CN109692676B - Macroporous kaolinite and preparation and application thereof - Google Patents

Macroporous kaolinite and preparation and application thereof Download PDF

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CN109692676B
CN109692676B CN201710994914.8A CN201710994914A CN109692676B CN 109692676 B CN109692676 B CN 109692676B CN 201710994914 A CN201710994914 A CN 201710994914A CN 109692676 B CN109692676 B CN 109692676B
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kaolinite
macroporous
kaolin
acid
roasting
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CN109692676A (en
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张杰潇
周治
李家兴
张万虹
严加松
田辉平
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • B01J35/615—
    • B01J35/633—
    • B01J35/647—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • 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

Abstract

The average pore diameter of the large-pore structure kaolinite is 2-50nm, and the pore volume of pores with the pore diameter of 10-50nm in the large-pore structure kaolinite accounts for more than 80% of the total pore volume. A preparation method of kaolinite with a macroporous structure comprises the following steps: roasting kaolin at the temperature of 650-800 ℃ for 0.5-3 hours for first roasting, then treating in an acid solution, roasting at the temperature of 650-800 ℃ for 0.5-3 hours for second roasting, then treating in an acid solution in the presence of a pore-expanding agent, filtering and drying. The macroporous kaolinite is used for a catalytic cracking catalyst, and can improve the cracking performance of the catalyst, improve the carbon deposit resistance and improve the metal pollution resistance.

Description

Macroporous kaolinite and preparation and application thereof
Technical Field
The invention relates to kaolinite with a macroporous structure, a preparation method and an application method thereof.
Background
With the gradual exhaustion of petroleum resources, the use of inferior residual oil is a difficult problem in the oil refining industry, and how to improve the refining effect of the inferior residual oil is important. The catalytic cracking (FCC) is always the most important crude oil secondary processing means in oil refining enterprises in China due to the advantages of strong adaptability to raw materials, high yield of light oil products, high gasoline octane number and the like, and currently, the catalytic cracking bears the production tasks of 75% of gasoline, 35% of diesel oil, propylene, ethylene and other chemical products in China. The core of catalytic cracking is a catalytic cracking catalyst, and the catalytic cracking raw material is degraded, so that the performance of the cracking catalyst is reduced, the product distribution of a catalytic cracking device is influenced, and the oil refining income is greatly influenced.
Conventional FCC catalysts are generally composed of a matrix and a molecular sieve, wherein the molecular sieve is the active center of the catalyst. To improve the heavy oil conversion capability of the FCC catalyst, the catalyst must have higher reaction activity, but the development requirement cannot be completely met by simply increasing the content of the active component, and at the same time, too high content of the active component may cause too high yield of coke in the product distribution, which affects the material, heat and benefit balance of the catalytic cracking unit. There are studies to improve the heavy oil conversion capability of catalysts by improving the matrix properties, and one of the methods is to modify kaolin.
The natural kaolin has stable chemical properties, but after being roasted at a certain temperature, the kaolin is subjected to phase transformation, silicon and aluminum in the kaolin begin to have chemical activity, and the kaolin can be converted into a matrix material with catalytic activity through acid or alkali treatment.
US4836913 describes a process for preparing alkali-modified kaolin, which comprises calcining kaolin at 1800 ℃ F. for 25 minutes to 6 hours, reacting with alkaline solution such as sodium hydroxide for more than 1 hour, filtering, washing and ion exchanging to obtain alkali-modified kaolin matrix. Because the catalytic cracking catalyst is an acidic system, the alkali-modified kaolin must be fully washed and ion-exchanged to ensure that the alkali metal content of the matrix reaches a relatively low level, but because the kaolin has a small particle size and is difficult to filter, the industrial production cost is inevitably high.
CN1195014A discloses a method for modifying kaolin, which comprises roasting kaolin at 850-920 ℃ for 10 minutes to 5 hours, and then treating the roasted kaolin at 90-150 ℃ with a mixed acid solution of inorganic monobasic acid and dibasic acid with the molar ratio of 1.0-5.0 and the acid solution concentration of 0.4-4N for 4-40 hours.
Disclosure of Invention
The invention aims to solve the technical problem of providing a large-pore structure kaolinite (referred to as large-pore kaolinite for short) and a preparation method thereof, and the invention aims to solve the other technical problem of providing an application method of the large-pore structure kaolinite in a catalytic cracking catalyst.
The invention provides a large-pore structure kaolinite, wherein the average pore diameter (the average pore diameter for short) of the large-pore structure kaolinite is 2-50nm, such as 10-30nm, 11-24nm or 11-16nm, and the pore volume of pores with the pore diameter of 10-50nm in the large-pore structure kaolinite accounts for more than 80 percent of the total pore volume, such as 80-95 percent or 81-92 percent.
The macroporous kaolinite provided by the invention has a preferable total pore volume of 0.20-0.30ml/g, such as 0.22-0.28 ml/g. Specific surface area of 100-250m2The/g is, for example, 100-2/g。
The total pore volume, the pore volume of 10-50nm pores and the specific surface area of the kaolinite with the macroporous structure are measured by a nitrogen low-temperature adsorption method (see GB/T5816-. The average pore diameter is equal to the result of dividing the corresponding pore volume by the corresponding specific surface, and is calculated by the formula: the average pore diameter k × total pore volume/specific surface area, k 8.
The macroporous structure kaolinite provided by the invention contains Al in the macroporous structure kaolinite on the basis of dry weight2O3The content is 33-45 wt.%, for example 35-42 wt.% or 35-40 wt.%.
The kaolinite with a macroporous structure provided by the invention is usually SiO2The content is 45-59.5 wt%, such as 48-59 wt%, or 50-59 wt%, or 53-59 wt%.
The iron content of the macroporous kaolinite provided by the invention is Fe based on the dry weight (calculated on a dry basis)2O3Preferably not more than 1.5% by weight, for example 0.5-1.5% by weight.
The macroporous kaolinite provided by the invention takes the dry weight as the reference and alpha-SiO2The content is not more than 2% by weight, for example, 1 to 2% by weight.
The content of CaO and MgO is not more than 2 wt%, for example, 1-2 wt% based on the dry weight of the kaolinite with a macroporous structure.
The invention provides the kaolinite with the macroporous structure, wherein the element composition can be determined by any method, such as X-ray fluorescence spectrometry.
