CN115672380B - Preparation method of low-coke catalytic cracking catalyst - Google Patents

Preparation method of low-coke catalytic cracking catalyst Download PDF

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CN115672380B
CN115672380B CN202110833591.0A CN202110833591A CN115672380B CN 115672380 B CN115672380 B CN 115672380B CN 202110833591 A CN202110833591 A CN 202110833591A CN 115672380 B CN115672380 B CN 115672380B
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catalyst
catalytic cracking
microsphere
cracking catalyst
molecular sieve
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CN115672380A (en
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周灵萍
严加松
沙昊
张杰潇
张蔚琳
袁帅
许明德
宋海涛
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention belongs to the technical field of catalyst preparation, and relates to a preparation method of a low-coke catalytic cracking catalyst, which comprises the steps of mixing unmodified NaY molecular sieve, alumina binder, silica binder, clay and water, pulping, spray drying, roasting for 1-4 hours at 280-380 ℃, carrying out rare earth ion exchange, treating at 350-450 ℃ with 40-60% water vapor, carrying out gas-phase ultrastable modification by SiCl 4, and carrying out contact treatment by composite acid. The catalytic cracking catalyst prepared by the method has the advantages of higher pore volume, higher specific surface area, good strength and excellent heavy oil conversion performance.

Description

Preparation method of low-coke catalytic cracking catalyst
Technical Field
The invention relates to a catalytic cracking catalyst and a preparation method thereof.
Background
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 activity stability when being used for heavy oil catalytic cracking reaction.
Disclosure of Invention
The invention aims to provide a novel preparation method of a catalytic cracking catalyst containing an ultrastable Y-type molecular sieve.
The invention provides a preparation method of a catalytic cracking catalyst, which comprises the following steps:
(1) Mixing unmodified NaY molecular sieve with alumina binder, silica binder, clay and water, pulping, spray drying, and calcining at 280-380deg.C for 1-4 hr 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; the sodium oxide content in the catalyst microsphere B is preferably 1.5-2.5 wt%;
(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) The catalyst microsphere C and SiCl 4 gas are in contact reaction under the condition of 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 in the catalyst microsphere C 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 in the catalyst microsphere C is more than 1 weight percent, the catalyst microsphere C is dried to ensure that the water content is less than 1 weight percent and then is contacted with the silicon tetrachloride for carrying out the reaction;
(5) The catalyst microsphere D is contacted with inorganic acid and organic acid solution for at least 60 minutes, such as 60-120 minutes, at the temperature of 25-70 ℃, and the catalyst finished product E, namely the catalytic cracking catalyst provided by the invention, is obtained after filtration, washing and drying.
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, better coke selectivity and stronger heavy oil conversion capability. The preparation method of the catalytic cracking catalyst provided by the invention can obtain the catalytic cracking catalyst with the sodium oxide content lower than 0.15 wt% under the condition of not using ammonia nitrogen, and the preparation process can be free of ammonia nitrogen pollution in the whole process, 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 provided by the invention has higher activity stability, higher heavy oil conversion activity in heavy oil catalytic cracking reaction, higher gasoline yield and lower coke selectivity.
Detailed Description
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.
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.
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 (15-40 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 US3639099, 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.
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 200-350g/L calculated by RE 2O3, and the weight ratio of the rare earth salt solution to the catalyst microsphere A is 0.03-0.3.
Preferably, the ion exchange in step (2) results in a sodium oxide content of preferably 1.5 to 2.5 wt.% in the catalyst microspheres B.
Preferably, the ion exchange results in a catalytic cracking catalyst having a rare earth content of preferably 1 to 4 wt% based on RE 2O3.
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 reaction temperature of the contact reaction of the catalyst microsphere C in the step (4) and SiCl 4 gas is 250-450 ℃, preferably 280-420 ℃.
In the preparation method of the catalytic cracking catalyst provided by the invention, the reaction time of the contact reaction of the catalyst microsphere C and SiCl 4 gas in the step (4) is 10 minutes to 5 hours, such as 0.2-2 hours, preferably 0.5 hours to 2 hours.
