Titanium sol and y-type molecular sieve catalytic material for increasing total liquid yield of fcc and preparation method thereof

Abstract

The present application relates to a kind of titanium sol, the Y type molecular sieve catalytic material for improving FCC total liquid recovery and its preparation method, the Y type molecular sieve catalytic material is obtained by the hydrothermal crystallization of titanium-containing reactive microspheres, with the dry base weight of titanium-containing reactive microspheres as benchmark, the titanium-containing reactive microspheres contain 85-98 wt.% alumina matrix and 2-15 wt.% titanium dioxide, and the titanium dioxide includes sharp titanium type titanium dioxide.The Y type molecular sieve catalytic material of the present application has better strength and cracking effect, and the catalyst containing the Y type molecular sieve catalytic material of the present application can improve the conversion rate and total liquid recovery of raw oil catalytic cracking.

Description

TECHNICAL FIELD

[0001] The present application relates to a titanium sol and a Y-type molecular sieve catalytic material for improving total liquid yield of FCC and a preparation method thereof and a titanium sol suitable for preparing the catalytic material. BACKGROUND

[0002] With the world's crude oil becoming heavier and poorer, heavy oil and residual oil have become the main processing raw materials used in catalytic cracking processes. Because heavy oil contains more gum, asphaltene and heavy metals, it requires that the FCC catalyst has high matrix activity, strong resistance to metal pollution, good catalytic activity and selectivity, among which the FCC catalyst containing Y-type zeolite is the largest amount of catalyst used at present.

[0003] Currently, there are two forms of Y-type molecular sieve cracking catalysts produced in the industry, the first of which is a semi-synthetic binder type, that is, the Y-type molecular sieve is modified by exchange and mixed with kaolin and a binder to be sprayed and formed. The second is an in-situ crystallization type, that is, the kaolin microspheres are calcined at high temperature and then hydrothermally crystallized in an alkaline system, so that Y-type molecular sieves grow on the inner and outer surfaces of the microspheres, and then the finished catalyst is obtained by modification. The in-situ crystallization type has the following characteristics compared with the semi-synthetic binder type catalyst: (1) Y-type molecular sieves and matrix are generated simultaneously by in-situ crystallization and are connected by chemical bonds, which have high thermal and hydrothermal stability; (2) Y-type molecular sieves are uniformly distributed on the inner and outer surfaces of the matrix, and the crystal size is about ten times smaller than that of NaY synthesized by gel method, which greatly improves the accessibility and cracking performance of heavy oil; (3) the kaolin microspheres calcined at high temperature contain aluminum-rich spinel structure, which has excellent resistance to vanadium and nickel pollution and mechanical grinding ability. Thus, the in-situ crystallization type cracking catalyst has advantages for processing heavy oil. Among them, the precursor of the in-situ crystallization type catalyst, kaolin microspheres, is the key to the preparation technology.

[0004] A series of patents on in-situ crystallization of cracking catalysts have been applied by Engelhard Corporation since 1960s. The main technical features of kaolin microspheres are disclosed in US3503990, US3506494, US3663165, US4493902, US4965233, US5023220, etc. The precursor microspheres contain a mixture of two different forms of chemically active calcined clay, metakaolin (calcined to undergo a strong endothermic reaction associated with dehydroxylation) and kaolin calcined under more severe conditions than those normally used to convert kaolin to metakaolin, i.e. calcined to undergo a characteristic exothermic reaction of kaolin, sometimes referred to as spinel-type calcined kaolin. However, the technology proposed in US4493902 requires high quality raw materials for spray forming, which requires the use of ultra-fine kaolin Satone-N02 and ultra-fine raw kaolin ASP-600. The price of such ultra-fine kaolin is high and it is not easy to buy in the market. In addition, the method consumes high energy, especially to obtain spinel-type kaolin, which requires calcination at a temperature as high as about 1100°C, greatly increasing the cost of the catalyst.

