CN109692702B - Macroporous kaolinite and preparation and application thereof - Google Patents
Macroporous kaolinite and preparation and application thereof Download PDFInfo
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- CN109692702B CN109692702B CN201710995041.2A CN201710995041A CN109692702B CN 109692702 B CN109692702 B CN 109692702B CN 201710995041 A CN201710995041 A CN 201710995041A CN 109692702 B CN109692702 B CN 109692702B
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- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- 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
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- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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Abstract
The macroporous kaolinite contains a first modified metal compound, the average pore diameter is 2-50nm, the pore volume of pores with the pore diameter of 10-50nm accounts for more than 80% of the total pore volume, and the first modified metal compound is one or more of tin, copper and chromium compounds. The preparation method of the macroporous kaolinite comprises the following steps: the preparation method comprises the following steps of carrying out first roasting on common kaolin, forming a mixture of the kaolin subjected to the first roasting, a first acidic solution and an optional first modified metal compound, carrying out first treatment, then carrying out second roasting, mixing the mixture with a second acidic solution, a pore-expanding agent and the optional first modified metal compound, carrying out second treatment, filtering and drying to obtain the macroporous kaolinite, wherein the first modified metal compound is introduced in at least one step. The macroporous kaolinite has high cracking activity, can be used for preparing a cracking catalyst, and the obtained catalyst has high gasoline yield and gasoline octane number and low coke selectivity.
Description
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. Thus, there is currently research into improving the heavy oil conversion capability of catalysts by enhancing the matrix properties, one of which is the modification of 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 A kaolin modification method, which comprises roasting kaolin at 850-920 ℃ for 10 minutes to 5 hours, and then treating the roasted kaolin 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 at 90-150 ℃.
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, which contains a first modified metal element, wherein the first modified metal is one or more of tin, copper and chromium, the average pore diameter (short for average pore diameter) of the large-pore structure kaolinite is 2-50nm, preferably 10-30nm, such as 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, such as 80-95 percent or 81-92 percent of the total pore volume.
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 100-250m2G e.g. 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 given 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 33-40 wt.%. SiO 22In an amount of 49.5 to 62.5% by weight, usually SiO2The content is 45-59.5 wt%, such as 46-58 wt%, or 47-55 wt%, or 50-53 wt%.
The kaolinite with a macroporous structure contains one or more metal elements of tin, copper and chromium, and is called as a first modified metal. The content of the first modified metal in terms of oxide is 0.1-6 wt%, preferably 1.5-4.5 wt%, based on the dry weight of the macroporous kaolinite (in terms of dry weight); wherein the tin content (Sn in SnO)2Calculated) from 0 to 6% by weight, for example from 0 to 4.5% by weight or from 0 to 3% by weight or from 0 to 1.5% by weight, and a copper content, calculated as CuO, of from 0 to 6% by weight, for example from 0 to 4.5% by weight or from 0 to 3% by weight or from 0 to 1.5% by weight, calculated as Cr2O3The chromium content is 0-6 wt.%, for example 0-4.5 wt.%, or 0-3 wt.%, or 0-1.5 wt.%. Preferably, the content of tin (Sn in SnO) in the macroporous kaolinite2Calculated as CuO) of 0.5 to 1.5 wt.%, and a copper content of 0.5 to 1.5 wt.%, calculated as Cr2O3Measuring chromium content to 0.5-1.5And (3) weight percent.
The macroporous kaolinite provided by the invention takes the dry basis weight of the macroporous kaolinite 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 in the macroporous kaolinite is not more than 2 wt%, for example, 1-2 wt% based on the dry weight of the macroporous kaolinite.
The macroporous kaolinite provided by the invention takes dry weight as a reference and Fe2O3In an amount of not more than 1.5 wt% such as 0.5 to 1.5 wt%,
the kaolinite with a macroporous structure provided by the invention can also contain a second modified metal, such as one or more of Rare Earth (RE), titanium and zirconium. The rare earth element comprises or is at least one of La, Ce, Sc, Pr and Nd. The second modifying metal is present in the macroporous kaolinite in an amount not exceeding 4 wt%, e.g., from 0 to 3 wt%, calculated as oxide, based on the dry weight of the macroporous kaolinite.
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 and/or halloysite.
The invention provides a preparation method of kaolinite with a macroporous structure, which comprises the following steps:
(1) roasting the kaolin at the temperature of 650-800 ℃ for 0.5-3 hours, wherein the roasting process is called first roasting to obtain the kaolin after the first roasting,
(2) forming a mixture of the first calcined kaolin and one or more of a first acid, water, optionally a first modifying metal compound such as tin compounds, copper compounds and chromium compounds, raising the temperature to 40-80 ℃, preferably 60-80 ℃, and contacting at a temperature of 40-80 ℃, preferably 60-80 ℃, for at least 0.5 hour, such as 0.5-2 hours, referred to as a first treatment, to produce a first kaolin slurry;
(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) mixing the second calcined kaolin, the second acid, water, the pore-expanding agent, and optionally one or more of the first metal compounds such as tin compounds, copper compounds, and chromium compounds, heating to 40-80 ℃, preferably 60-80 ℃, and stirring at 40-80 ℃, preferably 60-80 ℃ for at least 0.5 hour, for example, for 0.5-2 hours to obtain a second kaolin slurry, which is referred to as a second treatment;
(6) and filtering and drying the second kaolin slurry to obtain the large-pore structure kaolinite.
