A y-type molecular sieve catalytic material, a preparation method thereof and a method for producing gasoline and liquefied gas by catalytic cracking

Abstract

The present application relates to a kind of Y type molecular sieve catalytic material and its preparation method, catalytic cracking production gasoline and liquefied gas method, the Y type molecular sieve catalytic material is obtained by the hydrothermal crystallization of reactive microspheres containing zirconium titanium, with the dry base weight of reactive microspheres containing zirconium titanium as benchmark, the reactive microspheres containing zirconium titanium contains 70-97.9 wt.% alumina matrix, 0.1-15 wt.% zirconium oxide and 2-15 wt.% titanium oxide, and the total content of zirconium oxide and titanium oxide is 2.1-18 wt.%.The catalyst containing the Y type molecular sieve catalytic material of the present application has higher conversion rate of raw material, higher gasoline and LPG yield, lower LCO yield, oil slurry, coke yield and selectivity.

Description

Technical Field

[0001] This invention relates to a Y-type molecular sieve catalytic material and its preparation method, as well as a method for producing gasoline and liquefied petroleum gas by catalytic cracking. Background Technology

[0002] With the increasing weight and quality of crude oil worldwide, heavy oil and residual oil have become the main processing feedstocks used in catalytic cracking processes. Because heavy oil contains a significant amount of gums, asphaltenes, and heavy metals, FCC catalysts are required to possess high matrix activity, strong resistance to metal contamination, and good catalytic activity and selectivity. Among these, FCC catalysts containing Y-type zeolites are currently the most widely used type of catalyst.

[0003] Currently, there are two main forms of Y-type molecular sieve cracking catalysts used in industry. The first is called the semi-synthetic binder type, which involves exchanging and modifying Y-type molecular sieves and then mixing them with kaolin and a binder for spray molding. The second is called the in-situ crystallization type, which involves calcining kaolin spray microspheres at high temperature and then hydrothermally crystallizing them in an alkaline system, thereby growing Y-type molecular sieves on the inner and outer surfaces of the microspheres, and then exchanging and modifying them to obtain the finished catalyst. The in-situ crystallization type has the following characteristics compared to the semi-synthetic binder type catalyst: (1) In-situ crystallization simultaneously generates Y-type molecular sieves and a matrix, which are connected by chemical bonds, resulting in higher thermal and hydrothermal stability; (2) Y-type molecular sieves are uniformly distributed on the inner and outer surfaces of the matrix pores, and the crystal size is about ten times smaller than that of NaY synthesized by the gel method, greatly improving the accessibility and cracking performance of heavy feedstock oil; (3) The kaolin microspheres calcined at high temperature contain an aluminum-rich spinel structure, which has excellent resistance to vanadium-nickel contamination and mechanical wear. Therefore, the in-situ crystallization type cracking catalyst has advantages for the processing of heavy feedstock oil. Among them, the precursor used in the in-situ crystallization catalyst—kaolin microspheres—is the key to this preparation technology.

[0004] Since the 1960s, Engelhard Corporation of the United States has filed a series of patents related to the in-situ crystallization preparation of cracking catalysts, which disclose the main technical characteristics of kaolin microspheres. These include patents such as US3503990, US3506494, US3663165, US4493902, US4965233, and US5023220. This series of patents discloses that the precursor microspheres contain a mixture of two different forms of chemically active calcined clay. These two forms of calcined clay are metakaolin (kaolin calcined to undergo a strong endothermic reaction related to dehydroxylation) and kaolin calcined under more severe conditions than the usual conversion of kaolin to metakaolin, i.e., kaolin calcined to undergo a characteristic exothermic reaction, sometimes referred to as spinel-type calcined kaolin. However, the technology proposed in US4493902 has very high requirements for the raw materials used in spray molding, requiring the use of ultrafine kaolin Satone-NO2 and ultrafine raw clay ASP-600. These ultrafine clays are expensive and not readily available on the market. In addition, this method is energy-intensive, especially since obtaining spinel-type kaolin requires calcination at temperatures as high as 1100℃, which greatly increases the cost of the catalyst.

[0005] Lanzhou Petrochemical Company in China has developed LB-1 and LB-2 in-situ crystallization cracking catalysts. CN1232862 discloses the main technical characteristics of the precursor microspheres: a portion of the parent microparticles are calcined at high temperature to obtain high-temperature calcined microspheres, while another portion is calcined at a lower temperature to obtain metakaolin microspheres. The two types of microspheres are mixed in a certain proportion as the in-situ crystallization precursor microspheres. However, the Y-type molecular sieves prepared by this method have low crystallinity, generally less than 30%, and a silicon-to-aluminum ratio generally less than 5.0.

[0006] CN1778676 mentions adding a structural additive during the spraying process. This structural additive includes one or a mixture of starch, graphite powder, and carboxymethyl cellulose, primarily to improve the pore structure of the kaolin spray microspheres. The amount added is 2-10% of the kaolin mass. This invention can also calcine a portion of the spray microspheres containing this structural additive, with a main particle size of 20-110 μm, at high temperature to obtain high-temperature calcined clay, and calcine another portion of the spray microspheres at a lower temperature to obtain metakaolin. The two types of calcined kaolin are then mixed and used for in-situ crystallization.

[0007] US6942783 discloses an FCC catalyst for improving heavy oil conversion prepared by in-situ crystallization technology. The precursor microspheres are composed of metakaolinite and hydrated kaolinite. These microspheres containing metakaolinite and hydrated kaolinite are calcined at a low temperature before crystallization to avoid the transformation of hydrated kaolinite into metakaolinite.

[0008] US20170362513A1 describes a method for in-situ preparation of improved fluidized bed cracking zeolite catalysts, in which the microspheres are composed of a mixture of spinel kaolinite, transition alumina and metamorphic kaolinite.

[0009] Analysis of the aforementioned patented technologies reveals that the core of in-situ crystallization catalyst preparation lies in first preparing a solid material primarily composed of kaolin and its derivatives, and then, under specific synthesis conditions, generating molecular sieves "in-situ" on the solid material through a liquid-solid reaction. Finally, post-processing yields the desired catalyst. However, the aforementioned patents have not made significant improvements in the composition and preparation process of the precursor kaolin microspheres, essentially continuing Engelhard's earlier two-stage calcination method. The problems of high energy consumption and high cost remain unresolved.

[0010] There are existing patents for adding auxiliary components in the preparation of microsphere precursors to prepare microsphere precursors with multifunctional potential. CN 105813739 A provides an FCC catalyst composition that uses one or more boron oxide components to passivate metals, particularly nickel. Passivation with boron components reduces or prevents the influence of harmful metals (such as nickel) on the cracking reaction. The precursor preparation incorporates non-zeolite components: wherein the non-zeolite material is selected from kaolinite, halloysite, montmorillonite, bentonite, palygorskite, kaolin, amorphous kaolin, metakaolin, mullite, spinel, hydrated kaolin, clay, gibbsite (blue hydrated alumina), boehmite, iron dioxide, alumina, silicon dioxide, silica alumina, silicon dioxide oxide, and sepiolite. Summary of the Invention

[0011] The purpose of this invention is to provide a Y-type molecular sieve catalytic material and its preparation method, as well as a method for catalytic cracking to produce gasoline and liquefied petroleum gas. The Y-type molecular sieve catalytic material of this invention has better strength and cracking effect, can improve the selectivity of gasoline production from feedstock catalytic cracking, and has higher gasoline and LPG yields.

