CN113952978B - Catalytic cracking catalyst and preparation method and application thereof - Google Patents

Catalytic cracking catalyst and preparation method and application thereof Download PDF

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Publication number
CN113952978B
CN113952978B CN202010700308.2A CN202010700308A CN113952978B CN 113952978 B CN113952978 B CN 113952978B CN 202010700308 A CN202010700308 A CN 202010700308A CN 113952978 B CN113952978 B CN 113952978B
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solution
tail gas
gas
content
catalytic cracking
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CN113952978A (en
Inventor
许明德
杨凌
周翔
苏周全
张杰潇
于善青
田辉平
王福功
潘红年
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Sinopec Catalyst Co
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Sinopec Catalyst Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B01J35/30—
    • B01J35/615—
    • B01J35/633—
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J2029/081—Increasing the silica/alumina ratio; Desalumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • 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

Abstract

The invention relates to a catalytic cracking catalyst, a preparation method and application thereof, wherein the method comprises the following steps: absorbing tail gas generated by preparing a gas-phase ultra-stable molecular sieve by adopting a first solvent to obtain a first solution, a second solution and a third solution; mixing a silicon source with the first solution for reaction to obtain a first mixture, wherein the pH value of the first mixture is 3.0-4.5; mixing a gas-phase ultrastable molecular sieve, clay, a binder, a first mixture and a second solution, and performing first drying and roasting on the obtained mixture to obtain a first solid; after mixing the first solid, the second solvent, the third solution and optionally the ammonium source, the second solid is removed from the resulting slurry and subjected to a second drying. The method can comprehensively utilize chlorine in the tail gas, thereby effectively reducing the salt emission in the wastewater, and the prepared catalytic cracking catalyst can produce more low-carbon olefins, especially ethylene and propylene, and reduce the yields of dry gas and coke.

Description

Catalytic cracking catalyst and preparation method and application thereof
Technical Field
The invention provides a catalytic cracking catalyst, a preparation method and application thereof.
Background
During the preparation process of the catalytic cracking catalyst, a large amount of acid radical ions can be introduced by acidification of pseudo-boehmite, a washing process of sodium oxide in the catalyst, preparation of binder silica sol and the like, and the introduction of the fresh acid radical ions can cause the increase of salt emission in the sewage of the catalyst at the later stage, and meanwhile, the salt ions cannot be recycled.
Y-type molecular sieve and SiCl in preparation process of gas-phase ultrastable molecular sieve 4 The reaction of Y-type molecular sieves utilizing mainly SiCl is well known to those skilled in the art 4 The Si in the process is subjected to dealumination and silicon supplementing of the molecular sieve, the rest chlorine cannot be effectively utilized and can only be discharged into the atmosphere or sewage, and the environment is polluted by the atmosphere and the sewage discharged at the present stage, so that the realization of the comprehensive utilization of the acid radical ion in the whole process is an important environmental protection.
CN101733141A relates to a catalytic cracking catalyst and a preparation method thereof, and the preparation method of the catalyst comprises the steps of contacting sodium silicate with acid to prepare SiO with pH value of 10-11.5 2 And mixing alkaline silica sol with the content of 3-20 wt% with active component, pulping and drying. The cracking catalyst prepared by the method has higher pore volume, and has higher heavy oil cracking capability when being used for heavy oil catalytic cracking.
Patent 201811172635.4 relates to the technical field of gas-phase ultrastable molecular sieve treatment and discloses a treatment method of gas-phase ultrastable molecular sieve tail gas, an obtained mixture, application of the mixture and a preparation method of a catalytic cracking catalyst. The processing method provided by the invention comprises the following steps: 1) Contacting gas-phase super-stable molecular sieve tail gas with water in a first-stage absorption kettle (1) for first absorption to obtain a first absorption liquid and first tail gas; 2) And (3) contacting the first tail gas with water in a second-stage absorption kettle (2) for second absorption to obtain a second absorption liquid and second tail gas. The method can enable the tail gas finally discharged to reach the discharge standard, and is simple to operate and low in cost. The obtained liquid mixture containing chlorine-containing silicon-aluminum elements can be directly applied to the preparation process of the catalytic cracking catalyst, so that the introduction amount of fresh hydrochloric acid and aluminum stones in the preparation process of the catalytic cracking catalyst is reduced, the cost is reduced, the emission of chlorine-containing wastewater is reduced, and the cracking performance of the catalytic cracking catalyst is improved. However, the liquid mixture containing the chlorine-silicon-aluminum elements is not completely used, the rest Cl ions are wasted, the HCl concentration of the liquid mixture containing the chlorine-silicon-aluminum elements is too high, the absorption process is complex, the silica sol is unstable and easy to coagulate, the adhesive property is poor, the damage to a molecular sieve in the catalyst and the blocking of a pore canal are caused, and the performance of the catalyst is influenced.
CN106732745a discloses a preparation method of catalytic cracking catalyst, the method comprises the steps of contacting NaY molecular sieve raw powder with halogen-containing gas to carry out gas-phase ion exchange reaction, completing sodium reduction and superstabilization of NaY molecular sieve raw powder in one step, obtaining low-sodium high-silicon-aluminum ratio molecular sieve, compounding clay raw ores of different types, then carrying out high-concentration acid treatment to obtain acid-activated composite clay, mixing and pulping the low-sodium high-silicon-aluminum ratio molecular sieve and acid-activated composite clay with binder, rare earth and cation-removing water, spraying and granulating, roasting and solidifying, and obtaining the finished product of catalytic cracking catalyst without washing and drying. The catalytic cracking catalyst can obviously reduce the content of olefin in gasoline, improve the light oil yield, and has short preparation flow and no ammonia nitrogen emission.