The invention provides a preparation method of large-pore structure kaolinite, wherein the kaolinite is common kaolinite and is clay or clay rock which takes kaolinite group clay mineral as a main component. The kaolinite group clay mineral is such as kaolinite, halloysite, dickite, nacrite. The kaolin may be, for example, one or more of soft kaolin, hard kaolin, sandy kaolin, halloysite, coal gangue, and the kaolin preferably contains 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 of a kaolinite group clay mineral, and the preferred kaolinite group clay mineral is kaolinite and/or halloysite. For example, in one embodiment, the kaolin clay comprises Al2O333-40 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 is not less than 70% on a dry basis, for example 70-95% or 70-80%. The 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 an ammonium salt solution. Kaolinite clay mineral of kaolinite familyThe content of the substance can be measured by X-ray diffraction. 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 ℃, for example 650-750 ℃, and the roasting time is 0.5-3 hours, preferably 1-2 hours.
The invention provides a preparation method of the kaolinite with a macroporous structure, which comprises a first treatment (or first contact), wherein the first acid can be organic acid and/or inorganic acid, and the first acid can be one or more of hydrochloric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid, citric acid and sulfuric acid; the ratio of the first acid to water may be 0.5 to 5mol acid/L water, for example 0.5 to 3mol acid/L water or 1 to 5mol acid/L water. The weight ratio of water in the first treatment to the first calcined kaolin (on a dry basis) is from 0.5 to 15: 1, for example from 1 to 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 first acid comprises an organic acid and an inorganic acid, the molar ratio of inorganic acid to organic acid being 0.3-10: 1, preferably 0.4-5: 1, for example 1-5: 1 or 1-3: 1 or 0.4-0.8: 1. The first acid is more preferably hydrochloric acid and oxalic acid, the molar ratio of hydrochloric acid (HCl) to oxalic acid being 0.3-10: 1, preferably 0.4-5: 1, for example 1-5: 1 or 1-3: 1 or 0.4-0.8: 1. The first treatment, forming a mixture of the first calcined kaolin, water, the first acid, and optionally one or more of the first modified metal compounds such as tin, copper, and chromium compounds, the first calcined kaolin and a solution formed from the first acid, water, and optionally one or more of the tin, copper, and chromium compounds may be added to a vessel and mixed with stirring; or the first calcined kaolin and water are slurried and then a first acid, optionally a compound of one or more of tin, copper and chromium compounds, is added to the slurry, preferably to form a mixture in which the concentration of the first acid is 0.5 to 5 moles of acid per liter of water. One or more compounds of tin, copper, and chromium compounds may be added to the slurry containing the first calcined kaolin. The first treatment, the first calcined kaolin, water, the first acid, optionally one or more of tin, copper and chromium compounds to form a mixture, then the mixture is warmed to 40-80 ℃, preferably 60-80 ℃, and stirred at 40-80 ℃, preferably 60-80 ℃ for 0.5-2 hours, then filtered and dried.
The invention provides a preparation method of the kaolinite with the macroporous structure, and the second treatment, wherein the second acid is an organic acid and/or an inorganic acid, and the acid is one or more of hydrochloric acid, nitric acid, oxalic acid, phosphoric acid, sulfuric acid and citric acid; the ratio of the second acid to water may be from 0.5 to 10mol acid per liter of water, for example from 0.5 to 5mol acid per liter of water or from 1 to 3mol acid per liter of water. The weight ratio of water in the second treatment to the second calcined kaolin (on a dry basis) is from 0.5 to 15: 1, for example from 1 to 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 a mixture of the second acid, water, pore-expanding agent, optionally a first modifying metal compound such as one or more of tin, copper and chromium compounds, and then warmed and stirred at 40-80 c, preferably 60-80 c, for at least 0.5 hour, e.g. for 0.5-2 hours; it is also possible to slurry the second calcined kaolin with water, then add the second acid or a solution of the second acid, the pore-expanding agent, optionally the first modifying metal compound such as one or more of tin, copper and chromium compounds, then warm up and stir at 40-80 c, preferably 60-80 c, for at least 0.5 hour, for example for 0.5-2 hours, wherein the water and acid are used in such amounts that the resulting mixture has an acid to water ratio of 0.5-10 moles acid per liter of water, preferably 0.5-5 moles acid per liter of water, for example 1-3 moles acid per liter of water. In another embodiment, for example, the second calcined kaolin, the second acidic solution, and the pore-expanding agent, and optionally one or more of the first modified metal compounds, such as tin, copper, and chromium compounds, are added together in a vessel, and the temperature is raised to 40-80 ℃ with stirring, and the mixture is stirred for 0.5-2 hours. In one embodiment, the second acid is hydrochloric acid and oxalic acid in a molar ratio of 0.2 to 10: 1, preferably 0.3 to 5: 1, for example 1 to 5: 1, or 0.35 to 3: 1, or 0.3 to 0.8: 1.