[0012] To achieve the above objectives, the first aspect of the present invention provides a Y-type molecular sieve catalytic material, wherein the Y-type molecular sieve catalytic material is obtained by hydrothermal crystallization of zirconium-titanium-containing reactive microspheres, and based on the dry basis weight of the zirconium-titanium-containing reactive microspheres, the zirconium-titanium-containing reactive microspheres contain 70-97.9% by weight of alumina matrix, 0.1-15% by weight of zirconium oxide and 2-15% by weight of titanium oxide, and the total content of zirconium oxide and titanium oxide is 2.1-18% by weight.

[0013] Optionally, the zirconium-titanium reactive microspheres contain 72-97% by weight of alumina matrix, 0.5-14% by weight of zirconium oxide and 2.5-14% by weight of titanium oxide, and the total content of zirconium oxide and titanium oxide is 3-16% by weight.

[0014] The zirconium-titanium reactive microspheres have a sphericity of 85-100%, an abrasion index of 0.5-3% / h, and a particle size of 20-150 μm.

[0015] Optionally, based on the dry weight of the Y-type molecular sieve catalytic material, the zirconium oxide content is 1-12% by weight and the titanium oxide content is 3-12% by weight.

[0016] Optionally, the specific surface area of ​​the Y-type molecular sieve catalytic material is 200-700 m². 2 / g, the total pore volume is 0.20-0.50mL / g, the wear index is 0.1-2.5% / h, and the volume of medium and large pores with a pore size of 2-50nm accounts for 20-50% of the total pore volume;

[0017] Preferably, the specific surface area is 450-600 m². 2 / g, the total pore volume is 0.21-0.35mL / g, the wear index is 0.1-2.0% / h, and the volume of medium and large pores with a pore size of 2-50nm accounts for 25-48% of the total pore volume.

[0018] Preferably, the zirconium-titanium reactive microspheres are prepared by a method comprising the following steps:

[0019] A slurry is prepared by mixing alumina matrix raw material, zirconium sol, titanium sol and water, and the slurry is spray-dried to obtain the zirconium-titanium reactive microsphere precursor.

[0020] The zirconium-titanium-containing reactive microsphere precursor is further calcined to obtain the zirconium-titanium-containing reactive microspheres; the calcination conditions include: temperature of 300-1000℃ and time of 1-10 hours.

[0021] Optionally, the titanium sol is prepared by a method comprising the following steps:

[0022] (1) The titanium source is mixed with the hydrolysis inhibitor to obtain a third mixed solution, wherein the concentration of the third mixed solution, calculated as TiO2, is 0.5-30% by weight;

[0023] (2) Mix the third mixed solution, acid and dispersant, and react the resulting mixture at 20-90°C for 0.5-3 hours to obtain titanium sol; preferably, the pH value of the titanium sol is 0-7, more preferably 0.5-5.

[0024] Optionally, the zirconium sol has a particle size of 5-15 nm, an average particle size of 8-12 nm, a concentration of over 90%, a ZrO2 content of 0.5-20% by weight, a molar ratio of the stabilizer to Zr of 1-6, and a molar ratio of the alkaline cation to Zr of 1-8.

[0025] Optionally, the alumina matrix raw material contains hydrated kaolin and / or modified kaolin, optionally hydrated alumina, and optionally kaolin.

[0026] Preferably, the hydrated alumina is selected from one or more of boehmite, pseudo-boehmite, and gibbsite; more preferably, the hydrated alumina is calcined hydrated alumina or acidified hydrated alumina.

[0027] Preferably, based on the total weight of the alumina matrix raw material, the alumina matrix raw material contains 0-100% by weight, preferably 20-80% by weight of the hydrated kaolin, 0-100% by weight, preferably 10-80% by weight of the variable kaolin, 0-20% by weight of the hydrated alumina and 0-70% by weight, preferably 0-30% by weight of the kaolin.

[0028] Optionally, the titanium source is selected from one or more of tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium alkoxytitanium, titanium tetrachloride, titanium sulfate, and titanium oxysulfate;

[0029] The hydrolysis inhibitor is selected from one or more of water, lower alcohols with 1-5 carbon atoms, higher alcohols with 6 or more carbon atoms, hexanediol, ethanolamine, and acetylacetone; preferably one or more of ethanol, propanol, isopropanol, butanol, isobutanol, ethanolamine, and acetylacetone.

[0030] The acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, glycolic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid, preferably acetic acid or citric acid.

[0031] The dispersant is selected from one or more of polyethylene glycol, polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glycerol ester, fatty acid sorbitan, polysorbate, triethanolamine soap sucrose ester, polyol sucrose ester, sodium dodecyl sulfate, methyl ammonium bromide and hexadecyltrimethylammonium chloride.

[0032] The second aspect of the present invention provides a method for preparing the Y-type molecular sieve catalytic material provided in the first aspect of the present invention, the method comprising: mixing the zirconium-titanium-containing reactive microspheres, a first silicon source, a first directing agent, sodium hydroxide and water, and then subjecting the resulting mixture to hydrothermal crystallization treatment.

[0033] Optionally, the conditions for the hydrothermal crystallization treatment include: a temperature of 88-105°C and a time of 10-78 hours;

[0034] The weight ratio of the first silicon source, the first directing agent, sodium hydroxide and water is (2-15):1:(1-7):(40-400), wherein the first silicon source is calculated as SiO2, the first directing agent is calculated as Al2O3, and the sodium hydroxide is calculated as Na2O.

[0035] The weight ratio of the first directing agent (calculated as Al2O3) to the reactive microspheres containing zirconium and titanium is (0.001-2):1, preferably (0.01-0.5):1;

[0036] The first silicon source is selected from one or more of sodium silicate, silica gel, and organosilicon.

[0037] A third aspect of the present invention provides a zirconium-titanium-containing reactive microsphere suitable for hydrothermal crystallization preparation of Y-type molecular sieve catalytic materials. Based on the dry weight of the zirconium-titanium-containing reactive microsphere, the zirconium-titanium-containing reactive microsphere contains 0.1-15 wt% zirconium oxide, 2-15 wt% titanium oxide and 70-97.9 wt% alumina matrix.

[0038] Optionally, the zirconium-titanium reactive microspheres contain 72-97% by weight of an alumina matrix, 0.5-14% by weight of zirconium oxide and 2.5-14% by weight of titanium oxide;

[0039] The zirconium-titanium reactive microspheres have a sphericity of 85-100%, an abrasion index of 0.5-3% / h, and a particle size of 20-150 μm.

[0040] Optionally, based on the dry weight of the zirconium-containing reactive microspheres, the zirconium-containing reactive microspheres contain, on a dry basis, 10-95 wt%, preferably 15-80 wt%, preferably 20-50 wt% of hydrated kaolin or kaolin clay, 5-50 wt%, preferably 10-45 wt% of modified kaolin, 0-20 wt%, preferably 2-15 wt% of alumina, 0-30 wt%, preferably 5-28 wt%, preferably 10-25 wt% of kaolin, 0.5-15 wt%, preferably 1-12 wt%, preferably 2-10 wt% of zirconium oxide, and 0.1-15 wt%, preferably 1-10 wt%, preferably 2-8 wt% of titanium oxide.

[0041] Optionally, the zirconium oxide is derived from a zirconium sol containing a stabilizer, the zirconium sol containing the stabilizer containing ZrO2, a stabilizer, an alkaline cation, and water; the titanium sol contains TiO2, a hydrolysis inhibitor, an acidic substance, a dispersant, and water.

[0042] A fourth aspect of the present invention provides a method for preparing zirconium-titanium-containing reactive microspheres as provided in the third aspect of the present invention, comprising the following steps:

[0043] a. A slurry is formed by mixing water-containing kaolin or original kaolin, modified kaolin, optional kaolin, optional alumina, zircon sol containing stabilizer, titanium sol and water; the solid content of the slurry is 15-45% by weight, preferably 25-40% by weight.