In recent years, with the increasing strictness of environmental protection requirements, chlorine, which is a substance with stronger corrosiveness, cannot be discharged to the atmosphere, and can only be absorbed by water for sewage discharge, so that the increasing of salt content and the waste of chlorine element in the sewage can be caused.
Disclosure of Invention
The invention aims to provide a catalytic cracking catalyst and a preparation method and application thereof, and the method can prepare the catalytic cracking catalyst which is beneficial to the high yield of low-carbon olefin, can reduce the salt in wastewater and realize the comprehensive utilization of chloride ions.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing a catalytic cracking catalyst, the method comprising:
(1) Absorbing tail gas generated by preparing a gas-phase ultra-stable molecular sieve by adopting a first solvent to obtain a first solution, a second solution and a third solution;
(2) Mixing a silicon source with the first solution for reaction, and regulating the pH value of a reaction product to be 3.0-4.5 to obtain a first mixture;
(3) Mixing the gas-phase ultrastable molecular sieve, clay, binder, the first mixture and the second solution, and performing first drying and roasting on the obtained mixture to obtain a first solid;
(4) After mixing the first solid, the second solvent, the third solution and optionally the ammonium source, the second solid is removed from the resulting slurry and subjected to a second drying.
Optionally, the concentration of HCl in the first solution is 3-10 wt%, the concentration of HCl in the second solution is 5-15 wt%, and the concentration of HCl in the third solution is 3-10 wt%.
Optionally, in step (2), the pH of the first mixture is 3.0-4.5; the solids content of the first mixture is 25-40 wt.%.
Optionally, the silicon source is selected from one or more of water glass, sodium silicate and silicon dioxide;
preferably, the silicon source is water glass, and SiO in the water glass 2 The content of (2) is 10-35 wt%, and the modulus of the water glass is 3.0-5.0.
Optionally, in step (3), the gas phase ultrastable molecular sieve, the clay, the binder, the first mixture, and the second solution are used in amounts of weightThe weight ratio is (32-38): (22-42): (14-20): (12-20): (4.32-48), the binder is made of Al 2 O 3 The first mixture is calculated as SiO 2 And (5) counting.
Optionally, step (4) includes: washing the second solid at 5-70 ℃ and then performing second drying;
in the step (4), the weight ratio of the first solid to the second solvent is 1: (2-5) the weight ratio of the first solid to the third solution is 1: (0.01-0.1), said first solid being on a dry weight basis and said third solution being on a chlorine basis.
Optionally, the method for absorbing the tail gas comprises the following steps:
s1, contacting the tail gas generated by preparing a gas-phase ultra-stable molecular sieve with a first part of the first solvent for first absorption to obtain a first solution and first tail gas;
s2, contacting the first tail gas with a second part of the first solvent for second absorption to obtain a second solution and second tail gas;
s3, contacting the second tail gas with a third part of the first solvent for third absorption to obtain a third solution and third tail gas; or alternatively, the process may be performed,
the method for absorbing the tail gas comprises the following steps:
and (3) contacting the tail gas generated by preparing the gas-phase ultra-stable molecular sieve with the first solvent to absorb the tail gas to obtain a tail gas absorption liquid, and dividing the tail gas absorption liquid into the first solution, the second solution and the third solution.
Optionally, the tail gas contains 40-83 wt% chlorine, 5-25 wt% aluminum and 12-35 wt% silicon based on the total weight of the tail gas.
Optionally, in step (1), the method for preparing the gas-phase ultrastable molecular sieve comprises: making Y-type molecular sieve and SiCl 4 Carrying out dealumination and silicon supplementing reaction by a gas phase superstable method;
the conditions of the dealumination and silicon supplementing reaction by the gas-phase ultrastable method comprise: the temperature is 250-700 ℃ and the time is 0.15-100min, and the Y-type molecular sieve and the molecular sieve are preparedThe SiCl 4 The weight ratio of the dosage is 1: (0.05-0.3).
Optionally, the first drying conditions include: the temperature is 400-600 ℃ and the time is 0.5-2 hours;
the roasting conditions include: the temperature is 300-550 ℃ and the time is 0.5-2 hours;
the second drying conditions include: the temperature is 120-200 ℃ and the time is 1-2 hours.
Optionally, the first solvent and the second solvent are each independently selected from one or more of deionized water, distilled water, and decationized water;
the clay is one or more selected from diatomite, kaolin, rectorite, bentonite, montmorillonite and sepiolite;
the binder is one or more selected from pseudo-boehmite;
the ammonium source is selected from one or more of ammonium sulfate, ammonium chloride, ammonia water, ammonium phosphate, diammonium hydrogen phosphate and monoammonium hydrogen phosphate.
The second aspect of the invention provides a catalytic cracking catalyst prepared by the method provided by the first aspect of the invention.
A third aspect of the present invention provides the use of the catalytic cracking catalyst provided in the second aspect of the present invention in the catalytic cracking of crude oil.
Alternatively, al in the catalytic cracking catalyst is based on the dry weight of the catalytic cracking catalyst 2 O 3 The content of (C) is 30-45 wt%, siO 2 The content of Na is 45-60 wt% 2 The content of O is 0.05-0.3 wt%, fe 2 O 3 The content of RE is 0.2-1 wt% 2 O 3 The content of (C) is 0-6 wt%, the content of Cl is 0.1-1 wt%, and the content of SO is 4 2- The content of (C) is 0.1-2 wt%, and the specific surface area is 220-320m 2 Per g, pore volume of 0.28-0.38mL/g, abrasion index of 0.5-2%/h, and micro-reactivity of 65-80% after 100% water vapor aging deactivation treatment for 12 hours at 800 ℃.