In the preparation method of the catalytic cracking catalyst provided by the invention, the weight ratio of the reaction materials of the contact reaction of the catalyst microsphere C and SiCl 4 gas in the step (4) is SiCl 4: weight ratio of catalyst microsphere c=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, such as 60-120 minutes, 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 to obtain the catalytic cracking catalyst product E provided by the present invention. 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 above-mentioned inorganic acid solution with medium strength is aqueous solution of above-mentioned inorganic acid with medium strength, in which the mole concentration of above-mentioned inorganic acid with 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.
The following examples further illustrate the invention but are not intended to limit it.
In the examples and comparative examples, unmodified NaY molecular sieves (also referred to as NaY zeolite) were provided by zilut division, chinese petrochemical catalyst, ltd, with a sodium oxide content of 13.5 wt%, a framework silica alumina ratio (SiO 2/Al2O3 molar ratio) =4.6, a unit cell constant of 2.470nm, and a relative crystallinity of 90%, which is the pH of the filter cake of the as-synthesized NaY molecular sieves after washing with industrial water and washing of 7.6; rare earth chloride, rare earth nitrate and gallium nitrate are chemical pure reagents produced by Beijing chemical plant. 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 determined by X-ray powder diffraction (XRD) using standard methods RIPP-145, RIPP-146-90 (see "petrochemical analysis method (RIPP test method) Yang Cuiding, et al, science 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 Kang Da, 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 RIPP151,151-90 standard method (see petrochemical analysis methods (RIPP test method), code 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 RIPP standard method (see petrochemical analysis 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) 133Kg of deionized water is added into a catalyst gelling kettle, and then, the gelling raw materials are added in sequence under stirring: 46.3Kg of kaolin (solid content: 76% by weight, purchased from Kaolin Co., st. O.), 18.7Kg of alumina sol (alumina content: 21.5% of Qilu division Co., ltd.), 76.8Kg of silica sol (SiO 2 content: 25% by weight, qilu division Co., ltd., pH: 2.5) were stirred for 30 minutes. Then, 21.6Kg (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 800L of decationizing aqueous solution, stirring to uniformly mix, adding 6.54L of RE (NO 3)3 solution (the concentration of the rare earth solution is 330g/L calculated by RE 2O3), stirring, heating to 30 ℃ for 1h, filtering, washing, and drying a filter cake at 120 ℃ to obtain rare earth-containing catalyst microsphere 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, introducing heated and vaporized SiCl 4 gas, and reacting for 30Min at the temperature of 400 ℃ 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, washing and drying to obtain the SCAT-1 catalytic cracking catalyst product.
Example 2
(1) 137Kg of deionized water is added into a catalyst gelling kettle, and then the gelling raw materials are added in sequence under stirring: 52.7Kg of kaolin (solid content: 76% by weight, available from Kaolin Co., st. O.), 14.9Kg of alumina sol (alumina content: 21.5% by weight, available from Qilu Co., ltd.), 70.4Kg of silica sol (SiO 2 content: 25% by weight, available from Qilu Co., ltd.), and stirred for 30 minutes. Then, 20Kg (based on NaY dry basis) of unmodified NaY molecular sieve slurry (53 wt% concentration, available from zilut division, chinese petrochemical catalyst, inc.) was added thereto and stirred for 60 minutes. Then spray drying and forming are carried out, and roasting is carried out for 1 hour in a roasting furnace at 350 ℃ to obtain catalyst microspheres A2;
(2) Adding the prepared catalyst microsphere A2 into 800L of decationizing aqueous solution, stirring to uniformly mix, adding 5.4L of RE (NO 3)3 solution (the concentration of the rare earth solution is 330g/L calculated by RE 2O3), stirring, heating to 40 ℃ for 1h, filtering, washing, and drying a filter cake at 120 ℃ to obtain rare earth-containing catalyst microsphere 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, introducing heated and vaporized SiCl 4 gas, reacting for 2 hours at the temperature of 300 ℃, washing with 100L of decationizing 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, washing and drying to obtain the SCAT-2 catalytic cracking catalyst product.