The invention provides a preparation method of kaolinite with a macroporous structure, wherein the pore-enlarging agent can be one or more of ammonium phosphate, ammonium chloride, organic amine, polyethylene glycol, polyacrylamide and ammonium sulfate. In one embodiment, the weight ratio of the pore-expanding agent to the second calcined kaolin is from 0.05 to 1: 1, such as from 0.1 to 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 preparation method of large-pore structure kaolinite, wherein a first modified metal compound is introduced in at least one step of first contact and second contact. The mass ratio of the first modified metal compound (calculated as oxide) introduced by the first contact and the second contact is 0.5-2: 1. The first modified metal compound is one or more of tin, copper and chromium compounds, and can be a tin compound, a copper compound or a chromium compound, and also can be a tin compound, a copper compound or a chromium compound, such as a tin compound and/or a copper compound and/or a chromium compound.
When the prepared kaolinite with the macroporous structure simultaneously contains Cu, Cr and Sn, a tin compound is introduced in at least one step of the first contact and the second contact; the copper compound is introduced in at least one of the steps of the first contacting and the second contacting, and the chromium compound is introduced in at least one of the steps of the first contacting and the second contacting. The tin compound may be added in the first treatment, may be added in the second treatment, or may be added in both the first treatment and the second treatment. The copper compound may be added in the first treatment or in the second treatment, or the chromium compound may be added in both the first treatment and the second treatment, or in both the first treatment and the second treatment. Preferably, a tin compound, a copper compound and a chromium compound are introduced into the first treatment and the second treatment; the first and second treatments introduce tin in a ratio of 0.5 to 2: 1 by weight, e.g. 1 to 2: 1 by weight, copper in a ratio of 0.5 to 2: 1 by weight, e.g. 1 to 2: 1 by weight, and chromium in a ratio of 0.5 to 2: 1 by weight, calculated as oxides. The tin compound is one or more of stannous oxide, stannic oxide, stannous chloride, stannic chloride, stannous sulfate, stannic sulfate, potassium stannate, zinc stannate and stannous acetate; the copper compound is one or more of chloride, sulfate and nitrate of copper; such as chromium chloride, chromium sulfate, jarosite and chromium oxides. The first modified metal compound introduced in the first treatment and the second treatment may be the same or different, the tin compound introduced in the first treatment and the second treatment may be the same or different, the copper compound may be the same or different, and the chromium compound may be the same or different.
When the second modifying metal is contained in the macroporous kaolinite, the compound of the second modifying metal is also added into the mixture of the first treatment and/or the mixture of the second treatment. A compound of a second modifying metal such as one or more of a chloride of a rare earth, a nitrate, a chloride of titanium, a nitrate of titanium, a chloride of zirconium such as zirconium oxychloride. The rare earth element comprises at least one of La, Ce, Sc, Pr and Nd.
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 product performance caused by the volatilization of the acid is avoided.
The method for preparing the kaolinite with the macroporous structure, provided by the invention, is preferableThe obtained kaolinite with a macroporous structure contains CaO and MgO in an amount of not more than 2 wt% based on the dry weight, such as CaO and MgO in an amount of 1-2 wt%, and alpha-SiO2In an amount of not more than 2% by weight, e.g. 1-2% by weight, Fe2O3In an amount of not more than 1.5 wt.%, e.g. Fe2O30.5 to 1.5% by weight, the first modifier metal being present in an amount of 0.1 to 6% by weight, preferably 1.5 to 4.5% by weight, calculated as oxide, of tin, with a tin content of 0 to 6% by weight, for example 0.1 to 6% by weight or 0 to 4.5% by weight, a copper content of 0 to 6% by weight, for example 0.1 to 6% by weight or 0 to 4.5% by weight, a chromium content of 0 to 6% by weight, for example 0.1 to 6% by weight or 0 to 4.5% by weight, and the tin, copper and chromium contents not being simultaneously 0; more preferably, the tin content is 0.5 to 1.5 wt.%, the copper content is 0.5 to 1.5 wt.%, and the chromium content is 0.5 to 1.5 wt.%, calculated as oxide.
The invention provides a preparation method of a large-pore structure kaolinite, which comprises the following steps: al (Al)2O333-42 wt.% of Fe2O3Not more than 1.5 wt%, for example, 0.5 to 1.5 wt%, CaO + MgO in an amount of 1 to 2 wt%, and alpha-SiO2The content of the first modified metal is 1-2 wt%, the content of the first modified metal is 0.1-6 wt% calculated by oxide, wherein the content of tin is 0-6 wt%, the content of copper is 0-6 wt%, the content of chromium is 0-6 wt%, the first metal is one or more of tin, copper and chromium, preferably, the content of the first modified metal is 1.5-4.5 wt% calculated by oxide, more preferably, the content of tin is 0.5-1.5 wt%, the content of copper is 0.5-1.5 wt%, and the content of chromium is 0.5-1.5 wt% calculated by oxide; specific surface area of 100-250m2The/g is, for example, 100-2Pore volume of 0.20-0.30ml/g, e.g. 0.22-28 ml/g. The macroporous kaolinite has an average pore diameter of from 2 to 50nm, preferably from 10 to 30nm, for example from 10 to 24nm or from 10 to 17nm, or from 10 to 15 nm. The pore volume of the macroporous kaolinite with the pore diameter of 10-50nm accounts for more than 80 percent of the total pore volume, for example 80-95 percent, preferably 81-95 percent. Wherein the specific surface area is determined by nitrogen low-temperature adsorption method, the pore volume is determined by water dropping method, and the element composition is determined by X-ray fluorescence spectrometry. Said bigIn the pore structure kaolinite, SiO2The content may be 45-59.5 wt%, such as 46-58 wt%, or 47-55 wt%, or 50-53 wt%.