[0005] The LB-1 and LB-2 in-situ crystallization cracking catalysts have been developed by Lanzhou Petrochemical Company. CN1232862 discloses the main technical features of the precursor microspheres, i.e. a part of the parent particles is calcined at high temperature to obtain high-temperature calcined microspheres, and another part is calcined at a lower temperature to obtain metakaolin microspheres. The two kinds of microspheres are mixed in a certain proportion as the in-situ crystallization precursor microspheres. However, the crystallinity of the Y-type molecular sieve prepared by the method is low, generally less than 30%, and the silicon-aluminum ratio is generally less than 5.0.

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

[0007] US6942783 points out a method for preparing an FCC catalyst for improving the conversion of heavy oil by in-situ crystallization technology, in which the precursor microspheres are composed of metakaolin and hydrous kaolin. The microspheres containing metakaolin and hydrous kaolin are calcined at a lower temperature before crystallization to avoid the transformation of hydrous kaolin into metakaolin.

[0008] US20170362513A1 describes a method for in-situ preparation of an improved fluid catalytic cracking zeolite catalyst, the microspheres in the method are composed of a mixture of spinel kaolin, transition alumina and metakaolin.

[0009] From the analysis of the above patent technology, the technical core of in-situ crystallization catalyst preparation is to first prepare a solid material mainly composed of kaolin and its derivatives, and then generate zeolite "in-situ" on the solid material through liquid-solid reaction under certain synthesis conditions, and then obtain the required catalyst through post-processing. However, the composition and preparation process of the precursor kaolin microspheres have not been greatly improved, and the two-stage calcination method of the early Engelhard Company is basically continued, and the problems of high energy consumption and high cost have not been solved.

[0010] There are patents for adding auxiliary components to the preparation of microsphere precursors to prepare microsphere precursors with multiple potential functions. CN 105813739 A provides a FCC catalyst composition, which uses one or more boron oxide components to passivate metals, especially nickel. The influence of harmful metals (such as nickel) on cracking reactions is reduced or prevented by passivation through boron components. Non-zeolite components are added to the preparation of the precursor: the non-zeolite material is selected from kaolinite, halloysite, montmorillonite, bentonite, sepiolite, kaolin, amorphous kaolin, metakaolin, mullite, spinel, hydrous kaolin, clay, gibbsite (lanhydrous alumina), boehmite, iron oxide, alumina, silica, silica alumina, silica oxide and sepiolite. SUMMARY

[0011] The purpose of the present application is to provide a titanium sol and a Y-type molecular sieve catalytic material for improving the total liquid yield of FCC, and a preparation method thereof. The Y-type molecular sieve catalytic material of the present application has better strength and cracking effect. When the Y-type molecular sieve catalytic material of the present application is used in the catalytic cracking process of raw oil, the conversion rate and total liquid yield of the raw material can be improved.

[0012] In order to achieve the above-mentioned purpose, the first aspect of the present application provides a titanium sol, which comprises TiO2 colloidal particles, a hydrolysis inhibitor, an acidic substance, a dispersing agent and a solvent, and the titanium sol contains anatase titanium dioxide after being dried and calcined at 300-1000℃ for 1-10 hours.

[0013] Optionally, the content of TiO2 colloidal particles in the titanium sol is 5-25% by weight, the content of the dispersing agent is 0.1-5% by weight, the content of the hydrolysis inhibitor is 0.2-10% by weight, and the pH value of the titanium sol is 2.5-4.2.

[0014] The second aspect of the present application provides a Y-type molecular sieve catalytic material for improving total liquid yield of FCC, which is obtained by hydrothermally crystallizing a titanium-containing reactive microsphere, and the titanium-containing reactive microsphere contains 85-98 wt% of an alumina matrix and 2-15 wt% of titanium dioxide, based on the dry base weight of the titanium-containing reactive microsphere, and the titanium dioxide contains anatase titanium dioxide.

[0015] The titanium-containing reactive microsphere contains 86-97 wt% of an alumina matrix and 3-14 wt% of titanium dioxide.

[0016] The titanium-containing reactive microsphere has a sphericity of 85-100% and a particle size of 20-150 μm.

[0017] Optionally, the content of the titanium dioxide is 1.5-14 wt%, based on the dry base weight of the Y-type molecular sieve catalytic material.