The macroporous kaolinite provided by the invention is modified kaolinite and is obtained by modifying a kaolinite raw material. Such as kaolin.
The invention provides a preparation method of kaolinite with a macroporous structure, which comprises the following steps:
(1) roasting the common kaolin at the temperature of 650-800 ℃ for 0.5-3 hours, wherein the roasting process is called as first roasting to obtain the kaolin after the first roasting,
(2) contacting the first calcined kaolin clay and the first acidic solution to form a mixture at a temperature of 40 to 80 ℃, e.g., 50 to 80 ℃, preferably 60 to 80 ℃ for at least 0.5 hour, e.g., 0.5 to 2 hours (referred to as a first treatment) to produce a first kaolin clay slurry; for example, mixing the first calcined kaolin with a first acidic solution or mixing the first calcined kaolin with water and an acid, heating to 40-80 deg.C, preferably 60-80 deg.C, and stirring at this temperature (40-80 deg.C, preferably 60-80 deg.C) for 0.5-2 hours;
(3) filtering and drying the first kaolin slurry to obtain a first dried product (also called dried kaolin),
(4) roasting the first dried product at the temperature of 650-800 ℃ for 0.5-3 hours, wherein the process is called second roasting to obtain kaolin after the second roasting;
(5) forming a mixture of the second calcined kaolin, the second acidic solution and the pore-enlarging agent, and stirring at 40-80 ℃, e.g., 50-80 ℃, preferably 60-80 ℃ for at least 0.5 hour, e.g., for 0.5-2 hours, to obtain a second kaolin slurry, which is referred to as a second treatment, e.g., adding the second calcined kaolin, the second acidic solution and the pore-enlarging agent together into a container and continuously stirring or adding a slurry of the second calcined kaolin and water, then mixing with the acid and the pore-enlarging agent, and heating to 40-80 ℃, preferably 60-80 ℃, under stirring, and stirring at 40-80 ℃, preferably 60-80 ℃ for 0.5-2 hours;
(6) and filtering and drying the second kaolin slurry to obtain the large-pore structure kaolinite.
The invention provides a preparation method of kaolinite with a macroporous structure, which comprises the step (1)The common kaolin is kaolin, which is clay or clayey rock mainly comprising clay mineral of kaolinite group. The kaolinite group clay mineral is such as kaolinite, halloysite, dickite, nacrite. The kaolin can be one or more of soft kaolin, hard kaolin, sandy kaolin, halloysite, coal gangue and halloysite. In the ordinary kaolin, the content of the kaolinite group clay mineral is preferably not less than 65% by weight, for example, 70 to 100% by weight or 70 to 95% by weight or 70 to 80% by weight, and the preferred kaolinite group clay mineral is kaolinite and/or halloysite. In one embodiment, the regular kaolin is Al2O335-40 wt.% of Fe2O30.5-1.5 wt%, CaO + MgO 1-2 wt%, alpha-SiO2The content is 1-2 wt%, and the specific surface area is less than 40m2(ii)/g; the crystal structure of the kaolinite is mainly a sheet structure. The crystalline kaolinite content of the ordinary kaolin is not less than 70% by weight, for example 70-95% by weight or 70-80% by weight. The common kaolin may be raw kaolin ore powder extracted from kaolin ore, or washed kaolin obtained by washing the raw kaolin ore powder with water or ammonium salt solution. The content of the kaolinite group clay minerals in the ordinary kaolin can be measured by an X-ray diffraction method. Typically, the samples are first dried at 150 ℃ and 200 ℃ before measurement.
The preparation method of the kaolinite with the macroporous structure, provided by the invention, comprises the steps of carrying out first roasting at the roasting temperature of 650-800 ℃, preferably 650-750 ℃, wherein the roasting time is 0.5-3 hours, preferably 1-2 hours. The second roasting is carried out at the roasting temperature of 650-800 ℃, preferably 650-750 ℃ and the roasting time of 0.5-3 hours, preferably 1-2 hours.
The invention provides a preparation method of the kaolinite with a macroporous structure, which is characterized in that the first treatment (or first contact) is carried out, wherein the first acidic solution contains acid, the acid can be organic acid and/or inorganic acid, and the acid can be one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid, citric acid and the like; the molar concentration of the acid in the acid-type solution may be 0.5 to 5mol/L, for example 0.5 to 3mol/L or 1 to 5 mol/L. The weight ratio of water in the first acidic solution to the first calcined kaolin (on a dry basis) is 1-10: 1. wherein the first kaolin slurry formed has a solids content of 10 to 50 wt%, for example 15 to 45 wt%, or 15 to 35 wt%, or 15 to 25 wt%. Preferably, the acid in the first acidic solution comprises an organic acid and an inorganic acid, and the molar ratio of the inorganic acid to the organic acid is 0.3-10:1 preferably from 0.4 to 5:1 or 1 to 5:1 or 0.4-3: 1. the acid is more preferably hydrochloric acid and oxalic acid, and the molar ratio of the hydrochloric acid to the oxalic acid is 0.5-10: 1 is preferably 1 to 5:1 or 1 to 3: 1. the first calcined kaolin and the first acidic solution are mixed, and the first calcined kaolin and the first acidic solution can be added into a container to be mixed under stirring; or the first calcined kaolin and water are slurried and then an acid is added to the slurry, preferably to form a mixture having a solution with an acid concentration of 0.5 to 5mol acid/L. The first treatment is to form a mixture of the first calcined kaolin and the first acidic solution, then to heat the mixture to 40-80 ℃, preferably 60-80 ℃, and to stir the mixture at 40-80 ℃, preferably 60-80 ℃ for 0.5-hour.
The invention provides a preparation method of the kaolinite with the macroporous structure, and the second treatment, wherein the acid in the second acidic solution is an organic acid and/or an inorganic acid, and the acid is a solution containing one or more of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, phosphoric acid and citric acid; the molar concentration of the acid in the second acidic solution may be 0.5 to 10mol/L, for example 0.5 to 5mol/L or 1 to 3 mol/L. The weight ratio of water in the second acidic solution to the second calcined kaolin (on a dry basis) is 1-10: 1. the solids content of the second slurry formed is 10-50 wt%, for example 15-45 wt% or 15-35 wt%, preferably 15-25 wt%. The second calcined kaolin may be mixed with the second acidic solution, then warmed and stirred at 40-80 c, preferably 60-80 c, for at least 0.5 hours, e.g., for 0.5-2 hours; it is also possible to slurry the second calcined kaolin with water, then add the acid, then warm it up, and stir it at 40-80 c, preferably 60-80 c, for at least 0.5 hour, e.g. for 0.5-2 hours, wherein the water and acid are used in such amounts that the acid concentration in the resulting solution is e.g. 0.5-10mol/L, preferably 0.5-5mol/L, e.g. 1-3 mol/L. In one embodiment, the acid is hydrochloric acid and oxalic acid, and the molar ratio of hydrochloric acid to oxalic acid is 0.3-10:1, preferably 0.3-5:1, or 1-5:1, or 0.35-3: 1.