The invention provides a preferable preparation method of the macroporous kaolinite, which comprises the following steps:
(1) the kaolin is roasted for 1 to 2 hours at the temperature of 700-750 ℃, the roasting process is called as first roasting, the kaolin after the first roasting is obtained,
(2) mixing the first calcined kaolin with a first acid, water and one or more compounds selected from tin, copper and chromium compounds to form a mixture, heating to 60-80 ℃, and contacting at 60-80 ℃ for 1-2 hours 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 mol ratio of HCl to oxalic acid is 0.3-5: 1, preferably 0.8-1.5: 1 or 0.4-0.8: 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) mixing the second calcined kaolin, a second acid, water and one or more compounds selected from pore-expanding agents, tin, copper and chromium compounds to form a mixture, heating to 60-80 ℃, and stirring at 60-80 ℃ for at least 1-2 hours to obtain a second kaolin slurry, wherein the process is called 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 after the second roasting is 2-5: 1; the second acid is hydrochloric acid and oxalic acid, and the mol ratio of HCl to oxalic acid is 0.3-5: 1, preferably 0.8-1.5: 1 or 0.35-0.8: 1; the weight ratio of the pore-expanding agent to the kaolin after the second roasting is 0.1-0.5: 1, preferably 0.3-0.5: 1;
(6) filtering and drying the second kaolin slurry to obtain the kaolinite with a macroporous structure;
wherein the first treatment and the second treatment introduce one or more compounds of tin, copper and chromium compounds in a ratio of 0.5 to 2: 1 for example 1-2: 1 weight ratio. For example, when the tin compound is introduced during the preparation process, the first treatment and the second treatment introduce tin in a ratio of 0.5 to 2: 1, e.g., 1 to 2: 1, when the copper compound is introduced during the preparation process, the first treatment and the second treatment introduce copper in a ratio of 0.5 to 2: 1, e.g., 1 to 2: 1, and when the chromium compound is introduced during the preparation process, the first treatment and the second treatment introduce chromium in a ratio of 0.5 to 2: 1, e.g., 1 to 2: 1. Preferably, when the tin compound is introduced during the preparation process, the weight ratio of the tin compound (calculated as tin dioxide) added in the first treatment to the kaolin after the first calcination is 0.1-2: 100, such as 0.5-2: 100, and the weight ratio of the tin compound (calculated as tin dioxide) added in the second treatment to the kaolin after the second calcination is 0.1-2: 100, such as 0.5-2: 100; when the copper compound is introduced in the preparation process, the weight ratio of the copper compound (calculated by copper oxide) added in the first treatment to the kaolin after the first roasting is 0.5-2: 100, such as 0.8-2: 100, and the weight ratio of the copper compound (calculated by copper oxide) added in the second treatment to the kaolin after the second roasting is 0.5-2: 100, such as 0.8-2: 100; when the chromium compound is introduced in the preparation process, the weight ratio of the chromium compound (calculated by chromium oxide) added in the first treatment to the kaolin after the first roasting is 0.5-2: 100, such as 1-2: 100, and the weight ratio of the chromium compound (calculated by chromium oxide) added in the second treatment to the kaolin after the second roasting is 0.5-2: 100, such as 1-2: 100. The compound of one or more of tin, copper and chromium compounds is one or more of a tin compound, a copper compound and a chromium compound. The weight of the first calcined kaolin and the second calcined kaolin are on a dry basis.
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 content of the molecular sieve in the catalytic cracking catalyst provided by the invention is more than 25 wt%, for example, the content of the molecular sieve is preferably 25-35 wt%.
The catalytic cracking catalyst provided by the invention contains 25-35 wt% of molecular sieve (calculated on a dry basis) on the basis of dry basis weight (the dry basis weight is 800 ℃, and the weight of the catalyst after 1 hour of burning); 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%.
According to the preparation method of the catalytic cracking catalyst, the clay is a clay raw material which is well known to a person skilled in the art, the 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 the molecular sieve is preferably REY, REHY, REUSY and USY which adopt a gas phase chemical method (SiCl) aiming at the invention4Al 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. Preferably, the molecular sieve is a Y-type molecular sieve.
The invention also provides the catalytic cracking catalyst obtained by the preparation method.
The kaolinite with the macroporous structure provided by the invention has high average pore diameter, high proportion of 10-50nm mesopores and higher heavy oil cracking capability. Can be used for preparing catalytic cracking catalyst instead of clay.
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 mesopore content.
The cracking catalyst provided by the invention has better heavy oil cracking capability, higher low-carbon olefin yield, good coke selectivity, high gasoline yield and high gasoline octane number.
Drawings
FIG. 1 is an electron micrograph of macroporous kaolinite B prepared in example 1
Detailed description of the invention
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: a solid content of 72% by weight, produced by Kaolin corporation of China (Suzhou); (hard kaolin, having a crystalline kaolinite content of 70 wt.%), referred to in the subsequent examples as kaolin A.