[0044] b. Spray dry and optionally calcine the slurry obtained in step a. The calcine temperature is 300-1000℃, preferably 400-750℃, and the calcine time is 1-4h.

[0045] The fifth aspect of the present invention provides a Y-type molecular sieve catalytic material, which is obtained by crystallization of a mixture containing zirconium-titanium reactive microspheres provided in the third aspect of the present invention, a second silicon source, a second directing agent, sodium hydroxide and water;

[0046] Preferably, the weight ratio of the second silicon source, the second directing agent, sodium hydroxide, and water is (2-15):1:(1-7):(40-400), wherein the second silicon source is calculated as SiO2, the second directing agent is calculated as Al2O3, and the sodium hydroxide is calculated as Na2O.

[0047] The weight ratio of the second directing agent (calculated as Al2O3) to the reactive microspheres containing zirconium and titanium is (0.001-2):1.

[0048] The sixth aspect of the present invention provides a method for producing gasoline and liquefied petroleum gas by catalytic cracking, the method comprising: contacting a catalytic heavy feedstock oil with a catalytic cracking catalyst to carry out a catalytic cracking reaction, wherein the catalytic cracking catalyst contains the Y-type molecular sieve catalytic material provided in the first aspect of the present invention;

[0049] Preferably, the conditions for the catalytic cracking reaction include: a reaction temperature of 450-550°C, a catalyst-to-oil weight ratio of 5-7, and a weight hourly space velocity of 15-17 h⁻¹. -1 .

[0050] The present invention has the following advantages:

[0051] (1) The Y-type molecular sieve catalytic material of the present invention is obtained by hydrothermal crystallization of zirconium-titanium-containing reactive microspheres. The zirconium-titanium-containing reactive microspheres have a mesoporous and macroporous structure, which can form molecular sieve catalysts in situ on the mesoporous and macroporous structure.

[0052] (2) The present invention contains zirconium oxide and titanium oxide in the reactive microspheres containing zirconium and titanium. Through the co-catalytic effect of zirconium and titanium metal, the advantages of titanium oxide and zirconium oxide are fully utilized. The prepared catalyst has better strength and cracking effect, which improves the total yield of gasoline and liquefied petroleum gas (LPG) and the diesel yield is low.

[0053] (3) The method for producing gasoline and liquefied petroleum gas by catalytic cracking provided by the present invention can be used for heavy oil conversion, especially for conversion of low-density heavy oil. Under the conditions of conversion of low-density heavy oil, it can have significantly higher gasoline yield and liquefied petroleum gas yield.

[0054] Other features and advantages of the present invention will be described in detail in the following detailed description section. Detailed Implementation

[0055] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0056] The first aspect of this invention provides a Y-type molecular sieve catalytic material, which is obtained by hydrothermal crystallization of zirconium-titanium-containing reactive microspheres. Based on the dry weight of the zirconium-titanium-containing reactive microspheres, the zirconium-titanium-containing reactive microspheres contain 70-97.9% by weight of alumina matrix, 0.1-15% by weight of zirconium oxide and 2-15% by weight of titanium oxide, and the total content of zirconium oxide and titanium oxide is 2.1-18% by weight.

[0057] The Y-type molecular sieve catalytic material of the present invention is obtained by hydrothermal crystallization of zirconium-titanium-containing reactive microspheres. The molecular sieve can grow in situ on the reactive microspheres. The zirconium-titanium-containing reactive microspheres contain zirconium oxide and titanium oxide, which can serve as inert substances. During the crystallization process of the catalytic material, they provide a steric hindrance effect, reduce the competitive growth of molecular sieves in the channels, improve the retention of mesopores and macropores, and the zirconium-titanium metal oxides have a synergistic effect, promoting the catalytic cracking of heavy oil, increasing the yield of gasoline and liquefied petroleum gas, and reducing the yield of diesel and slurry oil.

[0058] In one specific embodiment of the present invention, the zirconium-titanium reactive microspheres contain 70-97.9% by weight, preferably 72-97% by weight, of an alumina matrix, 0.1-15% by weight, preferably 0.5-14% by weight, for example 1.5-9% by weight, of zirconium oxide, and 2-15% by weight, preferably 2.5-14% by weight, for example 2-7% by weight, of zirconium oxide and titanium oxide, and the total content of zirconium oxide and titanium oxide is 3-16% by weight, for example 6-14% by weight; the zirconium-titanium reactive microspheres have a sphericity of 85-100%, an abrasion index of 0.5-3% / h, and a particle size of 20-150 μm, preferably 90-100% sphericity and an abrasion index of 0.5-2.5% / h.

[0059] In one specific embodiment of the present invention, the Y-type molecular sieve catalytic material contains a Y-type molecular sieve and zirconium-titanium-containing reactive microspheres. Based on the dry weight of the Y-type molecular sieve catalytic material, the zirconium oxide content is 0.1-15% by weight, preferably 0.5-14% by weight, more preferably 1-12% by weight, and even more preferably 2-10% by weight, and the titanium oxide content is 2.5-14% by weight, and even more preferably 3-12% by weight.

[0060] In one specific embodiment of the present invention, the specific surface area of ​​the Y-type molecular sieve catalytic material is 200-700 m². 2 The total pore volume is 0.20-0.50 mL / g, the wear index is 0.1-2.5% / h, and the volume of medium-to-large pores with a pore size of 2-50 nm accounts for 20-50% of the total pore volume; preferably, the specific surface area is 450-600 m² / g. 2 / g, the total pore volume is 0.21-0.35mL / g, the wear index is 0.1-2% / h, and the volume of medium and large pores with a pore size of 2-50nm accounts for 25-48% of the total pore volume.

[0061] According to the present invention, the zirconium-titanium reactive microspheres are prepared by a method comprising the following steps: mixing alumina matrix raw material, zirconium sol, titanium sol and water to obtain a slurry, and spray drying the slurry to obtain the zirconium-titanium reactive microsphere precursor;

[0062] The zirconium-titanium-containing reactive microsphere precursor is spray-dried and then calcined to obtain the zirconium-titanium-containing reactive microspheres. The calcination conditions may include: a temperature of 300-1000℃ and a time of 1-10 hours; preferably, a temperature of 400-750℃ and a time of 1.5-8 hours.

[0063] In one specific embodiment of the present invention, the alumina matrix raw material contains hydrated kaolin and / or metamorphic kaolin, optionally hydrated alumina, and optionally kaolin. The hydrated kaolin is obtained by dispersing kaolin in water and removing associated sandy minerals; the metamorphic kaolin is obtained by calcining and dehydrating hydrated kaolin at 500-900℃; and the kaolin is obtained by calcining hydrated kaolin at 900-1050℃ through characteristic exothermic processes. The hydrated alumina may include, but is not limited to, one or more of boehmite, pseudo-boehmite, and gibbsite. More preferably, the hydrated alumina is calcined hydrated alumina or acidified hydrated alumina. The calcined hydrated alumina is obtained by calcining hydrated alumina at 400-700℃; the acidified hydrated alumina is obtained by acidifying the hydrated alumina under conditions with a pH value less than 3.5.

[0064] In one specific embodiment of the present invention, based on the total weight of the alumina matrix raw material, the alumina matrix raw material contains 10-95% by weight of the hydrated kaolin, 0-100% by weight, preferably 10-80% by weight, or 5-50% by weight of the variable kaolin, 0-20% by weight of the hydrated alumina, and 0-70% by weight, preferably 0-30% by weight of the kaolin.