The pore-expanding agent can be one or more of ammonium sulfate, ammonium phosphate, ammonium carbonate, organic amine, polyethylene glycol and polyacrylamide. In one embodiment, the weight ratio of the pore-expanding agent to the kaolin after the second calcination is from 0.05 to 1: 1 is, for example, 0.1 to 0.5: 1 or 0.3-0.5: 1. the organic amine is one or more of aliphatic amine, aromatic amine and alcohol amine; the general formula of the fatty amine is R3(NH2)nWherein R is3Is an alkyl or alkylene group having 1 to 4 carbon atoms, n ═ 1 or 2; the alcohol amine has a general formula of (HOR)4)mNH(3-m)Wherein R is4Is alkyl having 1 to 4 carbon atoms, m is 1, 2 or 3; the aromatic amine is an amine with one aromatic substituent. Preferably, the aliphatic amine is one or more of ethylamine, n-butylamine, butanediamine or hexamethylenediamine; the alcohol amine is one or more of monoethanolamine, diethanolamine or triethanolamine; the aromatic amine is one or more of aniline, toluidine and p-phenylenediamine.
The invention provides a preferable preparation method of the macroporous kaolinite, which comprises the following steps:
(1) roasting the common kaolin at the temperature of 700-750 ℃ for 1-2 hours, wherein the roasting process is called as first roasting to obtain the kaolin after the first roasting,
(2) forming a mixture of the first roasted kaolin, a first acid and water, heating to 60-80 ℃, and contacting for 1-2 hours at 60-80 ℃ to perform first treatment to prepare first kaolin slurry; wherein the ratio of the first acid to water is 1-3 moles acid: 1L of water, wherein the weight ratio of the water to the kaolin after the first roasting is 2-5: 1; the first acid is hydrochloric acid and oxalic acid, and the molar ratio of the HCl to the oxalic acid is 0.2-5: 1 preferably from 0.4 to 5:1 is, for example, 0.3 to 0.8: 1;
(3) filtering and drying the first kaolin slurry to obtain a first dried product (also called dried kaolin),
(4) roasting the first dried product at the temperature of 700-750 ℃ for 1-2 hours, wherein the process is called second roasting to obtain kaolin after the second roasting;
(5) forming a mixture of the second calcined kaolin, second acid, water and pore-enlarging agent, heating to 60-80 ℃, and stirring at 60-80 ℃ for at least 1-2 hours to obtain second kaolin slurry, wherein the process is called as second treatment; wherein the ratio of the second acid to water is 1-3 moles acid: 1L of water, wherein the weight ratio of the water to the kaolin subjected to the second roasting is 2-5: 1; the second acid is hydrochloric acid and oxalic acid, and the molar ratio of the HCl to the oxalic acid is 0.1-5: 1 is, for example, 0.2 to 0.5: 1 preferably from 0.3 to 5:1 is, for example, 0.2 to 0.5: 1 or 0.35-1: 1; the weight ratio of the pore-expanding agent to the kaolin after the second roasting is 0.05-0.8:1, preferably 0.1-0.5: 1, for example, 0.3 to 0.5: 1;
(6) and filtering and drying the second kaolin slurry to obtain the large-pore structure kaolinite.
According to the preparation method of the kaolinite with the macroporous structure, the first treatment and/or the second treatment are preferably carried out under a closed condition, so that the increase of the use amount of acid or the deterioration of the performance of the modified kaolinite caused by the volatilization of the acid is avoided.
The method for preparing the kaolinite with the large pore structure provided by the invention is preferable, and the content of the ferric oxide in the obtained kaolinite with the large pore structure is not more than 1.5 weight percent, such as Fe, based on the dry weight2O30.5-1.5 wt%, CaO + MgO in an amount of not more than 2 wt%, e.g. CaO + MgO in an amount of 1-2 wt%, alpha-SiO2The content is not more than 2% by weight, for example, 1 to 2% by weight.
The invention provides a preparation method of a large-pore structure kaolinite, which comprises the following steps: al (Al)2O335-42 wt.% of Fe2O30.5-1.5 wt%, CaO + MgO 1-2 wt%, and alpha-SiO2The content is 1-2 wt%, the specific surface area is 100-2The/g is, for example, 100-2Pore volume (referring to total pore volume) is 0.20 to 0.30ml/g, for example 0.22 to 0.28 ml/g. The average pore diameter of the macroporous kaolinite is 10-50nm, preferably 10-30nm, such as 11-24nm or 11.5-16nm, and the pore volume of the macroporous kaolinite according to the invention with a pore diameter of 10-50nm accounts for more than 80%, such as 80-95%, preferably 81-92% of the total pore volume. In the kaolinite with the macroporous structure, SiO is contained2The content may be 45-59.5 wt%, such as 46-58 wt%, or 47-55 wt%, or 48-51 wt%, or 51-55 wt%, or 49-59 wt%.
The present invention further provides a catalytic cracking catalyst comprising a molecular sieve, a binder and optionally clay and the above-described kaolinite having a macroporous structure according to the present invention.
Preferably, in the catalytic cracking catalyst provided by the invention, the content of the large-pore structure kaolinite is 2-50 wt%, and preferably 15-44 wt%.
Preferably, the catalytic cracking catalyst provided by the invention has a molecular sieve content of 25 wt% or more, for example, the molecular sieve content is 25-50 wt%, preferably 25-35 wt%.
The catalytic cracking catalyst provided by the invention contains 25-50 wt%, preferably 25-35 wt% of molecular sieve (calculated by dry basis) based on the dry basis weight of the catalytic cracking catalyst (the dry basis weight is 800 ℃, and the weight after 1 hour of ignition); clay (on a dry basis) 0-50 wt%, preferably 0-30 wt%; 10-30 wt.%, preferably 15-26 wt.% binder (calculated as oxide); the macroporous kaolinite (on a dry basis) is from 2 to 50% by weight, preferably from 15 to 44% by weight. The binder is preferably an alumina binder, in the form of Al2O3The alumina binder content is 10-30 wt%.