[0018] Optionally, the Y-type molecular sieve catalytic material has a specific surface area of 200-700 m 2 / g, a total pore volume of 0.20-0.5 mL / g, an attrition index of 0.1-3% per hour, and a volume of mesopores and macropores with a pore size of 2-50 nm accounts for 20-50% of the total pore volume.

[0019] Preferably, the specific surface area is 500-600 m 2 / g, the total pore volume is 0.22-0.35 mL / g, the attrition index is 0.1-2.5% per hour, and the volume of mesopores and macropores with a pore size of 2-50 nm accounts for 23-50% of the total pore volume.

[0020] Optionally, the titanium-containing reactive microsphere is prepared by a method comprising the following steps:

[0021] The alumina matrix raw material, titanium sol and water are mixed to obtain a slurry, and the slurry is spray dried to obtain the titanium-containing reactive microsphere precursor.

[0022] The titanium-containing microsphere precursor is further subjected to a calcination treatment to obtain the titanium-containing reactive microsphere, and the calcination treatment has a temperature of 300-1000 °C and a time of 1-10 hours.

[0023] Optionally, the titanium sol is prepared by a method comprising the following steps:

[0024] S1, mixing a titanium source and a hydrolysis inhibitor to obtain a mixed solution, and the concentration of the mixed solution is 0.5-30 wt% based on TiO2;

[0025] S2, mixing the mixed solution, the acid and the dispersing agent, and reacting the mixture obtained at 20-90°C for 0.5-3 hours to obtain a titanium sol.

[0026] Optionally, in step S2, the pH value of the titanium sol is 0-7, preferably 0.5-5.

[0027] Optionally, the titanium source is selected from one or more of titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium tetrachloride, titanium sulfate and titanyl sulfate;

[0028] The hydrolysis inhibitor is selected from one or more of water, lower alcohol with carbon atoms number 1-5, higher alcohol with carbon atoms number 6 or more, hexanediol, ethanolamine and acetylacetone; preferably one or more of ethanol, propanol, isopropanol, butanol, isobutanol, ethanolamine and acetylacetone;

[0029] 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;

[0030] The dispersing agent 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 glyceride, fatty acid sorbitan, polysorbate, triethanolamine sucrose ester, polyol sucrose ester, sodium dodecyl sulfate, methyl bromide ammonium and cetyltrimethylammonium chloride.

[0031] Optionally, the alumina matrix raw material contains hydrous kaolin and / or metakaolin, optionally hydrated alumina, optionally high clay;

[0032] Preferably, the hydrated alumina is selected from one or more of boehmite, bayerite and gibbsite; more preferably, the hydrated alumina is calcined hydrated alumina or acidified hydrated alumina;

[0033] Preferably, the alumina matrix raw material contains 0-100 wt%, preferably 10-95 wt%, preferably 20-80 wt% of the hydrous kaolin, 0-100 wt%, preferably 10-80 wt%, 5-50 wt%, preferably 15-45 wt% of the metakaolin, 0-20 wt% of the hydrated alumina and 0-70 wt%, preferably 0-30 wt%, preferably 10-25 wt% of the high clay, based on the total weight of the alumina matrix raw material.

[0034] The third aspect of the present application provides a method for preparing the Y-type molecular sieve catalytic material provided by the second aspect of the present application, which comprises: mixing the titanium-containing reactive microspheres, a first silicon source, a first directing agent, sodium hydroxide and water, and then subjecting the obtained mixture to hydrothermal crystallization treatment.

[0035] Optionally, the hydrothermal crystallization treatment is performed under conditions of a temperature of 88-105℃ and a time of 10-78 hours.

[0036] The first silicon source, the first directing agent, sodium hydroxide and water are used in a weight ratio of (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.

[0037] The first directing agent calculated as Al2O3 and the titanium-containing reactive microspheres are used in a weight ratio of (0.001-2) : 1.

[0038] The first silicon source is selected from one or more of sodium silicate, silica gel and organosilicon.

