metal salt to the second microsphere is preferably 3-6: 1, a step of;
preferably, with RE 2 O 3 And (3) the rare earth content in the finished catalytic cracking catalyst obtained in the step (S3) is 0.2-1 wt% higher than that of the second microspheres.
3. The method for preparing a catalytic cracking catalyst according to claim 1, comprising the steps of:
(1) Mixing unmodified NaY molecular sieve with alumina binder, silica binder, clay and water, pulping, spray drying, roasting at 280-380 deg.C for preferably 1-4 hr to obtain catalyst microsphere A; the aluminum oxide binder is aluminum sol;
(2) Making the catalyst microsphere A contact with rare earth salt solution to perform ion exchange reaction, filtering and washing to obtain a catalyst microsphere B;
(3) Roasting the catalyst microsphere B at the temperature of 350-450 ℃ under the atmosphere containing 40-60% by volume of water vapor for 4-6 hours, and optionally drying to obtain a catalyst microsphere C, wherein the water content of the catalyst microsphere C is preferably not more than 1% by weight;
(4) Allowing the catalyst microsphere C to react with SiCl 4 The gas contacts and reacts, and then the catalyst D is obtained through washing and filtering; wherein SiCl 4 : weight ratio of catalyst microsphere C on a dry basis = 0.03-0.2: 1, the reaction temperature is 250-450 ℃, and the reaction time is 10 minutes to 5 hours;
(5) The catalyst microsphere D is contacted with inorganic acid and organic acid solution for at least 60 minutes at the temperature of 25-70 ℃, and the catalyst microsphere E is obtained after filtration and washing;
(6) Contacting the catalyst microsphere E with a mixed solution containing rare earth salt and alkaline earth metal salt, filtering, then contacting with ammonia water, filtering, drying and roasting; preferably, the catalyst microsphere E is added into a mixed solution containing rare earth salt and alkaline earth metal salt under the condition of room temperature, preferably stirred for 5-30 minutes, filtered, then added into ammonia water, preferably 10-15 wt%, the concentration of the ammonia water is preferably stirred for 5-30 minutes, filtered, dried and roasted to obtain a catalyst finished product F, and the temperature of the room temperature is 10-30 ℃.
4. A process for preparing a catalytic cracking catalyst according to claim 3, wherein in step (1), said unmodified NaY molecular sieve is a hydrothermally synthesized NaY molecular sieve which has been washed with water only, for example, with industrial water and the pH of the NaY molecular sieve cake is determined to be 7 to 9 after washing, and the calcination temperature of said catalyst microspheres in step (1) is 300 to 350 ℃.
5. The method for preparing a catalytic cracking catalyst according to claim 3, wherein the temperature of the ion exchange reaction in step (2) is 20 to 60 ℃;
in the step (2), the temperature of the ion exchange reaction is preferably 25-45 ℃, the exchange time is 90-120 minutes, the rare earth salt solution is an aqueous solution of rare earth salt, and the rare earth salt is preferably rare earth chloride and/or rare earth nitrate; such as La, ce, pr, nd or a misch metal comprising one or more of the above rare earth elements.
6. A process for preparing a catalytic cracking catalyst according to claim 3, wherein in step (3), the calcination temperature is preferably 370 to 420 ℃; the roasting atmosphere is preferably an atmosphere containing 45-55% by volume of water vapor; the calcination time is preferably 5 to 6 hours.
7. The method for preparing a catalytic cracking catalyst according to claim 3, wherein in the step (4), the catalyst microspheres C and SiCl are mixed with each other 4 The temperature of the gas contact reaction is 280-420 ℃; the catalyst microsphere C and SiCl 4 The reaction time of the gas contact reaction is preferably 0.2 hours to 2 hours; the catalyst microsphere C and SiCl 4 Gas contact reaction of SiCl 4 The weight ratio to the catalyst microspheres C on a dry basis is preferably 0.05 to 0.15:1.
8. a process for the preparation of a catalytic cracking catalyst according to claim 3, characterized in that the catalyst microspheres D in step (5) are contacted with an inorganic acid and an organic acid solution, the catalyst microspheres D obtained in step (4) are first mixed with an inorganic acid solution of medium strength or higher, contacted at 25-70 ℃, preferably 40-60 ℃ for at least 60 minutes, such as 60-120 minutes, and then added with an organic acid, contacted at 25-70 ℃, preferably 40-60 ℃ for at least 60 minutes, such as 60-120 minutes, filtered, washed and dried.
9. The method for preparing a catalytic cracking catalyst according to claim 8, wherein the weight ratio of the organic acid to the catalyst microspheres D on a dry basis is 0.02 to 0.10:1, the weight ratio of the inorganic acid solution with medium strength to the catalyst microsphere D on a dry basis is 6-12:1, the molar concentration of the inorganic acid with medium strength or more in the inorganic acid solution with medium strength or more is preferably 0.01mol/L to 0.15mol/L;
Preferably, the mixed solution of the rare earth salt and the alkaline earth metal salt in the step (6), wherein the rare earth salt is lanthanum nitrate or lanthanum chloride, and the alkaline earth metal salt is magnesium nitrate or magnesium chloride; the ammonia water in the step (6) is ammonia water solution, the temperature of the catalyst microsphere E contacted with the mixed solution containing rare earth salt and alkaline earth metal salt is room temperature, the temperature of the catalyst microsphere E contacted with the ammonia water is room temperature, and the room temperature is 10-30 ℃.
10. The method for preparing a catalytic cracking catalyst according to claim 3, wherein the catalyst microsphere a contains 10 to 50 wt% of an unmodified NaY-type molecular sieve on a dry basis, 2 to 15 wt% of an alumina binder on an alumina basis, 10 to 30 wt% of a silicon binder on a silica basis, and 10 to 80 wt% of a clay on a dry basis; alternatively, the catalyst microsphere a contains: 20-50 wt% of unmodified NaY-type molecular sieve based on dry basis, 20-55 wt% of clay based on dry basis, 3-5 wt% of alumina sol based on alumina, and 10-25 wt% of silica sol based on silica.
11. A catalytic cracking catalyst obtained by the catalytic cracking catalyst production method according to any one of claims 1 to 10.
CN202210183718.3A 2022-02-28 2022-02-28 Catalytic cracking catalyst for resisting metal pollution and preparation method thereof Pending CN116689017A (en)

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