Alternatively, the second aspect of the present invention provides the use of a catalytic cracking catalyst in the catalytic cracking of crude oil.
Through the technical scheme, the method can be beneficial to the high yield of low-carbon olefin, in particular to the catalytic cracking catalyst capable of preparing high yield of ethylene and propylene; and can realize the comprehensive utilization of chloride ions so as to reduce Cl in the preparation process of the catalyst - 、NH 4 + 、SO 4 2- The extra introduction of the plasma reduces the discharge amount of salt in the sewage during the preparation process of the catalyst and shortens the preparation flow of the catalyst.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is a schematic flow diagram of one embodiment of the present invention for preparing a catalytic cracking catalyst.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In a first aspect, the present invention provides a process for preparing a catalytic cracking catalyst, the process comprising:
(1) Absorbing tail gas generated by preparing a gas-phase ultra-stable molecular sieve by adopting a first solvent to obtain a first solution, a second solution and a third solution;
(2) Mixing a silicon source with a first solution to react to obtain a first mixture, wherein the pH value of the first mixture is 3.0-4.5;
(3) Mixing a gas-phase ultrastable molecular sieve, clay, a binder, a first mixture and a second solution, and performing first drying and roasting on the obtained mixture to obtain a first solid;
(4) After mixing the first solid, the second solvent, the third solution and optionally the ammonium source, the second solid is removed from the resulting slurry and subjected to a second drying.
The method of the invention can comprehensively utilize chlorine in the tail gas generated by preparing the gas-phase ultra-stable molecular sieve, and simultaneously reduce Cl in the preparation process of the catalyst - 、NH 4 + 、SO 4 2- The additional introduction of the plasma is beneficial to reducing the salt discharge in the sewage. The prepared catalytic cracking catalyst is beneficial to the high yield of low-carbon olefin, especially ethylene and propylene, and the yield of dry gas and coke is reduced.
In one embodiment, a method for absorbing tail gas from a process for preparing a gas phase ultrastable molecular sieve using a first solvent may comprise:
s1, contacting tail gas generated in the preparation of a gas-phase ultra-stable molecular sieve with a first part of a first solvent for first absorption to obtain a first solution and first tail gas;
s2, contacting the first tail gas with a second part of the first solvent for second absorption to obtain a second solution and second tail gas;
s3, contacting the second tail gas with the first solvent of the third part to perform third absorption to obtain a third solution and third tail gas.
According to the present invention, the first solvent may be divided into the first solvent of the first portion, the first solvent of the second portion, and the first solvent of the third portion according to actual needs, which is not particularly limited in the present invention. In a preferred embodiment, for every 1m 3 The first solvent is used in an amount of 40 to 80L, preferably 40 to 60L, in the first portion of the offgas produced by the gas-phase ultrastable molecular sieve. Relative to every 1m 3 The amount of the first solvent used in the second portion is 20 to 40L, preferably 20 to 30L. Relative to every 1m 3 The amount of the first solvent in the third portion is 10 to 20L, preferably 10 to 15L.
In another embodiment, a method for absorbing tail gas from the production of a gas phase ultrastable molecular sieve with a first solvent may comprise: and (3) contacting and absorbing the tail gas generated by preparing the gas-phase super-stable molecular sieve with a first solvent to obtain a tail gas absorption liquid, and dividing the tail gas absorption liquid into a first solution, a second solution and a third solution. In this embodiment, the concentration of HCl in the first solution, the second solution, and the third solution is the same.
The apparatus used for absorbing the off-gas according to the present invention is not particularly limited as long as it is a container having a certain corrosion resistance and being closed, and may be, for example, an absorption tank, or an absorption tub.
According to the invention, the tail gas contains dust and silicon tetrachloride, the dust contains aluminum element and silicon element, and the tail gas contains 40-83 wt% of chlorine, 5-25 wt% of aluminum and 12-35 wt% of silicon based on the total weight of the tail gas.
According to the invention, the concentration of HCl in the first solution may be 3-10 wt.%, preferably 5-9 wt.%, the concentration of HCl in the second solution may be 5-15 wt.%, preferably 5-9 wt.%, and the concentration of HCl in the third solution may be 3-10 wt.%, preferably 5-9 wt.%.
According to the invention, in step (2), the pH of the first mixture may be from 3.0 to 4.5, preferably from 3.2 to 4.4; the solids content of the first mixture may be 25 to 40% by weight, preferably 25 to 30% by weight. The invention regulates and controls the pH value of the first mixture by controlling the dosage ratio of the silicon source and the first solution, when the pH value of the first mixture is in the range, the catalytic cracking catalyst with better reaction characteristics can be prepared, and when the catalyst is used in the catalytic cracking process of crude oil, the yield of dry gas coke can be further reduced, and the yields of ethylene and propylene are improved.
According to the present invention, in the step (2), the manner of mixing the silicon source and the first solution is not particularly limited, and for example, the silicon source and the first solution may be mixed in a batch manner or may be mixed in a continuous manner. The order in which the silicon source and the first solution are mixed is also not particularly limited, and in a preferred embodiment, the first solution is added to the silicon source. The conditions of the mixing reaction may include: the temperature is 12-30deg.C, preferably 15-25deg.C, and the time is 0.1-2 hr, preferably 0.2-1 hr.
According to the invention, the silicon source may be selected from water glass, sodium silicate andone or more of silica; preferably, the silicon source is water glass, siO in the water glass 2 The content of (2) may be 10-35 wt% and the modulus of the water glass may be 3.0-5.0.