Hydrochloric acid, oxalic acid, diammonium hydrogen phosphate, stannous chloride, copper chloride, chromium chloride hexahydrate and citric 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, with a solid content of 80 wt% and a rare earth content (as RE)2O3Calculated) 17.4 wt%;
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, and dried at 150 ℃ for 3 hours before measurement.
Preparation of Large pore structured Kaolin example 1
Roasting kaolin A at 750 ℃ for 2 hours to obtain a roasted material (called a first roasted material), adding 168g (calculated on a dry basis, the same below) of the roasted material into decationized water (pH is 3.1, the same below) and 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, 1.5g of stannous chloride, 2g of copper chloride and 4g of chromium chloride hexahydrate, heating to 70 ℃, stirring for 1 hour at 70 ℃, then 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, 50g of polyethylene glycol, 1g of stannous chloride, 1.2g of copper chloride and 2.5g of chromium chloride hexahydrate, heating to 70 ℃, stirring for 1 hour at 70 ℃, filtering to remove mother liquor, filtering a filter cake, and drying to obtain the kaolinite B with the macroporous structure, wherein the parameters and the analytical data of the preparation process are shown in tables 1-1 and 2.
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, 100g of oxalic acid, 1.5g of stannous chloride, 2g of copper chloride and 4g of chromium chloride hexahydrate, heating to 70 ℃, stirring at 70 ℃ for 1 hour, then filtering to remove a mother solution, and drying a filter cake to obtain a first-step product; roasting 120g of the product obtained in the first step at 650 ℃ for 0.5 hour to obtain a roasted material (called as a second roasted material), adding acidic 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, 50g of polyethylene glycol, 1g of stannous chloride, 1.2g of copper chloride and 2.5g of chromium chloride hexahydrate, heating to 70 ℃, stirring at 70 ℃ for 1 hour, filtering to remove mother liquor, filtering a filter cake, and drying to obtain the kaolinite C with a macroporous structure, wherein the parameters and analytical data of the preparation process are shown in tables 1-1 and 2.
Preparation of Large pore Structure Kaolin example 3
Roasting kaolin 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, 1g of stannous chloride, 1.5g of copper chloride and 4g of chromium chloride hexahydrate, heating to 70 ℃, stirring at 70 ℃ for 1 hour, filtering to remove a mother solution, 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 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, 50g of polyethylene glycol, 1g of stannous chloride, 1.2g of copper chloride and 2.5g of chromium chloride hexahydrate, heating to 70 ℃, stirring for 1 hour at 70 ℃, filtering to remove mother liquor, and drying a filter cake to obtain the kaolinite D with the macroporous structure, wherein the parameters and the analytical data of the preparation process are shown in tables 1-1 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 of the roasted material, stirring to obtain slurry with the solid content of 25 percent by weight, adding 200g of phosphoric acid with the concentration of 1mol/L, 100g of citric acid, 1g of stannous chloride, 1.5g of copper chloride and 4g of chromium chloride hexahydrate, heating to 70 ℃, stirring for 1 hour at 70 ℃, filtering to remove mother liquor, and drying a filter cake to obtain a first-step product; roasting 120g of the product of the first step at 750 ℃ for 2 hours to obtain a roasted material called as 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 sulfuric acid with the concentration of 1mol/L, 50g of citric acid, 50g of ammonium sulfate, 1g of stannous chloride, 1.2g of copper chloride and 2.5g of chromium chloride hexahydrate, heating to 70 ℃, stirring for 1 hour at 70 ℃, filtering to remove mother liquor, filtering a filter cake, and drying to obtain the kaolinite E with a macroporous structure, wherein the parameters and the analytical data of the preparation process are shown in tables 1-1 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, the second treatment was carried out, the concentration of the acid was 5M, the ratio of hydrochloric acid to oxalic acid was 5: 1, and the lower limit was adopted for the ratio of the pore-expanding agent to the kaolinite: 0.1: 1, adding tin, copper and chromium metal elements in the second treatment, and not adding the tin, copper and chromium metal elements in the first treatment. The resulting large pore structure kaolinite is denoted as F. The preparation process parameters and the analysis data are shown in the table 1-1 and the 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 800 ℃ for 1 hour, the temperature of the second calcination was 650 ℃ for 2 hours, and the first treatment was carried out with an acid concentration of 5M, wherein the molar ratio of hydrochloric acid to oxalic acid was 1: 1. And (2) second treatment, wherein the concentration of acid is 0.5M, the ratio of hydrochloric acid to oxalic acid is 1: 1, and the upper limit of the proportion of pore-expanding agent polyethylene glycol to kaolin is as follows: 0.5: 1. The obtained kaolinite with the macroporous structure is marked as G, and metal elements of tin, copper and chromium are added in the first treatment, and metal elements of tin, copper and chromium are not added in the second treatment. The preparation process parameters and analytical data are shown in tables 1-2 and 2
Preparation of Large pore structured Kaolin example 7
Roasting kaolin A at 750 ℃ for 2 hours to obtain a roasted material (called as a first roasted material), adding 168g (calculated on a dry basis, the same below) of the roasted material into decationized water (pH is 3.1, the same below) and stirring to prepare slurry with the solid content of 25 weight percent, adding 500g of hydrochloric acid with the concentration of 1mol/L, 100g of oxalic acid and 5g of stannous chloride, heating to 70 ℃, stirring for 1 hour at 70 ℃, 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, 50g of polyethylene glycol and 3g of stannous chloride, heating to 70 ℃, stirring at 70 ℃ for 1 hour, then filtering to remove mother liquor, filtering a filter cake, and drying to obtain the kaolinite H with the macroporous structure, wherein the parameters and the analytical data of the preparation process are shown in tables 1-2 and 2.