Example 3
(1) 152Kg of deionized water is added into a catalyst gelling kettle, and then the gelling raw materials are added in sequence under stirring: 46.4Kg of kaolin (solid content: 76% by weight, available from Kaolin Co., st. O.), 14.9Kg of alumina sol (alumina content: 21.5% by weight, available from Qilu Co., ltd.), 73.6Kg of silica sol (SiO 2 content: 25% by weight, available from Qilu Co., ltd.), and stirred for 30 minutes. Then, 23.2Kg (based on NaY dry basis) of unmodified NaY molecular sieve slurry (53 wt% strength, available from zilut division, chinese petrochemical catalyst, inc.) was added thereto, followed by rapid stirring 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 800L of decationizing aqueous solution, stirring to uniformly mix, adding 8.3L of RE (NO 3)3 solution (the concentration of the rare earth solution is 330g/L calculated by RE 2O3), stirring, heating to 35 ℃ for 1h, filtering, washing, and drying a filter cake at 120 ℃ to obtain rare earth-containing catalyst microsphere 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, introducing heated and vaporized SiCl 4 gas, reacting for 1h at the temperature of 350 ℃, washing with 100L of decationizing water, filtering, and drying a filter cake at 120 ℃ for 5 hours 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 filtering, washing and drying to obtain a catalytic cracking catalyst product SCAT-3; 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.
Comparative example 1
2000Kg (dry basis) NaY zeolite with framework SiO 2/Al2O3 of 4.6 (sodium oxide content 13.5 wt%, product of Miongpetrifaction catalyst Qilu Co.) is added into a primary exchange tank filled with 20m 3 water, stirred uniformly at 25 ℃, then 581L RECl 3 solution (rare earth concentration in RECl 3 solution is 330g/L calculated by RE 2O3) is added, stirring is continued for 60 minutes, and then filtration, washing and the filter cake is sent into a flash 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 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 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, then sending the molecular sieve material into a secondary exchange tank, adding water with the weight of 20m 3 into the secondary exchange tank in advance, adding the molecular sieve material with the weight of 2000Kg (dry basis weight) into the secondary exchange tank, uniformly stirring, then adding hydrochloric acid with the concentration of 10 wt% into the mixture, heating the mixture to 90 ℃, stirring the mixture for 70 minutes, then adding citric acid with the concentration of 125Kg, continuously stirring the mixture for 60 minutes at 90 ℃, filtering, washing and drying the mixture to obtain the modified Y-type molecular sieve, and marking the modified Y-type molecular sieve as DZ-1.
11.62 Kg of alumina sol having an alumina content of 21.5 wt% was added to 69.5 Kg of decationized water, stirring was started, 27.63 Kg of kaolin having a solid content of 76 wt% was added to disperse for 60 minutes, and then 46Kg of silica sol (SiO 2 content of 25 wt%, supplied by Qilu Co., ltd.) was added to stir 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 NaY zeolite with framework SiO 2/Al2O3 of 4.6 (sodium oxide content 13.5 wt%, product of Mitsui catalyst) is added into a primary exchange tank filled with 20m 3 decationized water, stirred uniformly at 90 ℃, then 685 and L RECl 3 solution (rare earth concentration in RECl 3 solution is 330g/L calculated by RE 2O3) are added, and stirred 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 the example 1 disclosed in the CN103787352A patent, 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, then sending the molecular sieve material into a secondary exchange tank, adding 20m 3 of decationized water into the secondary exchange tank in advance, adding 2000Kg (dry basis weight) of molecular sieve material into the secondary exchange tank, uniformly stirring, then adding 0.85m 3 of sulfuric acid solution with the concentration of 7 wt% into the secondary exchange tank, 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, and marking 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
Adding 20 kg of NaY molecular sieve (dry basis) into 200L of decationizing aqueous solution, stirring to uniformly mix, adding 10 kg of NaY (NH 4)2SO4, stirring, heating to 90-95 ℃ for 1 hour, filtering, washing, drying a filter cake at 120 ℃ and then carrying out hydrothermal modification treatment, roasting at the temperature of 650 ℃ for 5 hours under 100% water vapor, adding into 200L of decationizing aqueous solution, stirring to uniformly mix, adding 1.93L of RE (NO 3)3 solution (the concentration of RE is 330g/L in terms of RE 2O3) and 9 kg of RE (NH 4)2SO4), stirring, heating to 90-95 ℃ for 1 hour, filtering and washing, drying a filter cake at 120 ℃ and then carrying out second hydrothermal modification treatment, roasting at the temperature of 650 ℃ under 100% water vapor for 5 hours to obtain the twice ion-exchanged twice hydrothermal ultrastable rare earth-containing hydrothermal ultrastable Y-type molecular sieve which is DZ3.