According to the invention, in step (3), the weight ratio of the amounts of gas-phase ultrastable molecular sieve, clay, binder, first mixture and second solution may vary within a wide range, and may be, for example, (32-38): (22-42): (14-20): (12-20): (4.32-48), preferably (32-36): (26-40): (14-18): (14-20): (5.04-48), binder is Al 2 O 3 The first mixture is calculated as SiO 2 And (5) counting.
According to the present invention, the step (4) may include: the second solid taken out is washed at 5-70 ℃ and then is subjected to second drying. The method for removing the second solid is not particularly limited, and for example, filtration, centrifugal separation, etc. may be employed, and the filtration may be a plate filter, a belt filter, etc. The liquid used for washing is not particularly limited, and may be, for example, one or more of deionized water, distilled water, and decationized water.
According to the invention, in step (4), the weight ratio of the amounts of the first solid and the second solvent may vary within a wide range, for example 1: (2-5), preferably 1: (2-4); the weight ratio of the amounts of the first solid and the third solution may also vary within a wide range, for example 1: (0.01-0.1), preferably 1: (0.02-0.06), the first solid being on a dry weight basis and the third solution being on a chlorine basis.
According to the present invention, in step S1, a method of preparing a gas phase ultrastable molecular sieve may include: making Y-type molecular sieve and SiCl 4 And (3) performing dealumination and silicon supplementing reactions by a gas-phase superstable method. Dealumination and silicon supplementation reactions by gas-phase ultrastable are well known to those skilled in the art and are not described in detail herein, and may be carried out in a gas-phase ultrastable reactor. The conditions for the dealumination and silicon-supplementing reaction by the gas-phase ultrastable method can comprise: the temperature is 250-700 ℃ and the time is 0.15-100min, and the Y-type molecular sieve and SiCl 4 The weight ratio of the dosage is 1: (0.05-0.3), preferably at 400-600deg.C for 20-60min. Y-type molecular sieve and SiCl 4 The weight ratio of the dosage is 1: (0.1-0.2). In one embodiment, the unit cell of the gas phase ultrastable molecular sieve produced is 2.440-2.462nm.
The Y-type molecular sieves according to the present invention may be well known to those skilled in the art, and may be, for example, naY-type molecular sieves, HY-type molecular sieves, and rare earth ion exchanged REY-type molecular sieves.
According to the present invention, the conditions of the first drying may include: the temperature is 400-600 ℃ for 0.5-2 hours, preferably 500-600 ℃ for 0.5-1.5 hours. The first drying may be carried out in equipment known to those skilled in the art, for example in a spray dryer, oven, muffle, preferably a spray dryer. When spray drying is used for the first drying, the spray dryer may have an inlet temperature of 400-550℃and an outlet temperature of 120-200℃and a spray pressure of 8-14MPa. The conditions of firing may include: the temperature is 300-550 ℃ for 0.5-2 hours, preferably 300-450 ℃ for 0.5-1 hour. Calcination may also be well known to those skilled in the art, and may be carried out, for example, in a tube furnace, a muffle furnace, a continuous electric calcination vessel, preferably a continuous electric calcination vessel. The baking atmosphere is not particularly limited, and may be, for example, an air atmosphere or an inert atmosphere, and the inert atmosphere may contain an inert gas such as nitrogen, helium, argon, or the like. The conditions of the second drying may include: the temperature is 120-200deg.C for 1-2 hr, preferably 150-200deg.C for 1-1.5 hr. The second drying may also be carried out in equipment known to the person skilled in the art, for example a oven, a muffle, a gas flow dryer, preferably a gas flow dryer, may be used.
According to the present invention, the first solvent and the second solvent may each be independently selected from one or more of deionized water, distilled water and decationized water, preferably deionized water; clay, binder and ammonium source are well known to those skilled in the art, and clay may be selected from one or more of diatomaceous earth, kaolin, rectorite, bentonite, montmorillonite and sepiolite; the binder can be one or more selected from pseudo-boehmite; the ammonium source may be one or more selected from ammonium sulfate, ammonium chloride, aqueous ammonia, ammonium phosphate, diammonium phosphate and monoammonium phosphate.
The second aspect of the invention provides a catalytic cracking catalyst prepared by the method provided by the first aspect of the invention, and the catalytic cracking catalyst has better catalytic activity, and is favorable for high yield of low-carbon olefin, especially ethylene and propylene, when being used in the catalytic cracking process of crude oil.
According to the invention, al in the catalytic cracking catalyst is based on the dry weight of the catalytic cracking catalyst 2 O 3 The content of (C) may be 30-45 wt%, siO 2 The content of (C) may be 45-60 wt%, na 2 The content of O may be 0.05-0.3 wt%, fe 2 O 3 The content of (C) may be 0.2-1 wt%, RE 2 O 3 The content of (C) may be 0-6 wt%, the content of Cl may be 0.1-1 wt%, and the content of SO 4 2- The content of (C) may be 0.1-2 wt%, and the specific surface area may be 220-320m 2 The pore volume per gram can be 0.28-0.38mL/g, the abrasion index is 0.5-2%/h, and the microreactor is 65-80% after 100% water vapor aging deactivation treatment for 12 hours. Wherein RE 2 O 3 Refers to rare earth metal oxides, preferably wherein the rare earth elements in the rare earth oxides comprise one or more of La, ce, sc, pr and Nd.