The invention provides a preparation method of a catalytic cracking catalyst, which comprises the following steps: the method comprises the steps of pulping a binder, optional clay, a molecular sieve and macroporous kaolinite to obtain catalyst slurry, and carrying out spray drying, optional washing, optional drying and optional roasting on the catalyst slurry.
According to the catalytic cracking catalyst preparation method of the present invention, the catalyst slurry obtained by beating the binder, optional clay, molecular sieve and macroporous kaolinite can be prepared according to any existing method, and the solid content of the catalyst slurry can be 15-45 wt%, preferably more than 30 wt%, such as 30-40 wt%.
In the preparation method of the catalytic cracking catalyst, the clay is a clay raw material well known by a person skilled in the art, common clay types can be used in the invention, and for the invention, the clay is preferably one or more of kaolin, halloysite, montmorillonite, diatomite, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. More preferably, the clay is one or more of kaolin and halloysite.
According to the preparation method of the catalytic cracking catalyst, the binder can be a binder used in the catalytic cracking catalyst, such as one or more of acidified pseudo-boehmite, aluminum sol, silica sol, magnesium aluminum sol, zirconium sol and titanium sol, and preferably acidified pseudo-boehmite and aluminum sol.
According to the preparation method of the catalytic cracking catalyst, the molecular sieve is a well-known molecular sieve raw material in the field, the molecular sieve types commonly used in the field can be used in the invention, and for the invention, the preferred molecular sieves refer to REY, REHY, REUSY and USY, and a gas phase chemical method (SiCl) is adopted4Al removal and Si supplement method), liquid phase chemical method ((NH)4)2SiF6Aluminum extraction and silicon supplement) and other methods, and ZSM-5 type and beta type zeolites with other high silicon-aluminum ratios or the mixture thereof. According to the preparation method of the present invention, the content of the molecular sieve in the catalytic cracking catalyst is preferably 25 wt% or more.
The invention also provides the catalytic cracking catalyst obtained by the preparation method.
The kaolinite with a macroporous structure provided by the invention has high average pore diameter, high proportion of 10-50nm mesopores, higher heavy oil cracking capability and metal pollution resistance. The kaolinite with a macroporous structure provided by the invention can replace clay to be used for preparing a catalytic cracking catalyst.
The preparation method of the kaolin with the macroporous structure can obtain the kaolin with the macroporous structure, and has higher total pore volume and higher 10-50nm mesopore content.
The cracking catalyst provided by the invention has better heavy oil cracking capability and metal pollution resistance, higher gasoline yield, higher light oil yield and lower coke selectivity.
Drawings
FIG. 1 is an electron micrograph of the macroporous kaolinite B prepared in example 1.
Detailed Description
The following examples further illustrate the features of the present invention, but the present invention is not limited to the examples.
The raw material specifications used in the examples are as follows:
raw material kaolin: the solid content was 72% by weight, and was manufactured by china kaolin limited (suzhou) as hard kaolin having a crystalline kaolinite content of 70% by weight, and referred to in the following examples as kaolin a.
Hydrochloric acid and oxalic acid: analyzing and purifying; polyethylene glycol: analyzing and purifying;
aluminum sol: al (Al)2O322 wt%, produced by Qilu Branch of China petrochemical catalyst, Inc.;
pseudo-boehmite: solid content 72 wt%, Shandong aluminum industries, China;
the molecular sieves used in the catalyst preparation examples were REY type molecular sieves: produced by Qilu division of China petrochemical catalyst, the solid content is 80 weight percent, and the rare earth content is 17.4 weight percent;
the composition of the catalyst obtained in the catalyst preparation example was determined by calculation based on the charge amount of each raw material.
The analysis method comprises the following steps:
(1) XRF fluorescence analysis (RIPP 117-90 standard method (see "petrochemical analysis methods" (RIPP test methods) ed. Yangchi et al, science publishers, 1990)).
(2) The specific surface area and pore volume of the cracking catalyst were measured using an Autosorb-1 nitrogen desorption apparatus from Congta, USA, according to the method of GB/T5816-.
(3) Scanning electron microscope SEM determination: an experimental instrument: QUANTA 200F + EDAX. The experimental conditions are as follows: accelerating voltage 20kV, resolution 2nm, beam spot size 3.0-4.0, working distance 9.8-10.3mm, probe model LFD, ETD, and working pressure 80 Pa.
(4) Content of crystalline kaolinite, alpha-SiO2The content was measured by X-ray powder diffraction method. The samples were analyzed after drying at 150 ℃ for 3 h.
Preparation of Large pore structured Kaolin example 1
Roasting kaolin A at 750 ℃ for 2 hours to obtain a roasted material (called as a first roasted material), adding decationized water (pH is 3.1 and the same below) into 168g (dry basis) of the first roasted material, stirring to prepare slurry with the solid content of 25 weight percent, adding 500g of hydrochloric acid with the concentration of 1mol/L and 100g of oxalic acid, heating to 70 ℃, stirring for 1 hour, filtering to remove mother liquor, and drying a filter cake to obtain a first-step product; roasting 120g of the product obtained in the first step at 750 ℃ for 2 hours to obtain a roasted material (called as a second roasted material), adding decationized water into 100g (dry basis, the same below) of the second roasted material, stirring to obtain slurry with the solid content of 25 weight percent, adding 200g of hydrochloric acid with the concentration of 1mol/L, 50g of oxalic acid and 50g of polyethylene glycol, heating to 70 ℃, stirring for 1 hour, filtering to remove mother liquor, filtering a filter cake, and drying to obtain the kaolinite B with the macroporous structure, wherein the preparation process parameters are shown in Table 1, the characterization analysis data are shown in Table 2, and the scanning electron microscope image is shown in FIG. 1.