[0065] More preferably, the alumina matrix raw material contains 15-80 wt% and 20-80 wt% of the hydrated kaolin, 10-45 wt% and 15-45 wt% of the modified kaolin, 5-15 wt% of hydrated alumina, and 5-25 wt% and 10-25 wt% of the kaolin. The hydrated kaolin serves as an inert component in the Y-type molecular sieve catalytic material, the modified kaolin provides soluble alumina for molecular sieve growth, and the kaolin is used to prepare an aluminum-rich matrix.

[0066] According to the present invention, the solid content of the slurry can vary within a wide range. In one specific embodiment of the present invention, the solid content of the slurry is 20-60% by weight.

[0067] According to the present invention, spray drying is well known to those skilled in the art, and will not be described in detail here. In one specific embodiment of the present invention, the average diameter of the zirconium-titanium reactive microspheres obtained by spray drying is 20-150 μm.

[0068] In one specific embodiment of the present invention, the titanium sol contains TiO2, hydrolysis inhibitor, acidic substance, dispersant and water.

[0069] According to the present invention, titanium sol can be prepared by a titanium dioxide precursor hydrolysis method. In one specific embodiment of the present invention, the titanium sol is prepared by a method comprising the following steps: (1) mixing a titanium source with a hydrolysis inhibitor to obtain a third mixed solution, wherein the concentration of the third mixed solution, calculated as TiO2, is 0.5-30% by weight; (2) mixing the third mixed solution, an acid, and a dispersant, and reacting the resulting mixture at 20-90°C for 0.5-3 hours to obtain titanium sol.

[0070] In one specific embodiment of the present invention, in step (2), the obtained third mixture is aged at 20-90°C for 0.5-3 hours to obtain zirconium sol.

[0071] According to the present invention, in step (2), a dispersant is added after the third mixed solution and the acid are mixed. In one specific embodiment of the present invention, in step (2), the pH value of the titanium sol is 0-7, preferably 0.5-5.

[0072] According to the present invention, the titanium source is selected from one or more of tetraethoxy titanium, tetraisopropoxy titanium, tetrabutoxy titanium alkoxy titanium, titanium tetrachloride, titanium sulfate and titanium oxysulfate; preferably tetrabutoxy titanium alkoxy titanium.

[0073] According to the present invention, the hydrolysis inhibitor is selected from one or more of water, lower alcohols having 1-5 carbon atoms, higher alcohols having 6 or more carbon atoms, hexanediol, ethanolamine, and acetylacetone; preferably one or more of ethanol, propanol, isopropanol, butanol, isobutanol, ethanolamine, and acetylacetone.

[0074] According to the present invention, the acid is selected from inorganic acids and / or organic acids; the inorganic acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; the organic acid is selected from one or more of glycolic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid and citric acid, preferably acetic acid or citric acid.

[0075] According to the present invention, the dispersant is a cationic surfactant and anionic surfactant, selected from one or more of polyethylene glycol, polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glycerol ester, fatty acid sorbitan, polysorbate, triethanolamine soap sucrose ester, polyol sucrose ester, sodium dodecyl sulfate, methyl ammonium bromide and hexadecyltrimethylammonium chloride.

[0076] In one specific embodiment of the present invention, the zirconium sol has a particle size of 5-15 nm, an average particle size of 8-12 nm, and a concentration of over 90%. The concentration refers to the proportion of particles with a size of approximately 10 nm in the measured zirconium sol sample, which can be obtained by obtaining a zirconium sol sample image using TEM and then analyzing the image using computer image analysis. The particle size refers to the diameter of the largest circumcircle in the particle projection image, and the average particle size is the arithmetic mean of the sample particle sizes.

[0077] The second aspect of the present invention provides a method for preparing the Y-type molecular sieve catalytic material provided in the first aspect of the present invention, the method comprising: mixing the zirconium-titanium-containing reactive microspheres, a first silicon source, a first directing agent, sodium hydroxide and water, and then subjecting the resulting mixture to hydrothermal crystallization treatment.

[0078] According to the present invention, the conditions for the hydrothermal crystallization treatment may include: a temperature of 88-105°C and a time of 10-78 hours; preferably, a temperature of 90-96°C and a time of 12-70 hours.

[0079] In one specific embodiment of the present invention, the method further includes: filtering, washing, and drying the product obtained by the hydrothermal crystallization treatment; preferably, the filtered solid product is washed until the pH value of the washing solution is less than 10. Drying can be carried out in a constant temperature drying oven, and the drying conditions may include: a temperature of 100-150°C and a time of 100-150°C.

[0080] According to the present invention, the weight ratio of the first silicon source, the first directing agent, sodium hydroxide, and water can vary within a wide range, for example, it can be (2-15):1:(1-7):(40-400), preferably (3-16):1:(1.5-6.5):(42-380), wherein the first silicon source is calculated as SiO2, the first directing agent is calculated as Al2O3, and the sodium hydroxide is calculated as Na2O. The weight ratio of the first directing agent (calculated as Al2O3) to the zirconium-titanium reactive microspheres can also vary within a wide range, for example, it can be (0.001-2):1, preferably (0.01-1.5):1, and more preferably (0.01-0.5):1. The first silicon source is selected from one or more of sodium silicate, silica gel, and organosilicon.

[0081] In one specific embodiment of the present invention, the directing agent can be synthesized according to conventional methods, such as those described in USP3574538, USP3639099, USP3671191, USP4166099, and EUP0435625. The molar composition of the directing agent is: (10-17)SiO2 : (0.7-1.3)Al2O3 : (11-18)Na2O : (200-350)H2O. During synthesis, the raw materials are aged at 4-35°C, preferably 4-20°C, to obtain the directing agent.

[0082] A third aspect of the present invention provides a zirconium-titanium-containing reactive microsphere suitable for hydrothermal crystallization preparation of Y-type molecular sieve catalytic materials. Based on the dry weight of the zirconium-titanium-containing reactive microsphere, the zirconium-titanium-containing reactive microsphere contains 0.1-15 wt% zirconium oxide, 2-15 wt% titanium oxide and 70-97.9 wt% alumina matrix.

[0083] In one specific embodiment of the present invention, the zirconium-titanium reactive microspheres contain 72-97% by weight of alumina matrix, 0.5-14% by weight of zirconium oxide and 2.5-14% by weight of titanium oxide; preferably, the zirconium-titanium reactive microspheres have a sphericity of 85-100%, an abrasion index of 0.5-3% / h and a particle size of 20-150 μm.

[0084] In one specific embodiment of the present invention, based on the dry weight of the zirconium-containing reactive microspheres, the zirconium-containing reactive microspheres contain, on a dry basis, 10-95 wt%, preferably 15-80 wt%, preferably 20-50 wt% of hydrated kaolin or kaolin clay, 5-50 wt%, preferably 10-45 wt% of metakaolin (also known as kaolinite), 0-20 wt%, preferably 2-15 wt% of alumina, 0-30 wt%, preferably 5-28 wt%, preferably 10-25 wt% of kaolin, 0.5-15 wt%, preferably 1-12 wt%, preferably 2-10 wt% of zirconium oxide, and 0.1-15 wt%, preferably 1-10 wt%, preferably 2-8 wt% of titanium oxide.

[0085] In one specific embodiment of the present invention, the zirconium sol comprises 0.5-20 wt%, for example 1-18 wt% or 5-15 wt% of ZrO2, a stabilizer, an alkaline cation, and water, wherein the molar ratio of the stabilizer to Zr is 1-6, and the zirconium sol has a pH value of 1-7.