In a preferred embodiment, al is present in the catalytic cracking catalyst 2 O 3 The content of (C) is 35-45 wt%, siO 2 The content of (C) is 45-55wt%, na 2 The content of O is 0.05-0.20 wt%, fe 2 O 3 The content of RE is 0.2-0.5 wt% 2 O 3 The content of (C) is 0.1-5 wt%, the content of Cl is 0.1-0.8 wt%, and the content of SO is 4 2- The content of (C) is 0.5-1.5 wt%, and the specific surface area is 220-280m 2 Per gram, the pore volume is 0.30-0.36mL/g, the abrasion index is 0.5-1.2%/h, and the micro-reactive activity is 67-75% after 100% water vapor aging deactivation treatment for 12 hours.
The third aspect of the invention provides an application of the catalytic cracking catalyst provided by the second aspect of the invention in catalytic cracking of crude oil. When the catalytic cracking catalyst is used in the catalytic cracking process of crude oil, the catalyst is beneficial to the high yield of low-carbon olefin, the yield of coke and dry gas is reduced, and especially the yield of ethylene and propylene in the catalytic cracking reaction process is improved.
The reaction conditions for catalytic cracking of crude oil according to the present invention are well known to those skilled in the art and may include, for example: the temperature is 480-550 ℃, and the agent-oil ratio is 3-10.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
Sources of raw materials used in examples and comparative examples:
water glass (SiO) 2 30% of the content, 3.2% of the modulus), the China petrochemical catalyst Qilu division;
kaolin: the solids content was 81.2% by weight, produced by chinese kaolin limited (su zhou);
pseudo-boehmite: with Al 2 O 3 The calculated solids content was 64% by weight, from Shandong aluminum company;
silica sol: in SiO form 2 The calculated solid content was 25% by weight, and Zhejiang Yuda chemical Co., ltd;
fresh hydrochloric acid: the solids content in terms of HCl was 36% by weight;
REY type molecular sieve 1 is purchased from Qilu division company, china petrochemical catalyst, siCl 4 The REY type molecular sieve 2 is purchased from the company of the Ministry of fine chemical technology of Tianjin, and the company of the Qilu division of China petrochemical catalyst.
Specific surface area test: the specific surface area of the catalytic cracking 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.
Pore volume and wear index test: the measurement was carried out by the methods of RIPP28-90 and RIPP29-90 in petrochemical analysis method, RIPP test method (Yang Cui edition, scientific Press, 1990).
Catalyst composition test: the composition was determined by X-ray fluorescence spectroscopy (XRF).
Micro-reverse activity test: the micro-reactive activity of the light oil of the catalytic cracking catalyst is evaluated by adopting a standard method of RIPP92-90 (see the editions of petrochemical analysis method (RIPP test method) Yang Cuiding, scientific press, 1990, etc.), the sample loading is 5.0g, the reaction temperature is 460 ℃, the raw oil is straight-run light diesel oil with the distillation range of 235-337 ℃, the product composition is analyzed by gas chromatography, and the micro-reactive index is calculated according to the product composition.
The ratio of the salt emission to the catalyst yield was reduced = (mass of hydrochloric acid required for acidifying the alachlore in catalyst preparation + mass of ammonium sulfate required for washing the catalyst + mass of hydrochloric acid required for preparing the aluminum sol)/mass of catalyst x 100%, where,
the mass of hydrochloric acid (in terms of chloride) =mass of aluminum source×mass of aluminum acid ratio×mass concentration of hydrochloric acid/36.5×35.5 required for acidifying the aluminum stone in the catalyst preparation, wherein the ratio of aluminum acid in industry is 0.2, and the concentration of hydrochloric acid is 36 wt%;
the mass of ammonium sulfate required to wash the catalyst (calculated as sulfate) =0.02/132×96, wherein the ratio of the mass of ammonium sulfate used to wash the catalyst to the mass of the catalyst in the industry is 0.02;
the amount of hydrochloric acid (in terms of chloride) required to prepare an aluminum sol =mass of aluminum sol×solid content of aluminum sol×chloride content of aluminum sol, wherein the solid content of aluminum sol in industry is 22 wt% and the chloride content of aluminum sol is 7.5 wt%.
Preparation example 1
(1) REY-type molecular sieve 1 (Re at 500 DEG C 2 O 3 Content 12 wt%) and gaseous SiCl 4 Carrying out dealumination and silicon supplementing reaction by a gas-phase ultrastable method for 50min to obtain a gas-phase ultrastable molecular sieve 1 (unit cell constant 2.458 nm) and tail gas, wherein SiCl is obtained 4 And REY molecular sieve 1 in an amount of 0.1 by weight, and separating the tail gas after absorption with deionized water 38L into a first solution having an HCl content of 7.5 wt%, a silicon content of 1.9 wt%, an aluminum content of 1.0 wt%, a second solution having an HCl content of 7.5 wt%, a silicon content of 1.9 wt%, an aluminum content of 1.0 wt%, and a third solution having an HCl content of 7.5 wtWeight percent, silicon content of 1.9 weight percent, aluminum content of 1.0 weight percent;
(2) Mixing water glass and the first solution for 0.5h at 20 ℃ to obtain a first mixture with the pH value of 4.2 and the solid content of 25 weight percent;
(3) Pulping a gas-phase ultrastable molecular sieve and deionized water according to the solid content of 30 weight percent, adding a first mixture, adding kaolin, pseudo-boehmite and a second solution, mixing and stirring for 2 hours (the weight ratio of the gas-phase ultrastable molecular sieve to the kaolin to the pseudo-boehmite to the first mixture to the second solution is 34:35:16:15:10), performing spray drying (the inlet temperature is 600 ℃, the outlet temperature is 150 ℃, the pressure is 8 MPa), and roasting for 1 hour at 350 ℃ to obtain a first solid;
(4) Mixing and stirring the first solid, deionized water and ammonium sulfate for 0.2h, wherein the weight ratio of the first solid (based on dry basis) to the deionized water is 1:3 the weight ratio of the amount of the first solid (on a dry basis) to the amount of the third solution (on a chlorine basis) is 1:0.1, the dry basis mass ratio of the ammonium sulfate to the catalyst is 0.1; filtering to obtain a filter cake, adding deionized water into the filter cake after filtering, and stirring for 0.2h, wherein the weight ratio of the first solid (based on dry basis) to the dosage of the deionized water in the process is 1:8, filtering to obtain a second solid, drying the obtained second solid at 160 ℃ for 1h to obtain a final finished catalyst particle C1, wherein the composition and property parameters of the catalyst are shown in Table 2, the following preparation examples are the same, and the specific process flow of the preparation examples is shown in FIG. 1.