TABLE 1 conditions of the procedures of the preparation examples of kaolin with a macroporous structure
Figure BDA0001442281550000091
Preparation of Large pore Structure Kaolin example 2
Roasting kaolin A at 650 ℃ for 0.5 hour to obtain a roasted material (called as a first roasted material), adding decationized water into 168g of the first roasted material, stirring to obtain slurry with the solid content of 25 weight percent, adding 500g of hydrochloric acid with the concentration of 1mol/L and 100g of oxalic acid, heating to 70 ℃, stirring for 1 hour, then filtering to remove mother liquor, and drying a filter cake to obtain a first-step product; roasting 120g of the first-step product at 650 ℃ for 0.5 hour to obtain a roasted material (called as a second roasted material), adding acid water (decationized water) into 100g of the second roasted material, stirring to obtain slurry with the solid content of 25 weight percent, adding 200g of hydrochloric acid with the concentration of 1mol/L, 50g of oxalic acid and 50g of polyethylene glycol, heating to 70 ℃, stirring for 1 hour, filtering to remove mother liquor, filtering a filter cake, and drying to obtain the kaolinite C with the macroporous structure, wherein the parameters of the preparation process and the analysis data are shown in tables 1 and 2.
Preparation of Large pore Structure Kaolin example 3
Roasting the ridge soil A at 750 ℃ for 2 hours to obtain a roasted material (called as a first roasted material), adding 168g of the first roasted material into deionized water, stirring to obtain slurry with the solid content of 25 weight percent, adding 500g of hydrochloric acid with the concentration of 5mol/L, heating to 70 ℃, stirring for 1 hour, filtering to remove mother liquor, and drying a filter cake to obtain a first-step product; roasting 120g of the first-step product at 750 ℃ for 2 hours to obtain a roasted material (called as a second roasted material), adding deionized water into 100g of the second roasted material, stirring to obtain slurry with the solid content of 25 weight percent, adding 200g of hydrochloric acid with the concentration of 5mol/L and 50g of polyethylene glycol, heating to 70 ℃, stirring for 1 hour, filtering to remove mother liquor, and drying a filter cake to obtain the kaolinite D with the macroporous structure, wherein the parameters of the preparation process and the analytical data are shown in tables 1 and 2.
Preparation of Large pore Structure Kaolin example 4
Roasting kaolin A at 750 ℃ for 2 hours to obtain a roasted material (called as a first roasted material), adding decationized water into 168g (calculated by dry basis) of the first roasted material, stirring to obtain slurry with the solid content of 25 percent, adding 500g of phosphoric acid and 100g of citric acid with the concentration of 1mol/L, heating to 70 ℃, stirring for 1 hour at 70 ℃, filtering to remove mother liquor, and drying a filter cake to obtain a product in the first step; roasting 120g of the first-step product at 750 ℃ for 2 hours to obtain a roasted material called a second roasted material, adding decationized water into 100g of the second roasted material, stirring to obtain slurry with the solid content of 25 weight percent, adding 200g of phosphoric acid with the concentration of 1mol/L, 50g of citric acid and 50g of ammonium sulfate, heating to 70 ℃, stirring for 1 hour at 70 ℃, filtering to remove mother liquor, and drying a filter cake to obtain the kaolinite E with the macroporous structure, wherein the parameters of the preparation process and the analysis data are shown in tables 1 and 2.
Preparation of macroporous Kaolin example 5
The macroporous-structure kaolinite was prepared according to the method of preparation example 1 of macroporous-structure kaolinite, except that the temperature of the first calcination was 650 ℃, the calcination was 2 hours, the temperature of the second calcination was 750 ℃, the calcination was 1 hour, the first treatment was carried out, the concentration of the acid was 0.5M, wherein the molar ratio of hydrochloric acid to oxalic acid was 5: 1. second treatment, acid concentration 5M, hydrochloric acid and oxalic acid 5:1, the proportion of the pore-expanding agent to the kaolin subjected to the second roasting is that the weight ratio is 0.1: 1. the resulting large pore structure kaolinite is denoted as F. The preparation process parameters are shown in Table 1, and the characterization analysis data are shown in Table 2.
Preparation of macroporous Kaolin example 6
The macroporous-structure kaolinite was prepared according to the method of preparation example 1 of macroporous-structure kaolinite, except that the temperature of the first calcination was 750 ℃, the calcination was 1 hour, the temperature of the second calcination was 650 ℃ the calcination was 2 hours, the first treatment was carried out, the concentration of the acid was 5M, wherein the molar ratio of hydrochloric acid to oxalic acid was 1: 1.. Second treatment, acid concentration 0.5M, hydrochloric acid and oxalic acid 1: 1, the proportion of the pore-expanding agent polyethylene glycol to the second calcined kaolin is 0.5: 1 weight ratio. The resulting large pore structure kaolinite is denoted G. The preparation process parameters are shown in Table 1, and the characterization analysis data are shown in Table 2.
Preparation of Large pore structured Kaolin example 7
The macroporous kaolin was prepared according to the method of preparation example 1 of macroporous kaolin, except that the weight ratio of the pore-enlarging agent used to the kaolin after the second calcination was 0.3: 1. the temperature of the first treatment was 80 ℃ for 1 hour, and the temperature of the second treatment was 60 ℃ for 2 hours. The total pore volume, the specific surface area, the average pore diameter and the proportion of the pore volume of 10-50nm pores in the obtained macroporous kaolinite are approximately consistent with those in example 1, and the composition is close to that.
Preparation of macroporous Kaolin example 8
The macroporous kaolin was prepared according to the method of preparation example 1 of macroporous kaolin, except that the weight ratio of the pore-enlarging agent used to the kaolin after the second calcination was 0.3: 1, the pore-expanding agent is n-butylamine. The temperature of the first treatment was 60 ℃ for 2 hours, and the temperature of the second treatment was 80 ℃ for 1 hour. The total pore volume, the specific surface area, the average pore diameter and the proportion of the pore volume of 10-50nm pores in the obtained macroporous kaolinite are approximately consistent with those in example 1, and the composition is close to that.
Preparation of macroporous Kaolin comparative example 1
Roasting kaolin A at 750 ℃ for 2 hours to obtain a roasted material (called as a first roasted material), adding decationized water into 168g of the first roasted material, stirring to obtain slurry with the solid content of 25 weight percent, adding 700g of hydrochloric acid with the concentration of 1mol/L and 150g of oxalic acid, heating to 70 ℃, stirring for 1 hour, then filtering to remove mother liquor, and drying a filter cake to obtain a first-step product; and (3) roasting 120g of the product obtained in the first step at 750 ℃ for 2 hours to obtain a roasted material called a second roasted material, adding decationized water into 100g (dry basis) of the second roasted material, stirring to obtain slurry with the solid content of 25 weight percent, adding 50g of polyethylene glycol, heating to 70 ℃, stirring for 1 hour, filtering to remove mother liquor, and drying a filter cake to obtain the comparative kaolinite F, wherein the parameters of the preparation process and the analytical data are shown in tables 1 and 2.