[0039] The fourth aspect of the present application provides a titanium-containing reactive microsphere suitable for hydrothermal crystallization to prepare a Y-type molecular sieve catalytic material, wherein, based on the dry basis weight of the titanium-containing reactive microspheres, the titanium-containing reactive microspheres contain 85-98% by weight of an alumina matrix and 2-15% by weight of titanium dioxide, and the titanium dioxide contains anatase titanium oxide.

[0040] Optionally, the titanium-containing reactive microspheres contain 86-97% by weight of an alumina matrix and 3-14% by weight of titanium oxide.

[0041] The titanium-containing reactive microspheres have a sphericity of 85-100% and a particle size of 20-150μm.

[0042] Optionally, based on the dry basis weight of the titanium-containing reactive microspheres, the titanium-containing reactive microspheres contain 10-95% by weight, preferably 15-80% by weight, preferably 20-50% by weight of hydrous kaolin or kaolin raw soil on a dry basis, 5-50% by weight, preferably 10-45% by weight of metakaolin on a dry basis, 0-20% by weight, preferably 2-15% by weight of alumina on a dry basis, 0-30% by weight, preferably 5-28% by weight, preferably 10-25% by weight of high clay on a dry basis, and 3-15% by weight, preferably 3-12% by weight, preferably 3-10% by weight of titanium dioxide.

[0043] Optionally, the titanium oxide is derived from the titanium sol containing a dispersant, and the titanium sol containing a dispersant contains a hydrolysis inhibitor, titanium oxide, an acidic substance, a dispersant and water.

[0044] The fifth aspect of the present application provides a method for preparing the titanium-containing reactive microspheres provided by the fourth aspect of the present application, which comprises the following steps:

[0045] (1) mixing the aqueous kaolin or kaolin raw soil, metakaolin, optional high soil, titanium sol containing stabilizer, optional alumina and water to form a slurry; the solid content of the slurry is 15-45 wt%, preferably 25-40 wt%;

[0046] (2) spraying and drying the slurry obtained in step (1) and optionally calcining; the calcination temperature is 300-1000℃, preferably 400-750℃, and the calcination time is 1-4 h.

[0047] The sixth aspect of the present application provides a Y-type molecular sieve catalytic material, which is obtained by hydrothermal crystallization of a mixture containing the titanium-containing reactive microspheres provided by the fourth aspect of the present application, a second silicon source, a second directing agent, sodium hydroxide and water;

[0048] Preferably, the weight ratio of the amount 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;

[0049] The weight ratio of the amount of the second directing agent calculated as Al2O3 to the titanium-containing reactive microspheres is (0.001-2) : 1;

[0050] The second silicon source is selected from one or more of sodium silicate, silica gel and organosilicon.

[0051] The present application has the following advantages:

[0052] (1) The titanium sol provided by the present application is particularly suitable for preparing shaped microspheres for hydrothermal crystallization reaction, and the obtained microspheres have high sphericity, good strength after hydrothermal crystallization, and good synergistic effect with the crystallization product.

[0053] (2) The Y-type molecular sieve catalytic material of the present application is obtained by hydrothermal crystallization of the titanium-containing reactive microspheres. The titanium-containing reactive microspheres have mesoporous and macroporous structures, and can form molecular sieve catalysts in situ on the mesoporous and macroporous structures.

[0054] (3) The present application contains titanium dioxide in the titanium-containing reactive microspheres, which is uniformly distributed in the Y-type molecular sieve catalytic material after crystallization, fully plays the synergistic effect of titanium and aluminum matrix, and the titanium metal also has a catalytic effect, so that the catalyst containing the titanium-containing reactive microspheres has better strength and cracking effect.

[0055] Other features and advantages of the present application will be illustrated in the following detailed description of the embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0056] The accompanying drawings are included to provide a further understanding of the present application and are incorporated in and constitute a part of this specification, illustrate embodiments of the present application and together with the description serve to explain the present application. In the drawings:

[0057] Figure 1 is a crystal phase diagram of the titanium-containing reactive microspheres ZQ-1 and ZQ-2 and the reactive microspheres DB-1;

[0058] Figure 2 is an XRD spectrum of the Y-type molecular sieve catalytic material TY-1;

[0059] Figure 3 is an XRD spectrum of the molecular sieve catalytic material DBY-1. DETAILED DESCRIPTION

[0060] The specific embodiments of the present application will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative and explanatory and are not intended to limit the present application.