Preparation example 2
(1) REY-type molecular sieve 2 (Re at 500 DEG C 2 O 3 4 wt.%) and gaseous SiCl 4 Carrying out dealumination and silicon supplementing reaction for 60min by a gas-phase ultrastable method to obtain a gas-phase ultrastable molecular sieve 2 (with a unit cell constant of 2.448 nm) and tail gas after reaction, wherein SiCl is obtained 4 And REY molecular sieve 2 in an amount of 0.3, and absorbing the tail gas by 70L of deionized water;
specifically, 70L of deionized water was separated into 40L of a first portion of deionized water, 20L of a second portion of deionized water, and 10L of a third portion of deionized water. Firstly, enabling the tail gas generated after the reaction to contact with a first part of deionized water for first absorption to obtain a first solution and a first tail gas; then the first tail gas is contacted with a second part of deionized water for second absorption to obtain a second solution and second tail gas; and finally, contacting the second tail gas with a third part of deionized water for third absorption to obtain a third solution and third tail gas. Wherein the first solution has an HCl content of 7 wt%, a silicon content of 2.0 wt%, an aluminum content of 1.5 wt%, a second solution has an HCl content of 6 wt%, a silicon content of 1.6 wt%, an aluminum content of 1.2 wt%, and a third solution has an HCl content of 5 wt%, a silicon content of 1.3 wt%, and an aluminum content of 1.0 wt%;
(2) Mixing water glass and the first solution for 0.5h at 20 ℃ to obtain a first mixture with the pH value of 4.0 and the solid content of 30 weight percent;
(3) Pulping a gas-phase ultrastable molecular sieve and deionized water according to the solid content of 30 weight percent, adding a first mixture, adding kaolin, pseudo-boehmite and a second solution, mixing and stirring for 2 hours (the weight ratio of the gas-phase ultrastable molecular sieve to the kaolin to the pseudo-boehmite to the first mixture to the second solution is 38:24:18:20:20), performing spray drying (the inlet temperature is 600 ℃, the outlet temperature is 150 ℃, the pressure is 8 MPa), and roasting for 1 hour at 350 ℃ to obtain a first solid;
(4) Mixing and stirring the first solid, the third solution and ammonium sulfate for 0.2h, wherein the weight ratio of the first solid (based on dry basis) to the deionized water is 1:2 the weight ratio of the amount of the first solid (on a dry basis) to the amount of the third solution (on a chlorine basis) is 1:0.02, the mass ratio of the ammonium sulfate to the catalyst dry basis is 0.08; filtering to obtain a filter cake, mixing and stirring the filter cake after filtering with deionized water for 0.2h, wherein the weight ratio of the first solid (based on dry basis) to the dosage of the deionized water in the process is 1: and 6, filtering to obtain a second solid, and drying the obtained second solid at 160 ℃ for 1h to obtain the final finished catalyst particles C2.
Preparation example 3
A catalytic cracking catalyst C3 was prepared in the same manner as in example 1 except that in step (2), water glass and the first solution were mixed at 35℃for 3 hours to obtain a first mixture having a pH of 2.5 and a solids content of 22% by weight.
Preparation of comparative example 4
A catalytic cracking catalyst C4 was prepared in the same manner as in example 1 except that in step (1), the tail gas produced after the reaction was subjected to deionization absorption by 20L and then separated into a first solution having an HCl content of 11 wt%, a silicon content of 4.2 wt%, an aluminum content of 2.5 wt%, a second solution having an HCl content of 11 wt%, a silicon content of 4.2 wt%, an aluminum content of 2.5 wt%, and a third solution having an HCl content of 11 wt%, a silicon content of 4.2 wt% and an aluminum content of 2.5 wt%.
Preparation example 5
A catalytic cracking catalyst C5 was prepared in the same manner as in example 1 except that in step (2), silica was mixed with the first solution at 30℃for 2 hours to obtain a first mixture having a pH of 4.3 and a solids content of 25% by weight.
Preparation example 6
A catalytic cracking catalyst C6 was produced in the same manner as in production example 1 except that in step (3), a gas phase ultrastable molecular sieve, kaolin, pseudo-boehmite, a first mixture and a second solution were used in a weight ratio of 38:17:20:25:16.
preparation example 7
A catalytic cracking catalyst C7 was prepared in the same manner as in preparation example 1 except that in step (4), the first solid, deionized water and ammonium sulfate were mixed and stirred for 0.2h, wherein the weight ratio of the first solid (on a dry basis) to the deionized water amount was 1:3 the weight ratio of the amount of the first solid (on a dry basis) to the amount of the third solution (on a chlorine basis) is 1:0.15, the dry basis mass ratio of the ammonium sulfate to the catalyst is 0.1.