TABLE 2 Dry-based chemical composition and Properties of macroporous kaolinite
Figure BDA0001442281550000121
The contents of the components in Table 2 are on a dry basis, wherein the measurement conditions for the dry basis were 800 ℃ for 1 hour of calcination.
As can be seen from Table 2, the kaolinite with a macroporous structure obtained by the method provided by the invention has larger specific surface area and pore volume, the average pore diameter of the kaolinite B-G with a macroporous structure is 10-30nm, and the pore volume of the pores with the pore diameter of 10-50nm in the kaolinite B-G with a macroporous structure accounts for more than 80% of the total pore volume. As can be seen from FIG. 1, the macroporous kaolinite B morphology exists in a combination of a tubular structure and a sheet structure.
Catalyst preparation example 1
Adding 45.45Kg of alumina sol into a reaction kettle, stirring, adding 22.22Kg of pseudoboehmite (72 percent by weight of solid content, manufactured by Shandong aluminum Co., Ltd.), adding 60.69Kg of decationized water (also called acid water in the invention), stirring for 40min, adding 23.19Kg of macroporous kaolinite B and 31.94Kg of kaolinite A, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. 116.67Kg of molecular sieve slurry (43.75 Kg of molecular sieve and 73.79Kg of decationized water) is added, stirred for 30min and spray-dried to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain a sample C1. The catalyst formulation and product properties are shown in table 3.
Catalyst preparation example 2
Adding 45.45Kg of alumina sol into a reaction kettle, stirring, adding 22.22Kg of pseudo-boehmite (60.69 Kg of decationized water with solid content of 72 wt% of Shandong aluminum company, stirring for 40min, adding 63.77Kg of macroporous kaolinite B, stirring for 60min, adding 2Kg of hydrochloric acid with concentration of 22 wt%, stirring for 30min, adding 111.29Kg of molecular sieve slurry (37.5 Kg of molecular sieve and 73.79Kg of decationized water), stirring for 30min, spray drying to obtain catalyst microspheres, roasting the obtained catalyst microspheres at 500 ℃ for 1h, washing twice with decationized water with weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at 120 ℃ for 2 h to obtain a sample C2. catalyst formula and product performance shown in Table 3.
Catalyst preparation example 3
Adding 45.45Kg of alumina sol into a reaction kettle, stirring, adding 22.22Kg of pseudoboehmite (72 percent by weight of solid content, manufactured by Shandong aluminum industry Co.), adding 60.69Kg of decationized water, stirring for 40min, adding 56.52Kg of macroporous kaolinite B, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. 116.67Kg of molecular sieve slurry (43.75 Kg of molecular sieve and 73.79Kg of decationized water) is added, stirred for 30min and spray-dried to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain a sample C3. The catalyst formulation and product properties are shown in table 3.
Catalyst preparation example 4
Adding 45.45Kg of alumina sol into a reaction kettle, stirring, adding 22.22Kg of pseudoboehmite (72 percent by weight of solid content, manufactured by Shandong aluminum industry Co.), adding 60.69Kg of deionized water, stirring for 40min, adding 57.35Kg of macroporous kaolinite C, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. 116.67Kg of molecular sieve slurry (43.75 Kg of molecular sieve and 73.79Kg of deionized water) is added, stirred for 30min and spray-dried to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain a sample C4. The catalyst formulation and product properties are shown in table 3.
Catalyst preparation example 5
Adding 45.45Kg of alumina sol into a reaction kettle, stirring, adding 22.22Kg of pseudoboehmite (72 percent by weight of solid content, manufactured by Shandong aluminum industry Co.), adding 60.69Kg of decationized water, stirring for 40min, adding 57.35Kg of macroporous kaolinite D, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. 116.67Kg of molecular sieve slurry (43.75 Kg of molecular sieve and 73.79Kg of decationized water) is added, stirred for 30min and spray-dried to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain a sample C5. The catalyst formulation and product properties are shown in table 3.
Catalyst preparation example 6
Adding 45.45Kg of alumina sol into a reaction kettle, stirring, adding 22.22Kg of pseudoboehmite (72 percent by weight of solid content, manufactured by Shandong aluminum industry Co.), adding 60.69Kg of decationized water, stirring for 40min, adding 57.18Kg of macroporous kaolinite E, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. Adding 116.67Kg of molecular sieve slurry (43.75 Kg of molecular sieve and 73.79Kg of decationized water), stirring for 30min, and spray drying to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain a sample C6. The catalyst formulation and product properties are shown in table 3.
Catalyst preparation example 7
Adding 45.45Kg of alumina sol into a reaction kettle, stirring, adding 22.22Kg of pseudoboehmite (72 percent by weight of solid content, manufactured by Shandong aluminum industry Co.), adding 60.69Kg of decationized water, stirring for 40min, adding 57.18Kg of macroporous kaolinite F, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. Adding 116.67Kg of molecular sieve slurry (43.75 Kg of molecular sieve and 73.79Kg of decationized water), stirring for 30min, and spray drying to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain a sample C7. The catalyst formulation and product properties are shown in table 3.
Catalyst preparation example 8
Adding 45.45Kg of alumina sol into a reaction kettle, stirring, adding 22.22Kg of pseudoboehmite (72 percent by weight of solid content, manufactured by Shandong aluminum industry Co.), adding 60.69Kg of decationized water, stirring for 40min, adding 56.93Kg of macroporous kaolinite G, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. Adding 116.67Kg of molecular sieve slurry (43.75 Kg of molecular sieve and 73.79Kg of decationized water), stirring for 30min, and spray drying to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain a sample C8. The catalyst formulation and product properties are shown in table 3.