[0086] In one specific embodiment of the present invention, the zirconium sol is dried at 100°C for 6 hours and then calcined at 600°C for 2-6 hours for heat treatment. The resulting product contains both monoclinic and tetragonal ZrO2 phases, with the preferred ratio of monoclinic to tetragonal phase being (0.05-0.6):1. In another specific embodiment of the present invention, the zirconium sol is dried at 100°C for 6 hours and then calcined at 800°C for 2-6 hours for heat treatment. The resulting product contains ZrO2 in the monoclinic phase.

[0087] In one specific embodiment of the present invention, the stabilizer is an organic acid. In one embodiment, the stabilizer is preferably at least one of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, citric acid, etc., and more preferably one or more of acetic acid, oxalic acid, or citric acid.

[0088] In one specific embodiment of the present invention, the alkaline cation is, for example, a nitrogen-containing cation, such as an ammonium ion or a nitrogen-containing cation formed by the hydrolysis of a water-soluble organic base. The water-soluble organic base is, for example, one or more of the following: methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0089] In one specific embodiment of the present invention, the molar ratio of the alkaline cation to Zr is preferably 1-8.

[0090] In a preferred embodiment of the present invention, the zirconium sol further contains inorganic acid radicals and / or alcohols, wherein the molar ratio of the inorganic acid radicals and / or alcohols to Zr is 1-6, for example, 1-4:1. The inorganic acid radicals include, for example, one or more of sulfate, chloride, and nitrate, and the alcohols include, for example, one or more of methanol, ethanol, propanol, and butanol.

[0091] In a preferred embodiment of the present invention, the pH value of the zirconium sol is preferably 1.5-5, more preferably 2-4, and even more preferably 2-3.

[0092] According to the present invention, zirconium sol can be prepared by hydrolyzing zirconium salt using at least one of the following methods: alkali addition, oxidation, and ion exchange. Preferably, the zirconium sol is prepared by alkali addition. In a preferred embodiment of the present invention, the zirconium sol is prepared by a method comprising the following steps: S1, mixing a zirconium source with a first solvent to obtain a first mixed solution, wherein the concentration of the first mixed solution, calculated as ZrO2, is 0.5-20% by weight, preferably 1-18% by weight or 5-15% by weight; S2, reacting the first mixed solution with a stabilizer at 20-90°C for 0.5-3 hours to obtain a second mixed solution, wherein the molar ratio of the first mixed solution to the stabilizer is 1:(1-6), and the first mixed solution is calculated as zirconium; S3, mixing the second mixed solution with an alkali source at 20-50°C to obtain the zirconium sol, wherein the pH value of the zirconium sol is 0-10, preferably 1-7.

[0093] In one specific embodiment of the present invention, in step S1, the mixing temperature can be 15-40°C, and the first solvent is deionized water.

[0094] In one specific embodiment of the present invention, in step S3, an alkali source is slowly added to the second mixed solution to obtain a clear and transparent zirconium sol. The slow addition can be, for example, dropwise, or by controlling a certain addition rate, such as 0.05-50 mL / min / L of the second mixed solution, for example, 0.1-30 mL of alkali solution / min / L of the second mixed solution, or 1-35 mL of alkali solution / min / L of the second mixed solution, or 0.05-10 mL / min / L of the second mixed solution, or 0.1-5 mL / min / L of the second mixed solution. In one embodiment, an alkali solution is slowly added to the second mixed solution using a pump, such as a peristaltic pump. Preferably, the amount of alkali solution added is such that the pH value of the zirconium sol is 1.5-5, for example, 2-4, more preferably 2-3.

[0095] In one specific embodiment of the present invention, the zirconium source is an inorganic zirconium salt and / or an organic zirconium salt, wherein the inorganic zirconium salt is one or more of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium nitrate, zirconium oxynitrate, zirconium oxysulfate, and zirconium oxycarbonate; and the organic zirconium salt is one or more of zirconium n-propoxide, zirconium isopropoxide, zirconium ethoxide, and zirconium butoxide.

[0096] In one specific embodiment of the present invention, the stabilizer is an organic acid that can form a coordination polymer with zirconium. The stabilizer is preferably one or more of glycolic acid, acetic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid, and more preferably one or more of acetic acid, oxalic acid, and citric acid.

[0097] In one specific embodiment of the present invention, the alkali source is selected from ammonia water or a water-soluble organic base, such as methylamine, dimethylamine, trimethylamine, methanolamine, diethanolamine, triethanolamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetraisopropylammonium hydroxide, tetrabutylammonium hydroxide, monomethyltriethylammonium hydroxide, monomethyltriethanolammonium hydroxide, and monomethyltributylammonium hydroxide.

[0098] The fourth aspect of this invention provides a method for preparing zirconium-titanium reactive microspheres as provided in the third aspect of this invention, comprising the following steps: a) mixing hydrated kaolin or kaolin clay, modified kaolin, optionally kaolin, optionally alumina, zirconium sol containing a stabilizer, titanium sol and water to form a slurry; the solid content of the slurry is 15-45% by weight, preferably 25-40% by weight; b) spray drying and optionally calcining the slurry obtained in step a, wherein the calcination temperature is 300-1000℃, preferably 400-750℃, and the calcination time is 1-4 hours.

[0099] In this invention, alumina may include, but is not limited to, one or more of hydrated alumina, γ-alumina, η-alumina and κ-alumina.

[0100] The fifth aspect of this invention provides a method for preparing a Y-type molecular sieve catalytic material, which is obtained by crystallization of a mixture containing zirconium-titanium-containing reactive microspheres provided in the third aspect of this invention, a second silicon source, a second directing agent, sodium hydroxide, and water; wherein the weight ratio of the second silicon source, the second directing agent, sodium hydroxide, and water is (2-15):1:(1-7):(40-400), wherein the second silicon source is calculated as SiO2, the second directing agent is calculated as Al2O3, and the sodium hydroxide is calculated as Na2O; the weight ratio of the second directing agent (calculated as Al2O3) to the zirconium-titanium-containing reactive microspheres is (0.001-2):1.

[0101] A sixth aspect of the present invention provides a method for producing gasoline and liquefied petroleum gas by catalytic cracking, the method comprising: contacting a heavy feedstock oil with a catalytic cracking catalyst to carry out a catalytic cracking reaction, wherein the catalytic cracking catalyst contains the Y-type molecular sieve catalytic material provided in the first aspect of the present invention; preferably, the conditions for the catalytic cracking reaction include: a reaction temperature of 450-550°C, a feedstock-to-oil weight ratio of 5-7, and a weight hourly space velocity of 15-17 h⁻¹. -1 .

[0102] A seventh aspect of the present invention provides a catalyst comprising the Y-type molecular sieve catalytic material and a modifying component provided in the first aspect of the present invention. In one specific embodiment of the present invention, the modifying metal is selected from one or more of lanthanum, cerium, praseodymium, neodymium, and phosphorus.

[0103] The present invention will be further illustrated by the following examples, but the present invention is not limited thereto.

[0104] The molecular sieve content in the molecular sieve catalytic materials of the examples and comparative examples was determined according to the RIPP 146-90 standard method (the RIPP standard method can be found in "Analytical Methods for Petrochemical Products (RIPP Test Methods)", edited by Yang Cuiding et al., Science Press, published in 1990, the same below), and was obtained from the relative crystallinity.

[0105] The contents of zirconium oxide, titanium oxide and alumina matrix in the zirconium-titanium reactive microspheres were determined by XRF method.