Preparation of comparative example 1
(1) Adding 25g of pseudo-boehmite into 50g of deionized water, stirring for 0.5h, adding 3g of hydrochloric acid with an acid-aluminum ratio (hydrochloric acid-pseudo-boehmite dry basis weight ratio) of 0.2, stirring for 1h, adding 42.6g of kaolin and 60g of silica sol, stirring for 3h, finally adding 113.33g (solid content of 30 wt%) of slurry containing a gas-phase ultra-stable molecular sieve, stirring for 1h, spray-drying (inlet temperature is 600 ℃, outlet temperature is 150 ℃, pressure is 8 MPa), and roasting the dried solid particles at 150 ℃ for 1h to obtain roasted catalyst particles;
(2) Adding deionized water and ammonium sulfate into the roasted catalyst particles, and stirring for 0.2h, wherein the weight ratio of the deionized water to the catalyst particles (based on dry basis) is 8:1, the weight ratio of the dosage of the ammonium sulfate to the dosage of the catalyst particles (based on dry basis) is 0.1, filtering to obtain a filter cake, adding deionized water into the filter cake obtained after filtering, and stirring for 0.2h, wherein the weight ratio of the dosage of the deionized water to the dosage of the catalyst particles (based on dry basis) is 8:1, re-filtering, and drying the solid obtained by re-filtering at 160 ℃ for 1h to obtain the final product of the comparative catalytic cracking catalyst particles D1.
Preparation of comparative example 2
A comparative catalytic cracking catalyst D2 was prepared in the same manner as in comparative example 1 except that in step (1), 28.13g of pseudo-boehmite was added to 26.4g of deionized water and stirred for 0.5 hours, 3.6g of hydrochloric acid having an aluminum acid ratio (dry basis weight ratio of hydrochloric acid to pseudo-boehmite) of 0.2 was added and stirred for 1 hour, 29.3g of kaolin and 80g of silica sol were further added and stirred for 3 hours, and 126.67g (solid content: 30% by weight) of slurry containing a gas-phase ultrastable molecular sieve was finally added and stirred for 1 hour, spray-drying (inlet temperature: 600 ℃ C., outlet temperature: 150 ℃ C., pressure: 8 MPa) was performed, and the dried solid particles were calcined at 500 ℃ C. For 2 hours to obtain calcined catalyst particles.
Preparation of comparative example 3
Comparative catalytic cracking catalyst D3 was prepared in the same manner as in preparation example 1 except that in step (2), water glass and the first solution were mixed at 50 ℃ for 2 hours to obtain a first mixture having a pH of 2.8 and a solid content of 26% by weight.
Preparation of comparative example 4
Comparative catalytic cracking catalyst D4 was prepared by the same method as in preparation example 1 except that step (2) was different, and the preparation of an alumina sol by the preparation method of example 1 in patent 201610124722.7 was performed instead of preparing the first mixture of example 1, as follows:
s1, carrying out first contact on 0.8mol of metallic aluminum (China aluminum company) and 1mol of (HCl) hydrochloric acid, wherein the temperature of the first contact process is controlled to be 50 ℃, the first contact time is 3 hours, and the initial concentration of the hydrochloric acid is 32 wt%;
s2, standing the mixture after the first contact for 6 hours at the normal temperature of 20 ℃, and then mixing with gamma-Al 2 O 3 (Shandong aluminum works) and eta-Al 2 O 3 (Shandong aluminum plant) carrying out a second contact at 30 ℃ for 4 hours with gamma-Al in terms of aluminum 2 O 3 eta-Al in aluminum 2 O 3 The molar ratio to the metallic aluminum of step S2 is 0.05:0.05:1.
examples 1 to 7
The catalytic cracking catalysts C1 to C7 prepared in the preparation examples were subjected to a 100% steam aging deactivation treatment at 800℃for 12 hours, respectively. The catalyst loading is 9g, the reaction raw material is Wu mixed three raw material oil, the raw materials are shown in table 3, the reaction temperature is 500 ℃, and the catalyst-oil ratio (weight) is 6. The measured catalyst performance parameters are shown in Table 1 and the reaction results are shown in Table 4.
Comparative examples 1 to 4
D1-D4 prepared in the preparation comparative example was subjected to 100% steam aging deactivation treatment at 800℃for 12 hours, respectively. The catalyst loading is 9g, the reaction raw material is Wu mixed three raw material oil, the raw materials are shown in table 3, the reaction temperature is 500 ℃, and the catalyst-oil ratio (weight) is 8. The measured catalyst performance parameters are shown in Table 2 and the reaction results are shown in Table 5.