Catalyst preparation comparative example 1
Adding 45.45Kg of alumina sol into a reaction kettle, stirring, adding 22.22Kg of pseudoboehmite (72% of solid content, manufactured by Shandong aluminum industry Co., Ltd.), adding 60.69Kg of acidic water, stirring for 40min, adding 57.18Kg of comparative kaolinite H, stirring for 60min, adding 2Kg of hydrochloric acid with concentration of 22% by weight, and stirring for 30 min. 116.67Kg of molecular sieve slurry (43.75 Kg of molecular sieve and 73.79Kg of acidic water) is added, stirred for 30min and spray-dried to obtain the catalyst microspheres. And roasting the obtained catalyst microspheres for 1h at 500 ℃, washing twice, washing with decationized water with the weight being 8 times of the dry basis weight of the catalyst microspheres for each time, and drying at constant temperature of 120 ℃ for 2 hours to obtain a sample D1. The catalyst formulation and product properties are shown in table 3.
Catalyst evaluation
The cracking reaction performance of the catalyst of the present invention and the comparative catalyst was evaluated.
The raw oil is Wu-MI-Sanyuan oil, and the physicochemical property data are shown in Table 4.
Table 5 lists the results of the evaluations on the fixed fluidized bed apparatus. The catalyst is aged and deactivated by 100 percent of water vapor at 800 ℃ for 17 hours, the loading of the catalyst is 9g, the catalyst-oil ratio is 5 (weight ratio), and the reaction temperature is 500 ℃.
Wherein, the conversion rate is gasoline yield, liquefied gas yield, dry gas yield and coke yield
Yield of light oil is gasoline yield and diesel oil yield
Liquid yield is liquefied gas, gasoline and diesel oil
Coke selectivity-coke yield/conversion
TABLE 3
Figure BDA0001442281550000151
TABLE 4
Figure BDA0001442281550000161
TABLE 5
Catalyst and process for preparing same C1 C2 C3 C4 C5 C6 C7 C8 D1 (comparative example 1)
Product yield, wt.%
Dry gas 1.86 1.93 2.06 1.98 2.12 2.22 2.15 2.26 2.45
Liquefied gas 16.01 16.22 15.8 16.45 16.57 16.23 17.15 16.79 16.6
Gasoline (gasoline) 49.78 50.11 51.1 48.56 47.46 47.15 46.89 46.49 45.02
Diesel oil 14.22 13.34 12.36 14.21 15.02 15.45 14.34 15.69 15.08
Heavy oil 10.98 9.99 9.69 9.78 9.88 9.86 9.96 9.9 11.41
Coke 7.15 8.41 8.99 9.02 8.95 9.09 9.51 8.87 9.44
Total up to 100 100 100 100 100 100 100 100 100
Slightly counteractive activity, is 79 78 82 79 78 77 77 77 75
Conversion rate% 74.8 76.67 77.95 76.01 75.1 74.69 75.7 74.41 73.51
Yield of light oil,% 64 63.45 63.46 62.77 62.48 62.6 61.23 62.18 60.1
Coke selectivity,% of 9.56 10.97 11.53 11.87 11.92 12.17 12.56 11.92 12.84
The data in table 5 show that the catalyst prepared from the macroporous kaolinite prepared by the method of the present invention has better heavy oil cracking performance and higher conversion rate, higher gasoline yield, lower heavy oil yield, higher light oil yield and good coke selectivity compared with the catalyst prepared by the prior art under the premise of the same usage amount of the molecular sieve; as can be seen in example 2, which uses a lower amount of molecular sieve, the catalyst C2 prepared still has better and better heavy oil cracking performance and higher conversion and gasoline yield than the comparative example.
Catalysts C1-C8 and D1 were subjected to cyclic fouling (to deposit Ni and V) on a cyclic aging unit, and the Ni and V contents on the cyclically fouled catalyst mixture are shown in Table 6, wherein,
the step of circulating pollution comprises the following steps: after the catalyst mixture is introduced with heavy metals (Ni and V) by the Michelle impregnation method, the catalyst material after the introduction of the heavy metals is loaded into a small fixed fluidized bed and treated on a small fixed fluidized bed device according to the following steps:
(a) heating to 600 ℃ at a heating rate of 20 ℃/min in a nitrogen atmosphere;
(b) heating to 780 ℃ at the heating rate of 1.5 ℃/min, keeping the temperature at 780 ℃, and changing the treatment atmosphere according to the following steps in the constant temperature process;
(i) the mixture was treated in an atmosphere containing 40% by volume of nitrogen (containing 5% by volume of propylene) and 60% by volume of water vapor for 10 minutes,
(ii) treated in an atmosphere containing 40% by volume of nitrogen (pure nitrogen, no propylene), 60% by volume of water vapor for 10 minutes,
(iii) to contain 40% by volume of air (containing 4000ppm SO)2) An atmosphere of 60% by volume of water vapor was treated for 10 minutes,
(iv) treating for 10 minutes in an atmosphere containing 40 vol% nitrogen and 60 vol% water vapor; then repeating the steps (i) - (iv) once more in the aforementioned order, and then repeating the step (i) to finish the cyclic contamination step;
then, the aging step is carried out: aging the circularly contaminated catalyst mixture at 800 ℃ for 8 hours in an atmosphere containing 100 vol% of water vapor;
the catalytic performance of the catalyst mixture after cyclic fouling-aging was then examined on an ACE unit, where the feedstock oil (properties see table 4) entered into contact with the catalyst mixture at the bottom of the reactor, and the specific evaluation conditions and results are shown in table 6.
TABLE 6
Figure BDA0001442281550000181
The data in table 6 show that the catalyst prepared from the macroporous kaolinite prepared by the method of the present invention has better metal contamination resistance, the cracking activity is reduced compared with the activity of an uncontaminated fresh agent, but still has better cracking activity compared with a comparative catalyst, and simultaneously has higher conversion rate and gasoline yield compared with a contaminated comparative agent.

Claims (25)

1. The macroporous kaolinite is characterized in that the average pore diameter of the macroporous kaolinite is 2-50nm, and the pore volume of pores with the pore diameter of 10-50nm in the macroporous kaolinite accounts for more than 80% of the total pore volume, and the preparation method comprises the following steps:
(1) roasting common kaolin at the temperature of 650-800 ℃ for 0.5-3 hours for the first roasting;
(2) forming a mixture of the first calcined kaolin and the first acidic solution, reacting at 40-80 ℃ for 0.5-2 hours for first contact to obtain first kaolin slurry, filtering the first kaolin slurry, and drying to obtain a first dried product;
(3) roasting the first dried product at the temperature of 650-800 ℃ for 0.5-3 hours for second roasting to obtain kaolin after the second roasting;
(4) mixing the kaolin subjected to the second roasting, the second acidic solution and the pore-expanding agent, reacting at the temperature of 40-80 ℃ for 0.5-2 hours for second contact, filtering and drying to obtain the kaolinite with the macroporous structure.