[0106] In this invention, sphericity is represented by the sphericity index SPHT, which is the ratio of the surface area of ​​a sphere of the same volume as the object to the surface area of ​​the object itself. The formula for calculating sphericity is as follows: Sphericity index SPHT = 4πA 2 / P 2 Where A is the projected area of ​​the particle and P is the projected perimeter of the particle. The sphericity of the catalytic cracking catalyst was tested using a CamsizerXT dynamic digital imaging particle analyzer from Leych GmbH, Germany, according to the ASTM D4464 method.

[0107] The wear index of both molecular sieve catalytic materials and zirconium-containing reactive microspheres was determined using the method NB / SH / T0943-2017.

[0108] The specific surface area of ​​the molecular sieve catalytic material was determined by nitrogen adsorption method (GB / T5816-1995). The total pore volume (Vtotal pores) and the pore volume of pores with a diameter of 2-50 nm (Vpores with a diameter of 2-50 nm) were determined by nitrogen adsorption method (RIPP151-90). The mesoporous ratio was calculated by the following formula: mesoporous ratio = (Vtotal pores - Vpores with a diameter of 2-50 nm) / Vtotal pores × 100%.

[0109] In the examples and comparative examples, the directing agent was prepared as follows: 250 kg of sodium silicate solution (containing 20.05 wt% SiO2 and 6.41 wt% Na2O) was taken and slowly added to 120 kg of sodium aluminate solution (containing 3.15 wt% Al2O3 and 21.1 wt% Na2O) at 30°C with rapid stirring. The mixture was stirred for 1 hour and aged at 20°C for 48 hours to obtain the directing agent.

[0110] Example 1 of the preparation of zirconium sol

[0111] S1. Add 130g of deionized water to a beaker, then add 125g of zirconium oxychloride, and stir at 20℃ for 10min to obtain the first mixed solution.

[0112] S2. Slowly add 93g of acetic acid to the first mixed solution, stir at 50℃ and react for 30min to obtain the second mixed solution;

[0113] S3. At 25°C, concentrated ammonia was slowly added to the second mixed solution using a pump over a period of 30 minutes, while controlling the pH value to 2.5, to obtain a clear and transparent zirconium sol A1.

[0114] Example 2 of the preparation of zirconium sol

[0115] Zirconium sol A2 was prepared using the same method as in Example 1 of zirconium sol preparation, except that in step S2, 70 g of oxalic acid was slowly added to the first mixed solution.

[0116] Example 3 of the preparation of zirconium sol

[0117] Zirconium sol A3 was prepared using the same method as in Example 1 of zirconium sol preparation, except that in step S1, 170g of deionized water was added to a beaker, followed by 176g of zirconium isopropoxide; in step S2, 70g of oxalic acid was slowly added to the first mixed solution; and in step S3, triethanolamine was slowly added to the second mixed solution using a pump.

[0118] Table 1

[0119] Zirconium sol preparation example number Example 1 Example 2 Example 3 Zirconium sol number A1 A2 A3 <![CDATA[ZrO2, wt%]]> 10.8 11.9 11.3 pH value 2.5 2.5 2.5 Molar ratio of basic cations to Zr 2 1.67 1.74 stabilizer to Zr molar ratio 4 4 4 Average particle size, nm 10 9.8 9.7 Particle size range, nm 8-10 8-10 8-10 Concentration, % 95 93 92 The ratio of monoclinic phases to tetragonal phases* 0.4:1 0.35:1 0.3:1

[0120] * The sample was dried at 100℃ for 6 hours and then calcined at 600℃ for 4 hours.

[0121] Example 4 of titanium sol preparation

[0122] Add 50g of titanium tetrachloride aqueous solution (Ti concentration 18% by weight) to a beaker, slowly add 38g of oxalic acid, stir for 30min to obtain a mixed solution; then slowly add triethanolamine to the above solution using a pump over 30min, controlling the pH to 4, to obtain a clear and transparent titanium sol C1.

[0123] Preparation Examples of Zirconium-Titanium Reactive Microspheres 1-3, 6

[0124] Hydrous kaolin is calcined in a muffle furnace at 1000℃ for 3 hours, resulting in characteristic exothermic reactions, to obtain kaolin. Hydrous kaolin is calcined in a muffle furnace at 870℃ for 1 hour to obtain modified kaolin. False monohydrate diaspore is calcined in a muffle furnace at 600℃ for 2 hours to obtain γ-Al2O3, i.e., calcined hydrated alumina.

[0125] According to the dosage ratio shown in Table 2, hydrated kaolin, modified kaolin, kaolin, calcined hydrated alumina, zircon sol, titanium sol and water are mixed and slurried. The resulting slurry with a solid content of 40% by weight is spray-dried to obtain zirconium-titanium reactive microspheres ZQ-1 to ZQ-3 and ZQ-6 with a particle size of 20-150 μm.

[0126] The data in Table 2 for the amount of raw materials represent the weight ratio of the amounts of hydrated kaolin, modified kaolin, kaolin, calcined (acidified) hydrated alumina, and zirconium sol.

[0127] Preparation of zirconium-titanium reactive microspheres: Examples 4-5

[0128] Hydrous kaolin is calcined in a muffle furnace at 1000℃ for 3 hours, resulting in characteristic exothermic reactions to obtain kaolin. Hydrous kaolin is then calcined in a muffle furnace at 870℃ for 1 hour to obtain modified kaolin. Pseudo-monohydrate diatomite is acidified with hydrochloric acid to form a sol with a pH of 1-3, i.e., acidified hydrated alumina.

[0129] According to the dosage ratio shown in Table 2, hydrated kaolin, modified kaolin, kaolin, acidified hydrated alumina, zirconium sol, titanium sol and water were mixed and slurried. The resulting slurry with a solid content of 40% by weight was spray-dried to obtain a zirconium-titanium reactive microsphere precursor. The zirconium-titanium reactive microsphere precursor was calcined at 800℃ for 3 hours to obtain zirconium-titanium reactive microspheres ZQ-4 and ZQ-5 with a particle size of 20-150μm. The composition of the prepared zirconium-titanium reactive microspheres is shown in Table 3, and the same applies below.

[0130] Preparation of Zirconium-Titanium Reactive Microspheres Example 7

[0131] The same method as in Example 1 for preparing zirconium-containing reactive microspheres was used, except that zirconium oxychloride was used instead of zirconium sol to prepare the slurry, and titanium tetrachloride was used instead of titanium sol.

[0132] Preparation of reactive microspheres without zirconium and titanium: Comparative Example 1

[0133] Hydrous kaolin is calcined in a muffle furnace at 1000℃ for 3 hours, resulting in characteristic exothermic reactions, to obtain kaolin. Hydrous kaolin is calcined in a muffle furnace at 870℃ for 1 hour to obtain modified kaolin. False monohydrate diaspore is calcined in a muffle furnace at 600℃ for 2 hours to obtain γ-Al2O3, i.e., calcined hydrated alumina.

[0134] According to the dosage ratio shown in Table 2, hydrated kaolin, modified kaolin, kaolin, calcined hydrated alumina and water are mixed and slurried. The resulting slurry with a solid content of 40% by weight is spray-dried to obtain a reactive microsphere precursor. The reactive microsphere precursor is calcined at 800℃ for 3 hours to obtain reactive microspheres DB-1 with a particle size of 20-150μm.

[0135] Preparation of Zirconium-Containing Reactive Microspheres (Comparative Example 2)

[0136] According to the dosage ratio shown in Table 2, hydrated kaolin, modified kaolin, kaolin, acidified hydrated alumina, zircon sol and water are mixed and slurried. The resulting slurry with a solid content of 40% by weight is spray-dried to obtain a zirconium-containing reactive microsphere precursor. The zirconium-containing reactive microsphere precursor is calcined at 800℃ for 3 hours to obtain zirconium-containing reactive microspheres DB-2 with a particle size of 20-150μm.