7.15 Kg of alumina sol having an alumina content of 21 wt% was added to 15.66 kg of decationized water, stirring was started, and 27.63 kg of kaolin having a solid content of 76 wt% was added to disperse for 60 minutes. 20.49 kg of pseudo-boehmite with the alumina content of 61 weight percent is taken and added into 81.46 kg of decationized water, 2.1L of hydrochloric acid with the mass concentration of 36 percent is added under the stirring state, the dispersed kaolin slurry is added after acidification is carried out for 60 minutes, then 15 kg (dry basis) of ground DZ3 molecular sieve is added, and after uniform stirring, spray drying, roasting and washing treatment are carried out, and the catalyst which is marked as DC3 is obtained after drying. Wherein the obtained DC3 catalyst contains 30 weight percent of DZ3 molecular sieve, 42 weight percent of kaolin, 25 weight percent of pseudo-boehmite and 3 weight percent of alumina sol based on dry basis.
Comparative example 4
A catalyst was prepared according to the method of example 1, except that after the catalyst was spray-dried and formed, the catalyst microspheres were calcined in a calciner at 500℃for 1 hour.
Examples 4 to 6
Examples 4 to 6 illustrate the catalytic cracking reaction performance of the catalytic cracking catalyst provided by the present invention.
The catalytic cracking reaction performance of the SCAT-1, SCAT-2 and SCAT-3 catalysts was evaluated on a small fixed fluidized bed reactor (ACE) after being aged by 100% steam at 800 ℃ for 17 hours, and the cracked gas and the product gas were collected and analyzed by gas chromatography respectively. The catalyst loading is 9g, the reaction temperature is 500 ℃, the weight hourly space velocity is 16h －1, the catalyst-oil ratio (weight ratio) is shown in table 3, 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
Coke selectivity = coke yield/conversion
Comparative examples 5 to 8
Comparative examples 5 to 8 illustrate the catalytic cracking reaction performance of ultrastable Y-type zeolite prepared by the methods provided in comparative examples 1 to 4.
After the DC1, DC2, DC3, DC4 catalysts were aged with 100% by volume of steam at 800℃for 17 hours, the catalytic cracking reaction performance was evaluated on a small fixed fluidized bed reactor (ACE) by the method shown in example 4, the raw material properties of the ACE experiments are shown in Table 2, and the evaluation results are shown in Table 3.
TABLE 1
As shown in the results in 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, high relative crystallinity of molecular sieve in the catalyst and no ammonia nitrogen pollution in the preparation of the catalyst.
Table 2 ACE evaluation of raw oil Properties
TABLE 3 Table 3
As can be seen from the results shown in Table 3, the catalytic cracking catalyst provided by the invention has significantly lower coke selectivity and higher heavy oil conversion activity. Surprisingly, the gasoline yield is significantly higher. The catalyst has higher conversion rate after 17 hours aging, and is higher in activity stability.

Claims (16)

1. A method for preparing a catalytic cracking catalyst, comprising the steps of:
(1) Mixing unmodified NaY molecular sieve with alumina binder, silica binder, clay and water, pulping, spray drying, and roasting at 280-380 deg.C for 1-4 hr to obtain catalyst microsphere A; the alumina binder is alumina sol, and the weight of the catalyst microsphere A is taken as a reference, and the catalyst microsphere A contains 10-50 wt% of unmodified NaY molecular sieve, 2-15 wt% of alumina binder, 10-30 wt% of silicon binder and 10-80 wt% of clay;
(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 ℃ in an atmosphere containing 40-60% by volume of water vapor for 4-6 hours, and optionally drying to obtain a catalyst microsphere C;
(4) Enabling the catalyst microsphere C to react with SiCl 4 gas in a contact way, and then washing and filtering to obtain a catalyst microsphere D; 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) And (3) contacting the catalyst microsphere D with inorganic acid and organic acid solution at the temperature of 25-70 ℃ for at least 60 minutes, and filtering, washing and drying to obtain a catalyst finished product E.
2. The method for preparing a catalytic cracking catalyst according to claim 1, wherein in the step (1), the unmodified NaY molecular sieve is a hydrothermally synthesized NaY molecular sieve, and the pH of the NaY molecular sieve cake is 7 to 9 as measured after washing with water only, and the calcination temperature in the step (1) is 300 to 350 ℃.
3. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the temperature of the ion exchange reaction in step (2) is 20 to 60 ℃.
4. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the temperature of the ion exchange reaction in the step (2) is 25-45 ℃ and the exchange time is 90-120 minutes, and the rare earth salt solution is an aqueous solution of rare earth salt.
5. The method for preparing a catalytic cracking catalyst according to claim 1, wherein in step (3), the baking temperature is 370 to 420 ℃, the baking atmosphere is an atmosphere containing 45 to 55% by volume of water vapor, and the baking time is 5 to 6 hours.
6. The method for preparing a catalytic cracking catalyst according to claim 1, wherein in the step (4), the temperature of the contact reaction of the catalyst microsphere C with SiCl 4 is 280-420 ℃; the reaction time of the contact reaction of the catalyst microsphere C and SiCl 4 gas is 0.2 to 2 hours; the catalyst microsphere C is in contact reaction with SiCl 4 gas, and the weight ratio of SiCl 4 to the catalyst microsphere C is 0.05-0.15: 1.
7. The method for preparing a catalytic cracking catalyst according to claim 1, wherein 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 mixed with an inorganic acid solution having a medium strength or higher, contacted at 25 to 70 ℃ for at least 60 minutes, then an organic acid is added, contacted at 25 to 70 ℃ for at least 60 minutes, filtered, washed and dried.
8. The method for preparing a catalytic cracking catalyst according to claim 7, 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, wherein the molar concentration of the inorganic acid with the medium strength or more in the inorganic acid solution with the medium strength or more is 0.01mol/L to 0.15mol/L.
9. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the catalyst microspheres a contain 15 to 45 wt.% of unmodified NaY-type molecular sieve on a dry basis, 2 to 10 wt.% of alumina sol on an alumina basis, 20 to 25 wt.% of silica sol on a silica basis, and 20 to 55 wt.% of clay on a dry basis.
10. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the catalyst microspheres a contain: 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. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the content of rare earth in the catalytic cracking catalyst is 1 to 4% by weight in terms of RE 2O3.
12. The method for preparing a catalytic cracking catalyst according to claim 1, wherein the water content of the catalyst microspheres C is not more than 1 wt%.
13. The method for producing a catalytic cracking catalyst according to claim 2, wherein in step (1), the water is washed with industrial water.
14. The method for preparing a catalytic cracking catalyst according to claim 4, wherein the rare earth salt is rare earth chloride and/or rare earth nitrate.
15. The method for preparing a catalytic cracking catalyst according to claim 7, wherein in the step (5), the catalyst microspheres D obtained in the step (4) are mixed with an inorganic acid solution with a medium strength or more and contacted at a temperature of 40-60 ℃ for 60-120 minutes; after adding the organic acid, the mixture is contacted for 60 to 120 minutes at the temperature of 40 to 60 ℃.
16. A catalytic cracking catalyst obtained by the catalytic cracking catalyst preparation method according to any one of claims 1 to 15.
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CN101745416A (en) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 Catalytic cracking catalyst and preparation method thereof
CN101767027A (en) * 2008-12-31 2010-07-07 中国石油化工股份有限公司 Preparation method of cracking catalyst containing ultrastable molecular sieve
CN101767028A (en) * 2008-12-31 2010-07-07 中国石油化工股份有限公司 Preparation method of fluid catalytic cracking catalyst
CN103157507A (en) * 2011-12-15 2013-06-19 中国石油天然气股份有限公司 Heavy oil catalytic cracking catalyst and preparation method thereof
CN108452830A (en) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 A kind of catalytic cracking catalyst
CN108452837A (en) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 A kind of catalytic cracking catalyst

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101745416A (en) * 2008-11-28 2010-06-23 中国石油化工股份有限公司 Catalytic cracking catalyst and preparation method thereof
CN101767027A (en) * 2008-12-31 2010-07-07 中国石油化工股份有限公司 Preparation method of cracking catalyst containing ultrastable molecular sieve
CN101767028A (en) * 2008-12-31 2010-07-07 中国石油化工股份有限公司 Preparation method of fluid catalytic cracking catalyst
CN103157507A (en) * 2011-12-15 2013-06-19 中国石油天然气股份有限公司 Heavy oil catalytic cracking catalyst and preparation method thereof
CN108452830A (en) * 2017-02-21 2018-08-28 中国石油化工股份有限公司 A kind of catalytic cracking catalyst
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