Preparation of macroporous Kaolin example 8
Roasting kaolin A at 750 ℃ for 2 hours to obtain a roasted material (called a first roasted material), adding 168g (calculated on a dry basis, the same below) of the roasted material into decationized water (pH is 3.1, the same below) and stirring to prepare slurry with the solid content of 25 weight percent, adding 500g of hydrochloric acid with the concentration of 1mol/L, 100g of oxalic acid and 6g of copper chloride, heating to 70 ℃, stirring for 1 hour at 70 ℃, 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, 50g of polyethylene glycol and 4g of copper chloride, heating to 70 ℃, stirring at 70 ℃ for 1 hour, then filtering to remove mother liquor, filtering a filter cake, and drying to obtain the kaolinite I with the macroporous structure, wherein the parameters and the analytical data of the preparation process are shown in tables 1-2 and 2.
Preparation of Large pore structured Kaolin example 9
Roasting kaolin A at 750 ℃ for 2 hours to obtain a roasted material (called a first roasted material), adding 168g (calculated on a dry basis, the same below) of the roasted material into decationized water (pH is 3.1, the same below) and stirring to prepare slurry with the solid content of 25 weight percent, adding 500g of hydrochloric acid with the concentration of 1mol/L, 100g of oxalic acid and 12g of chromium chloride hexahydrate, heating to 70 ℃, stirring for 1 hour at 70 ℃, then 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, 50g of polyethylene glycol and 8g of chromium chloride hexahydrate, heating to 70 ℃, stirring for 1 hour at 70 ℃, filtering to remove mother liquor, and drying a filter cake to obtain the kaolinite J with the macroporous structure, wherein the parameters and the analytical data of the preparation process are shown in tables 1-2 and 2.
Preparation of macroporous Kaolin example 10
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 analysis result shows that the total pore volume, the specific surface area, the average pore diameter and the proportion of the pore volume of the 10-50nm pores in the total pore volume of the obtained macroporous kaolinite are almost consistent with those of the example 1, and the composition is close to that.
Preparation of macroporous Kaolin example 11
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 analysis result shows that the total pore volume, the specific surface area, the average pore diameter and the proportion of the pore volume of the 10-50nm pores in the total pore volume of the obtained macroporous kaolinite are almost consistent with those of the example 1, and the composition is close to that.
Preparation of modified kaolinite comparative example 1
Roasting kaolin A at 750 ℃ for 2 hours to obtain a roasted material (called as a first roasted material), adding 168g of the roasted material into decationized water, 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 at 70 ℃, 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 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 at 70 ℃ for 1 hour, filtering to remove mother liquor, drying a filter cake, contacting with a solution containing stannous chloride, copper chloride and chromium chloride hexahydrate, introducing tin, copper and chromium, and drying to obtain a comparative kaolinite K, wherein the parameters and the analysis data of the preparation process are shown in tables 1-2 and 2.
TABLE 1-1 conditions of the procedures of the preparation examples of Large pore structured Kaolin
In tables 1-1 and 1-2, BT1 represents the first calcined kaolin and BT2 represents the second calcined kaolin. BT1 and BT2 on a dry basis.
TABLE 1-2 conditions of the procedures of the preparation examples of kaolin having a macroporous structure
TABLE 2 chemical composition and Properties of macroporous Kaolin
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; meanwhile, the average pore diameter of the kaolinite B-J with the macroporous structure is 10-30nm, and the pore volume of the pores with the pore diameter of 10-50nm accounts for more than 80 percent 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, available from Shandong aluminum Co., Ltd.), adding 60.69Kg of decationized water (also called acid water in the invention), stirring for 40min, adding 22.28Kg of macroporous kaolinite B and 31.94Kg of kaolinite, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. Adding 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 C1. The catalyst formulation and product properties are shown in Table 3-1.
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 61.28Kg 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 REY type 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, washing with decationized water with weight 8 times of 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 properties shown in Table 3-1.
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 54.32Kg 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. Adding 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 C3. The catalyst formulation and product properties are shown in Table 3-1.
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 555.48Kg 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. Adding 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 C4. The catalyst formulation and product properties are shown in Table 3-1.
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 55.48Kg 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. Adding 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 C5. The catalyst formulation and product properties are shown in Table 3-1.
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 55.32Kg 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 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 3-1.
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 55.08Kg 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 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 3-2.
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 55.08Kg 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 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 3-2.
Catalyst preparation example 9
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 55.08Kg of macroporous kaolinite H, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. Adding 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 C9. The catalyst formulation and product properties are shown in Table 3-2.