[0137] Preparation of titanium-containing reactive microspheres (Comparative Example 3)

[0138] According to the dosage ratio shown in Table 2, hydrated kaolin, modified kaolin, kaolin, acidified hydrated alumina, titanium sol and water are mixed and slurried. The resulting slurry with a solid content of 40% by weight is spray-dried to obtain a titanium-containing reactive microsphere precursor. The titanium-containing reactive microsphere precursor is calcined at 800℃ for 3 hours to obtain titanium-containing reactive microspheres DB-3 with a particle size of 20-150μm.

[0139] Table 2

[0140]

[0141]

[0142] Table 3

[0143]

[0144]

[0145] Example 1 of the preparation of molecular sieve catalytic materials

[0146] One kilogram of zirconium-titanium reactive microspheres ZQ-1 were mixed with 6 kilograms of sodium silicate solution (containing 20.05 wt% SiO2 and 6.41 wt% Na2O), 1.5 kilograms of directing agent, and 2 kilograms of 15 wt% sodium hydroxide solution under stirring. The mixture was then subjected to hydrothermal crystallization at 94°C and 400 rpm for 24 hours. After hydrothermal crystallization, the crystallization tank was rapidly cooled and filtered. The filtered solid product was washed with deionized water until the pH of the washing solution was less than 10, yielding the Y-type molecular sieve catalyst ZTMY-1. The parameter characteristics are shown in Table 4.

[0147] Example 2 of preparing molecular sieve catalytic materials

[0148] The Y-type molecular sieve catalytic material ZTMY-2 was prepared using the same method as in Example 1, except that zirconium-titanium-containing reactive microspheres ZQ-2 were used instead of ZQ-1.

[0149] Example 3 of the preparation of molecular sieve catalytic materials

[0150] Y-type molecular sieve catalytic material ZTMY-3 was prepared using the same method as in Example 1, except that 7 kg of sodium silicate was added and zirconium-titanium-containing reactive microspheres ZTMY-3 were used instead of ZQ-1.

[0151] Example 4 of the preparation of molecular sieve catalytic materials

[0152] The Y-type molecular sieve catalytic material ZTMY-4 was prepared using the same method as in Example 1, except that 7 kg of sodium silicate was added and zirconium-titanium reactive microspheres ZQ-4 were used instead of ZQ-1.

[0153] Example 5 of the preparation of molecular sieve catalytic materials

[0154] The Y-type molecular sieve catalytic material ZTMY-5 was prepared using the same method as in Example 1, except that 7 kg of sodium silicate was added and zirconium-titanium reactive microspheres ZQ-5 were used instead of ZQ-1.

[0155] Example 6 of the preparation of molecular sieve catalytic materials

[0156] The Y-type molecular sieve catalytic material ZTMY-6 was prepared using the same method as in Example 1, except that zirconium-titanium reactive microspheres ZQ-6 were used instead of ZQ-1.

[0157] Example 7 of the preparation of molecular sieve catalytic materials

[0158] The Y-type molecular sieve catalytic material ZTMY-7 was prepared using the same method as in Example 1, except that zirconium-titanium reactive microspheres ZQ-7 were used instead of ZQ-1.

[0159] Comparative Example 1 for the preparation of molecular sieve catalytic materials

[0160] The molecular sieve catalytic material DY-1 was prepared using the same method as in Example 1, except that reactive microspheres DB-1 were used instead of ZQ-1.

[0161] Comparative Example 2 for the Preparation of Molecular Sieve Catalytic Materials

[0162] Add DY-1 to deionized water and adjust the concentration to 50% by weight. Add 5% by weight of zirconium sol A1 and 2% by weight of titanium sol C1 (based on the weight of DY-1) and impregnate for 6 hours. Dry at 120 degrees Celsius to obtain molecular sieve catalyst material DY-2.

[0163] Comparative Example 3 for the Preparation of Molecular Sieves Catalysts

[0164] The molecular sieve catalytic material DY-3 was prepared using the same method as in Example 1, except that reactive microspheres DB-2 were used instead of ZQ-1.

[0165] Comparative Example 4 for the Preparation of Molecular Sieves Catalytic Materials

[0166] The molecular sieve catalytic material DY-4 was prepared using the same method as in Example 1, except that reactive microspheres DB-3 were used instead of ZQ-1.

[0167] Table 4

[0168]

[0169] Example 1 of catalyst preparation

[0170] Molecular sieve catalyst ZTMY-1 was added to deionized water and slurried to form a slurry with a solid content of 10% by weight. Lanthanum chloride was added to water and slurried to form a lanthanum chloride solution with a La2O3 concentration of 5% by weight. The lanthanum chloride solution was added to the slurry, with a weight ratio of lanthanum chloride (based on La2O3) to molecular sieve (based on dry basis) of 1:19. The mixture was stirred at 70°C for 1 hour, filtered, washed, dried at 150°C for 8 hours, and calcined at 500°C for 4 hours. The mixture was then washed with ammonium sulfate solution, with a weight ratio of ammonium sulfate to molecular sieve catalyst dry basis of 1:20. The mixture was stirred at 70°C for 1 hour, filtered, washed, dried at 150°C for 8 hours, and calcined at 500°C for 2 hours. The resulting catalyst was designated REGY-1.

[0171] Examples 2-7 of catalyst preparation

[0172] The catalyst was prepared using the same method as in Example 1, except that the Y-type molecular sieve catalytic materials prepared in Examples 2-7 were used to prepare the catalyst.

[0173] Comparative Examples 1-4 for Catalyst Preparation

[0174] The catalyst was prepared using the same method as in Example 1, except that the molecular sieve catalytic materials prepared in Comparative Examples 1-4 were used to prepare the catalyst.

[0175] Test case

[0176] The catalysts prepared in the examples and comparative examples were treated in an aging unit at 800°C / 100% steam for 17 hours and evaluated on a fixed fluidized bed microreactor (ACE). The feedstock was heavy feedstock from catalytic cracking (composition and properties are shown in Table 5). The evaluation conditions were: reaction temperature 500°C, catalyst-to-oil ratio (by weight) 6, and WHSV 16 h. -1 The results are listed in Table 6.

[0177] The conversion rate is calculated as follows: gasoline yield + liquefied petroleum gas yield + dry gas yield + coke yield.

[0178] The sum of the yields of gasoline and LPG = gasoline yield + LPG yield, where LPG refers to liquefied petroleum gas.

[0179] Table 5

[0180]

[0181]

[0182] Table 6

[0183]

[0184]

[0185] As shown in Table 6, under the same modification conditions, the catalyst prepared using the Y-type molecular sieve catalytic material of the present invention has a better cracking effect in the catalytic cracking of heavy oil, with a higher conversion rate and a higher sum of gasoline and LPG yields, while the diesel yield and slurry yield are lower.