Wherein conversion = gasoline yield + liquefied gas yield + dry gas yield + coke yield;
light oil yield = gasoline yield + diesel yield;
liquid yield = liquefied gas yield + gasoline yield + diesel yield;
coke selectivity = coke yield/conversion;
Figure BDA0002592764010000171
TABLE 1
Figure BDA0002592764010000172
Figure BDA0002592764010000181
TABLE 2
Figure BDA0002592764010000182
TABLE 3 Table 3
Figure BDA0002592764010000191
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TABLE 4 Table 4
Figure BDA0002592764010000192
Figure BDA0002592764010000201
TABLE 5
Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4
D1 D2 D3 D4
Catalytic cracking product yield
Dry gas, weight percent 1.74 1.7 1.71 1.79
Liquefied gas, weight percent 25.08 24.99 25.48 16.51
Gasoline, weight percent 37.06 37.56 37.46 46.56
Diesel oil, wt% 16.44 16.34 16.14 15.16
Heavy oil, weight percent 12.81 13.08 12.86 12.58
Coke, weight% 6.87 6.33 6.35 7.4
Total weight percent 100 100 100 100
Micro-inverse Activity,% 71 71 70 72
Ethylene yield% 2.23 2.55 2.67 1.15
Propylene yield% 6.68 6.97 7.01 5.14
Conversion, wt.% 70.75 70.58 71 72.26
Liquid yield, wt% 62.14 62.55 62.94 63.07
Light oil yield, wt% 78.58 78.89 79.08 78.23
Coke selectivity,% 9.71 8.97 8.94 10.24
The catalytic cracking catalyst prepared by the method can produce more low-carbon olefins, especially ethylene and propylene, and simultaneously reduce the yields of dry gas and coke.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (12)

1. A method of preparing a catalytic cracking catalyst, the method comprising:
(1) Absorbing tail gas generated by preparing a gas-phase ultra-stable molecular sieve by adopting a first solvent to obtain a first solution, a second solution and a third solution; the tail gas contains 40-83 wt% of chlorine, 5-25 wt% of aluminum and 12-35 wt% of silicon based on the total weight of the tail gas;
(2) Mixing a silicon source with the first solution for reaction to obtain a first mixture, wherein the pH value of the first mixture is 3.0-4.5;
(3) Mixing the gas-phase ultrastable molecular sieve, clay, binder, the first mixture and the second solution, and performing first drying and roasting on the obtained mixture to obtain a first solid; the gas phase ultrastable molecular sieve, clay, binder, first mixture and second solution are used in a weight ratio of (32-38): (22-42): (14-20): (12-20): (4.32-48), the binder is made of Al 2 O 3 The first mixture is calculated as SiO 2 Counting; the first drying conditions include: the temperature is 400-600 ℃;
(4) Mixing the first solid, the second solvent, the third solution and optionally an ammonium source, removing the second solid from the resulting slurry and performing a second drying; the weight ratio of the first solid to the second solvent is 1: (2-5) the weight ratio of the first solid to the third solution is 1: (0.01-0.1), said first solid being on a dry weight basis and said third solution being on a chlorine basis;
the concentration of HCl in the first solution is 3-10 wt%, the concentration of HCl in the second solution is 5-15 wt%, and the concentration of HCl in the third solution is 3-10 wt%.
2. The method of claim 1, wherein in step (2), the pH of the first mixture is 3.0-4.5; the solids content of the first mixture is 25-40 wt.%.
3. The method of claim 1, wherein the silicon source is selected from one or more of water glass, sodium silicate, and silicon dioxide.
4. The method of claim 1, wherein the silicon source is water glass in which SiO 2 The content of (2) is 10-35 wt%, and the modulus of the water glass is 3.0-5.0.
5. The method of claim 1, wherein step (4) comprises: washing the second solid at 5-70 deg.c and then drying.
6. The method of claim 1, wherein the absorbing the tail gas comprises:
s1, contacting the tail gas generated by preparing a gas-phase ultra-stable molecular sieve with a first part of the first solvent for first absorption to obtain a first solution and first tail gas;
s2, contacting the first tail gas with a second part of the first solvent for second absorption to obtain a second solution and second tail gas;
s3, contacting the second tail gas with a third part of the first solvent for third absorption to obtain a third solution and third tail gas; or alternatively, the process may be performed,
the method for absorbing the tail gas comprises the following steps:
and (3) contacting the tail gas generated by preparing the gas-phase ultra-stable molecular sieve with the first solvent to absorb the tail gas to obtain a tail gas absorption liquid, and dividing the tail gas absorption liquid into the first solution, the second solution and the third solution.
7. The method of claim 1, wherein in step (1), the method of preparing the gas phase ultrastable molecular sieve comprises: making Y-type molecular sieve and SiCl 4 Carrying out dealumination and silicon supplementing reaction by a gas phase superstable method;
the conditions of the dealumination and silicon supplementing reaction by the gas-phase ultrastable method comprise: the temperature is 250-700 ℃ and the time is 0.15-100min, and the Y-type molecular sieve and the SiCl are mixed together 4 The weight ratio of the dosage is 1: (0.05-0.3).
8. The method of claim 1, wherein the first drying is spray drying, the spray dryer having an inlet temperature of 400-550 ℃ and an outlet temperature of 120-200 ℃;
the roasting conditions include: the temperature is 300-550 ℃ and the time is 0.5-2 hours;
the second drying conditions include: the temperature is 120-200 ℃ and the time is 1-2 hours.
9. The method of claim 1, wherein the first solvent and the second solvent are each independently selected from one or more of deionized water, distilled water, and decationized water;
the clay is one or more selected from diatomite, kaolin, rectorite, bentonite, montmorillonite and sepiolite;
the binder is pseudo-boehmite;
the ammonium source is selected from one or more of ammonium sulfate, ammonium chloride, ammonia water, ammonium phosphate, diammonium hydrogen phosphate and monoammonium hydrogen phosphate.
10. A catalytic cracking catalyst prepared by the process of any one of claims 1-9.
11. The catalytic cracking catalyst of claim 10, wherein Al in the catalytic cracking catalyst is based on the dry weight of the catalytic cracking catalyst 2 O 3 The content of (C) is 30-45 wt%, siO 2 The content of Na is 45-60 wt% 2 The content of O is 0.05-0.3 wt%, fe 2 O 3 The content of RE is 0.2-1 wt% 2 O 3 The content of (C) is 0-6 wt%, the content of Cl is 0.1-1 wt%, and the content of SO is 4 2- The content of (C) is 0.1-2 wt%, and the specific surface area is 220-320m 2 Per g, pore volume of 0.28-0.38mL/g, abrasion index of 0.5-2%/h, and micro-reactivity of 65-80% after 100% water vapor aging deactivation treatment for 12 hours at 800 ℃.
12. Use of the catalytic cracking catalyst of claim 10 in catalytic cracking of crude oil.
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