Catalyst preparation example 10
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 55.08Kg of macroporous kaolinite I, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. Adding 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 C10. The catalyst formulation and product properties are shown in Table 3-2.
Catalyst preparation example 11
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 55.08Kg of macroporous kaolinite J, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. Adding 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 C11. The catalyst formulation and product properties are shown in Table 3-2.
Catalyst preparation comparative 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 industry Co.), adding 60.69Kg of acidic water, stirring for 40min, adding 55.24Kg of macroporous kaolinite K, stirring for 60min, adding 2Kg of hydrochloric acid with the concentration of 22 percent by weight, and stirring for 30 min. Adding 117.54Kg of molecular sieve slurry (43.75 Kg of REY type 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 D1. The catalyst formulation and product properties are shown in Table 3-2.
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 3-1
TABLE 3-2
TABLE 4
TABLE 5
As can be seen from table 5, compared with the contrast agent, the catalyst prepared from the macroporous kaolinite prepared by the method of the present invention has the advantages of superior heavy oil cracking performance, higher conversion rate, high gasoline yield, high liquefied gas yield, higher gasoline octane number and better coke selectivity under the premise of the same usage amount of the molecular sieve; the catalyst C2 prepared in example 2 using a lower molecular sieve content still had better and better heavy oil cracking performance and higher conversion, gasoline yield and gasoline octane number than the comparative example.
Claims (28)
1. A kind ofThe large-pore structure kaolinite is characterized by comprising a first modified metal, wherein the first modified metal is one or more of tin, copper and chromium, the content of the first modified metal is 0.1-6 wt% calculated by oxide, 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; the specific surface area of the kaolinite with the macroporous structure is 100-250m2(ii)/g, total pore volume is 0.20-0.30 ml/g; al of the macroporous kaolinite2O333-45 wt.% of SiO2The content is 45-59.5 wt%.
2. The macroporous kaolinite according to claim 1, wherein the macroporous kaolinite has an average pore diameter of preferably 10 to 30 nm.
3. The macroporous kaolinite according to claim 1, wherein the macropore structure kaolinite has a pore volume of pores having a pore diameter of 10 to 50nm of 80 to 95% of the total pore volume.
4. The macroporous kaolinite as claimed in claim 1, wherein the macroporous kaolinite has a specific surface area of 100-200m2The total pore volume is 0.22-0.28 ml/g.
5. The macroporous structural kaolinite as recited in claim 1, wherein said first modifier metal is present in an amount of from 1.5 to 4.5 wt.% as oxide, based on the dry weight of the macroporous structural kaolinite.
6. The macroporous kaolinite as recited in claim 1, wherein said macroporous kaolinite comprises both tin, copper and chromium; calculated by oxide, the content of tin is 0.5-1.5 wt%, the content of copper is 0.5-1.5 wt%, and the content of chromium is 0.5-1.5%.
7. The macroporous structure of claim 1Ling stone, wherein Al of the macroporous kaolinite is based on the dry weight of the macroporous kaolinite2O3The content is 35-42 wt%.
8. The macroporous kaolinite as claimed in claim 1, wherein said macroporous kaolinite has a CaO + MgO content of not more than 2 wt% and an α -SiO content2Not more than 2% by weight of Fe2O3The content is not more than 1.5 wt%.
9. The macroporous kaolinite of claim 8, wherein said macroporous kaolinite has a CaO + MgO content of 1-2 wt% and an α -SiO content21-2 wt.% of Fe2O3The content is 0.5-1.5 wt%.
10. The macroporous kaolinite according to claim 3, wherein the macroporous kaolinite has a pore volume of pores having a pore diameter of 10 to 50nm of 81 to 93% of the total pore volume.
11. 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 the first roasting;
contacting the kaolin subjected to the first roasting, water, a first acid and an optional first modified metal compound at the temperature of 40-80 ℃ for 0.5-2 hours to perform first treatment to obtain first kaolin slurry, filtering the first kaolin slurry, and drying to obtain a first dried product; the compound of the first metal is one or more of tin, copper and chromium compounds;
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;
contacting the kaolin subjected to the second roasting, water, a second acid, a pore-expanding agent and an optional first modified metal compound at the temperature of 40-80 ℃ for 0.5-2 hours for second treatment, filtering and drying to obtain the kaolinite with a macroporous structure; the first modified metal compound is one or more of tin, copper and chromium compounds;
wherein the compound of the first modifier metal is introduced in at least one step of the first treatment and/or the second treatment.
12. The method according to claim 11, wherein the contact temperature of the first treatment is 60 to 80 ℃ and the contact temperature of the second treatment is 60 to 80 ℃.
13. The method of claim 11, wherein the kaolin is one or more of soft kaolin, hard kaolin, sandy kaolin, coal gangue, halloysite.
14. The method as claimed in claim 11, wherein the first calcination temperature is 650-750 ℃ and the calcination time is 1-2 hours.
15. The method as claimed in claim 11, wherein the second calcination is carried out at a calcination temperature of 650-750 ℃ for a calcination time of 1-2 hours.
16. The method of claim 11, wherein the first acid is one or more of hydrochloric acid, nitric acid, phosphoric acid, oxalic acid, acetic acid, citric acid; the second acid is one or more of hydrochloric acid, phosphoric acid, nitric acid, oxalic acid, sulfuric acid and citric acid.