[0186] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0187] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0188] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A Y-type molecular sieve catalytic material, wherein the Y-type molecular sieve catalytic material is obtained by hydrothermal crystallization of zirconium-titanium-containing reactive microspheres, and based on the dry weight of the zirconium-titanium-containing reactive microspheres, the zirconium-titanium-containing reactive microspheres contain 70-97.9% by weight of alumina matrix, 0.1-15% by weight of zirconium oxide and 2-15% by weight of titanium oxide, and the total content of zirconium oxide and titanium oxide is 2.1-18% by weight; The zirconium-titanium reactive microspheres have a sphericity of 85-100%, an abrasion index of 0.5-3% / h, and a particle size of 20-150 μm. The specific surface area of ​​the Y-type molecular sieve catalytic material is 450-600 m². 2 / g, total pore volume is 0.21-0.35mL / g, abrasion index is 0.1-2.0% / h, and medium and large pores with a pore size of 2-50nm account for 25-48% of the total pore volume; The zirconium-titanium reactive microspheres were prepared using a method comprising the following steps: A slurry is prepared by mixing alumina matrix raw material, zirconium sol, titanium sol and water, and the slurry is spray-dried to obtain the zirconium-titanium reactive microsphere precursor. The zirconium-titanium-containing reactive microsphere precursor is further calcined to obtain the zirconium-titanium-containing reactive microspheres; the calcination conditions include: The temperature is 300-1000℃, and the time is 1-10 hours.

2. The Y-type molecular sieve catalytic material according to claim 1, wherein, The zirconium-titanium reactive microspheres contain 72-97% by weight of alumina matrix, 0.5-14% by weight of zirconium oxide and 2.5-14% by weight of titanium oxide, with a total content of 3-16% by weight of zirconium oxide and titanium oxide.

3. The Y-type molecular sieve catalytic material according to claim 1, wherein, Based on the dry weight of the Y-type molecular sieve catalytic material, the content of zirconium oxide is 1-12% by weight and the content of titanium oxide is 3-12% by weight.

4. The Y-type molecular sieve catalytic material according to claim 1, wherein, The titanium sol was prepared using a method comprising the following steps: (1) The titanium source and the hydrolysis inhibitor are mixed to obtain a third mixed solution, wherein the concentration of the third mixed solution, calculated as TiO2, is 0.5-30% by weight%. (2) Mix the third mixed solution, acid and dispersant, and react the resulting mixture at 20-90°C for 0.5-3 hours to obtain titanium sol.

5. The Y-type molecular sieve catalytic material according to claim 4, wherein, The pH value of the titanium sol is 0-7.

6. The Y-type molecular sieve catalytic material according to claim 4, wherein, The pH value of the titanium sol is 0.5-5.

7. The Y-type molecular sieve catalytic material according to claim 1, wherein, The zirconium sol has a particle size of 5-15 nm, an average particle size of 8-12 nm, a concentration of over 90%, and a ZrO2 content of 0.5-20% by weight.

8. The Y-type molecular sieve catalytic material according to claim 1, wherein, The alumina matrix raw material contains hydrated kaolin and / or modified kaolin, hydrated alumina, and kaolin. Based on the total weight of the alumina matrix raw material, the alumina matrix raw material contains 0-100% by weight of the hydrated kaolin, 0-100% by weight of the modified kaolin, 0-20% by weight of the hydrated alumina and 0-70% by weight of the kaolin.

9. The Y-type molecular sieve catalytic material according to claim 8, wherein, The hydrated alumina is selected from one or more of boehmite, pseudo-monohydrate diaspore, and trihydrate gibbsite.

10. The Y-type molecular sieve catalytic material according to claim 8, wherein, The hydrated alumina is calcined hydrated alumina or acidified hydrated alumina.

11. The Y-type molecular sieve catalytic material according to claim 8, wherein, Based on the total weight of the alumina matrix raw material, the alumina matrix raw material contains 20-80% by weight of the hydrated kaolin, 10-80% by weight of the modified kaolin, 0-20% by weight of the hydrated alumina and 0-30% by weight of the kaolin.

12. The Y-type molecular sieve catalytic material according to claim 4, wherein, The titanium source is selected from one or more of tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium alkoxytitanium, titanium tetrachloride, titanium sulfate and titanium oxysulfate. The hydrolysis inhibitor is selected from one or more of water, lower alcohols with 1-5 carbon atoms, higher alcohols with 6 or more carbon atoms, hexanediol, ethanolamine, and acetylacetone. The acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, glycolic acid, oxalic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid. The dispersant is selected from one or more of polyethylene glycol, polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glycerol ester, fatty acid sorbitan, polysorbate, triethanolamine soap sucrose ester, polyol sucrose ester, sodium dodecyl sulfate, methyl ammonium bromide and hexadecyltrimethylammonium chloride.

13. The Y-type molecular sieve catalytic material according to claim 12, wherein, The hydrolysis inhibitor is one or more of ethanol, propanol, isopropanol, butanol, isobutanol, ethanolamine, and acetylacetone; The acid is acetic acid or citric acid.

14. A method for preparing the Y-type molecular sieve catalytic material according to any one of claims 1-13, the method comprising: The zirconium-titanium reactive microspheres, the first silicon source, the first directing agent, sodium hydroxide and water are mixed, and the resulting mixture is subjected to hydrothermal crystallization treatment. Based on the dry weight of the zirconium-titanium reactive microspheres, the zirconium-titanium reactive microspheres contain 0.1-15% by weight of zirconium oxide, 2-15% by weight of titanium oxide and 70-97.9% by weight of alumina matrix; The zirconium-titanium reactive microspheres were prepared by a method comprising the following steps: a. A slurry is formed by mixing hydrated kaolin or original kaolin, modified kaolin, kaolin, alumina, zirconium sol containing stabilizers, titanium sol, and water; the solid content of the slurry is 15-45% by weight. b. Spray dry the slurry obtained in step a and optionally calcine it, wherein the calcine temperature is 300-1000℃ and the calcine time is 1-4h.

15. The method according to claim 14, wherein, The solid content of the slurry is 25-40% by weight; the calcination temperature is 400-750℃, and the calcination time is 1-4 hours.

16. The method of claim 14, wherein, The conditions for the hydrothermal crystallization treatment include: a temperature of 88-105℃ and a time of 10-78 hours; The weight ratio of the first silicon source, the first directing agent, sodium hydroxide and water is (2-15):1:(1-7):(40-400), wherein the first silicon source is calculated as SiO2, the first directing agent is calculated as Al2O3, and the sodium hydroxide is calculated as Na2O. The weight ratio of the first directing agent (calculated as Al2O3) to the reactive microspheres containing zirconium and titanium is (0.001-2):1; The first silicon source is selected from one or more of sodium silicate, silica gel, and organosilicon.

17. The method according to claim 16, wherein, The weight ratio of the first directing agent (calculated as Al2O3) to the reactive microspheres containing zirconium and titanium is (0.01-0.5):

1.

18. The method according to claim 14, wherein, The zirconium-titanium reactive microspheres contain 72-97% by weight of alumina matrix, 0.5-14% by weight of zirconium oxide and 2.5-14% by weight of titanium oxide; The zirconium-titanium reactive microspheres have a sphericity of 85-100%, a wear index of 0.5-3% / h, and a particle size of 20-150 μm.

19. The method of claim 14, wherein, The zirconium oxide is derived from a zirconium sol containing a stabilizer, the zirconium sol containing the stabilizer containing ZrO2, a stabilizer, an alkaline cation, and water; the titanium sol contains TiO2, a hydrolysis inhibitor, an acidic substance, a dispersant, and water.

20. A Y-type molecular sieve catalytic material, which is prepared by any one of the methods of claims 14-19.

21. A method for producing gasoline and liquefied petroleum gas by catalytic cracking, the method comprising: The heavy feedstock oil is brought into contact with a catalytic cracking catalyst to carry out a catalytic cracking reaction, wherein the catalytic cracking catalyst contains the Y-type molecular sieve catalytic material as described in any one of claims 1-13.

22. The method according to claim 21, wherein, The conditions for the catalytic cracking reaction include: a reaction temperature of 450-550℃, a catalyst-to-oil weight ratio of 5-7, and a weight hourly space velocity of 15-17 h⁻¹. -1 .

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