2. The macroporous kaolinite according to claim 1, wherein the macropore structure kaolinite has a pore volume of pores with a pore diameter of 10 to 50nm in an amount of 80 to 95% of the total pore volume.
3. The macroporous kaolinite according to claim 2, wherein the macroporous kaolinite has a pore volume of pores having a pore diameter of 10 to 50nm of 81 to 92% of the total pore volume.
4. The macroporous kaolinite as claimed in claim 1, wherein the macroporous kaolinite has a specific surface area of 100-250m2The total pore volume is 0.20-0.30 ml/g.
5. The macroporous kaolinite as recited in claim 4, wherein said macroporous kaolinite has a specific surface area of 100-200m2/g。
6. The macroporous kaolinite according to claim 1, wherein the macroporous kaolinite has an average pore diameter of 10 to 30 nm.
7. The macroporous kaolinite as recited in claim 1, wherein said macroporous kaolinite has an Al content on a dry weight basis2O333-45 wt.% of SiO2The content is 45-59.5 wt%.
8. The macroporous kaolinite of claim 7, wherein Al of said macroporous kaolinite is2O3Content is 35-42 wt%.
9. The macroporous kaolinite as recited in claim 1, wherein in said macroporous kaolinite, Fe is present2O3The content is not more than 1.5 wt%, the content of CaO and MgO is not more than 2 wt%, and the content of alpha-SiO2The content is not more than 2 wt%.
10. The macroporous kaolinite of claim 9, wherein in said macroporous kaolinite, Fe is present2O30.5-1.5 wt%, CaO + MgO 1-2 wt%, alpha-SiO2The content is 1-2 wt%.
11. A method for preparing the macroporous kaolinite according to claim 1, comprising the steps of:
roasting common kaolin at the temperature of 650-800 ℃ for 0.5-3 hours for the first roasting;
forming a mixture of the first calcined kaolin and the first acidic solution, reacting at 40-80 ℃ for 0.5-2 hours for first contact to obtain first kaolin slurry, filtering the first kaolin slurry, and drying to obtain a first dried product;
roasting the first dried product at the temperature of 650-800 ℃ for 0.5-3 hours for second roasting to obtain kaolin after the second roasting;
mixing the kaolin subjected to the second roasting, the second acidic solution and the pore-expanding agent, reacting at the temperature of 40-80 ℃ for 0.5-2 hours for second contact, filtering and drying to obtain the kaolinite with the macroporous structure.
12. The method according to claim 11, wherein the regular kaolin is one or more of soft kaolin, hard kaolin, sandy kaolin, coal gangue, halloysite.
13. The method as claimed in claim 11, wherein the first calcination temperature is 650-750 ℃ and the calcination time is 1-2 hours.
14. The method as claimed in claim 11 or 13, wherein the second calcination is carried out at a calcination temperature of 650-750 ℃ for a calcination time of 1-2 hours.
15. The method of claim 11, wherein the first acidic solution comprises one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid, citric acid; the second acidic solution contains one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid and citric acid.
16. The method of claim 15, wherein the acid in the first acidic solution comprises hydrochloric acid and oxalic acid in a ratio of 0.3 to 10:1, the acid in the second acidic solution comprises hydrochloric acid and oxalic acid, and the ratio of the hydrochloric acid to the oxalic acid is 0.3-10: 1.
17. the method of claim 15, wherein the ratio of hydrochloric acid to oxalic acid in the second acidic solution is 0.3 to 5: 1.
18. the method of claim 11, wherein the first acidic solution and the second acidic solution each have a molar concentration of 0.5 to 5 mol/L; in the first contacting, the weight ratio of the first acidic solution to the first calcined kaolin is 1-10: 1; in the second contact, the weight ratio of the second acidic solution to the second calcined kaolin is 1-10: 1.
19. the method of claim 11 wherein the pore-expanding agent is one or more of ammonium sulfate, ammonium phosphate, ammonium carbonate, organic amines, polyethylene glycol, and polyacrylamide.
20. The method of claim 19, wherein the weight ratio of the pore-expanding agent to the second calcined kaolin is from 0.05 to 1: 1.
21. the method of claim 20, wherein the weight ratio of the pore-expanding agent to the second calcined kaolin is from 0.1 to 0.5: 1.
22. the method of claim 11, wherein the first contacting temperature is 60-80 ℃; the temperature of the second contact is 60-80 ℃.
23. The method of claim 16, wherein the first acidic solution has a ratio of hydrochloric acid to oxalic acid of 0.4 to 5: 1.
24. a catalytic cracking catalyst comprising a molecular sieve, a macroporous kaolinite, a binder and optionally a clay, wherein the macroporous kaolinite comprises from 2 to 50 wt%, the molecular sieve comprises from 25 to 50 wt%, the binder comprises from 10 to 30 wt%, and the clay comprises from 0 to 50 wt%, and the macroporous kaolinite is the macroporous kaolinite of any one of claims 1 to 10 or prepared according to any one of claims 11 to 23.
25. A method for preparing a catalytic cracking catalyst, wherein the method comprises: pulping a binder, optionally clay, molecular sieve and macroporous kaolinite to obtain a catalyst slurry, and spray-drying the catalyst slurry, wherein the macroporous kaolinite is the macroporous kaolinite according to any one of claims 1 to 10 or prepared according to any one of claims 11 to 23.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101045202A (en) * 2006-03-31 2007-10-03 中国石油化工股份有限公司 Method for modifying kaolinite
CN101491764A (en) * 2008-01-23 2009-07-29 中国石油化工股份有限公司 Residual oil hydrogenation catalyst and preparation method and use thereof
WO2016175706A1 (en) * 2015-04-30 2016-11-03 Nanyang Technological University A pillared clay catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101045202A (en) * 2006-03-31 2007-10-03 中国石油化工股份有限公司 Method for modifying kaolinite
CN101491764A (en) * 2008-01-23 2009-07-29 中国石油化工股份有限公司 Residual oil hydrogenation catalyst and preparation method and use thereof
WO2016175706A1 (en) * 2015-04-30 2016-11-03 Nanyang Technological University A pillared clay catalyst

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
改性高岭土的结构特性研究;朱慧红等;《石化技术与应用》;20070930;第25卷(第5期);第399-401页 *

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