17. The method of claim 11, wherein the first acid comprises hydrochloric acid and oxalic acid in a ratio of 0.3 to 10: 1 molar ratio; the second acid comprises hydrochloric acid and oxalic acid, and the ratio of the hydrochloric acid to the oxalic acid is 0.2-10: 1 molar ratio.
18. The method of claim 17, wherein the ratio of hydrochloric acid to oxalic acid in the first acid is from 0.4 to 5: 1 molar ratio, the ratio of hydrochloric acid to oxalic acid in the second acid is 0.3-5: 1 molar ratio.
19. The method of claim 11, wherein in the first treatment, the ratio of the first acid to water is 0.5 to 5mol acid/L water; in the second treatment, the ratio of the second acid to the water is 0.5-5mol of acid per L of water; the weight ratio of water to the kaolin after the first contact and the first roasting is 0.5-15: 1; in the second contact, the weight ratio of water to the kaolin after the second roasting is 0.5-15: 1.
20. the method of claim 19, wherein the first contacting is performed with a weight ratio of water to the first calcined kaolin of from 1 to 10: 1; and in the second contact, the weight ratio of water to the kaolin subjected to second roasting is 1-10: 1.
21. the method of claim 11, wherein the pore-expanding agent is one or more of ammonium phosphate, ammonium chloride, ammonium sulfate, organic amine, polyethylene glycol and polyacrylamide.
22. The method of claim 21, wherein the weight ratio of the pore-expanding agent to the second calcined kaolin is from 0.05 to 1: 1.
23. the method of claim 22, wherein the weight ratio of pore-expanding agent to the second calcined kaolin is from 0.1 to 0.5: 1.
24. the method according to claim 11, wherein the compound of the first modified metal is one or more of a tin compound, a chromium compound and a copper compound, and the tin compound is one or more of stannous oxide, stannic oxide, stannous chloride, stannic chloride, stannous sulfate, stannic sulfate, potassium stannate, zinc stannate and stannous acetate; the copper compound is one or more of chloride, sulfate and nitrate of copper; the chromium compound is chromium chloride, chromium sulfate, chromium potassium alum and chromium oxide; the first modified metal compound introduced by the first treatment and the second treatment may be the same or different.
25. The method of claim 11 or 24, wherein the first treatment and the second treatment each incorporate a compound of the first modifier metal in a weight ratio of 0.5 to 2, calculated as oxide, of the first modifier metal incorporated by the first treatment to the second modifier metal incorporated by the second treatment: 1.
26. the method of claim 25, wherein the first and second treatments each introduce a tin compound, a copper compound, and a chromium compound, the first and second treatments introducing tin in a ratio of SnO2In terms of 0.5-2: 1 weight ratio, the ratio of copper introduced by the first treatment and the second treatment is 0.5-2 in terms of CuO: 1 weight ratio, the ratio of chromium introduced by the first treatment and the second treatment is Cr2O3In terms of 0.5-2: 1 weight ratio.
27. A catalytic cracking catalyst comprising a molecular sieve, a macroporous kaolinite as claimed in any one of claims 1 to 10 or a macroporous kaolinite preparable by a process according to any one of claims 11 to 26, a binder and optionally a clay, wherein the macroporous kaolinite is present in an amount of 2 to 50 wt%, the molecular sieve is present in an amount of 25 to 35 wt%, the binder is present in an amount of 10 to 30 wt% and the clay is present in an amount of 0 to 50 wt%.
28. A method for preparing a catalytic cracking catalyst, wherein the method comprises: a binder, optionally clay, molecular sieve and macroporous kaolinite, the binder, the optional clay, the molecular sieve and the macroporous kaolinite being as defined in any one of claims 1 to 10 or preparable by a method according to any one of claims 11 to 26, to obtain a catalyst slurry, and the catalyst slurry is spray dried.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861756A (en) * | 2005-05-12 | 2006-11-15 | 中国石油天然气股份有限公司 | Assitants for catalyzing cyacking of reducing gasoline sulphur content, preparation process and application thereof |
| CN101045202A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Method for modifying kaolinite |
| CN101210196A (en) * | 2006-12-29 | 2008-07-02 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
| CN101209391A (en) * | 2006-12-30 | 2008-07-02 | 中国石油化工股份有限公司 | Method for removing oxysulfide and/or nitrogen oxide from flue gas and hydrocarbon oil cracking method |
-
2017
- 2017-10-23 CN CN201710995041.2A patent/CN109692702B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1861756A (en) * | 2005-05-12 | 2006-11-15 | 中国石油天然气股份有限公司 | Assitants for catalyzing cyacking of reducing gasoline sulphur content, preparation process and application thereof |
| CN101045202A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Method for modifying kaolinite |
| CN101210196A (en) * | 2006-12-29 | 2008-07-02 | 中国石油化工股份有限公司 | Conversion method for hydrocarbon oil |
| CN101209391A (en) * | 2006-12-30 | 2008-07-02 | 中国石油化工股份有限公司 | Method for removing oxysulfide and/or nitrogen oxide from flue gas and hydrocarbon oil cracking method |
Non-Patent Citations (1)
| 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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