[0061] The present application provides a titanium sol comprising TiO2 colloidal particles, a hydrolysis inhibitor, an acidic substance, a dispersant and water, the titanium sol containing anatase-type titanium oxide after being dried and calcined at 500°C for 1-10 hours.

[0062] In one embodiment of the present application, the content of the TiO2 colloidal particles of the titanium sol is 5-25% by weight, the content of the dispersant is 0.1-5% by weight, the content of the hydrolysis inhibitor is 0.2-10% by weight, and the pH value of the titanium sol is 2.5-4.2.

[0063] According to the present application, the titanium sol can be prepared by a titanium dioxide precursor hydrolysis method. In one embodiment of the present application, the titanium sol is prepared by a method comprising the following steps: S1, mixing a titanium source with a hydrolysis inhibitor to obtain a mixed solution, the concentration of the mixed solution being 0.5-30% by weight in terms of TiO2; S2, mixing the mixed solution, an acid and a dispersant, and allowing the obtained mixture to react at 20-90°C for 0.5-3 hours to obtain the titanium sol.

[0064] In one embodiment of the present application, after the mixture is allowed to react at 20-90°C for 0.5-3 hours in step S2, aging is performed to obtain the titanium sol.

[0065] In one embodiment of the present application, the temperature of the mixing in step S1 is 15-30℃, and the mixing time is 0.5-2.5 min.

[0066] According to the present application, the dispersant is a cationic surfactant and an anionic surfactant, and 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 glyceride, fatty acid sorbitan, polysorbate, triethanolamine sucrose ester, polyol sucrose ester, sodium dodecyl sulfate, methyl bromide ammonium, and cetyltrimethylammonium chloride.

[0067] According to the present application, the titanium source is selected from one or more of titanium alkoxide of tetraethoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, titanium tetrachloride, titanium sulfate, and titanyl sulfate; and is preferably titanium alkoxide of tetrabutoxytitanium.

[0068] According to the present application, the hydrolysis inhibitor is selected from one or more of water, lower alcohol with carbon atom number of 1-5, higher alcohol with carbon atom number of 6 or more, hexanediol, ethanolamine, and acetylacetone; and is preferably one or more of ethanol, propanol, isopropanol, butanol, isobutanol, ethanolamine, and acetylacetone.

[0069] According to the present application, the acid is selected from inorganic acid and / or organic acid; the inorganic acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; and 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, and is preferably acetic acid or citric acid.

[0070] According to the present application, the dispersant is a cationic surfactant and an anionic surfactant, and 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 glyceride, fatty acid sorbitan, polysorbate, triethanolamine sucrose ester, polyol sucrose ester, sodium dodecyl sulfate, methyl bromide ammonium, and cetyltrimethylammonium chloride.

[0071] The second aspect of the present application provides a Y-type molecular sieve catalytic material, which is obtained by hydrothermally crystallizing a titanium-containing reactive microsphere, and the titanium-containing reactive microsphere contains 85-98 wt% of an alumina matrix and 2-15 wt% of titanium dioxide, and the titanium dioxide contains anatase titanium dioxide, based on the dry weight of the titanium-containing reactive microsphere.

[0072] The Y-type molecular sieve catalytic material of the present application is prepared from the titanium-containing reactive microspheres by hydrothermal crystallization. The molecular sieve can be in-situ grown on the reactive microspheres, and the titanium dioxide is contained in the titanium-containing reactive microspheres, which can be uniformly distributed in the Y-type molecular sieve catalytic material after crystallization, so that the synergistic effect of titanium and the alumina matrix is fully played, and the prepared catalyst has better strength and cracking effect, which can improve the conversion rate of the raw material of catalytic cracking and the total liquid yield.

[0073] In one embodiment of the present application, the titanium-containing reactive microspheres contain 85-98 wt% of the alumina matrix and 2-15 wt% of the titanium dioxide, preferably 86-97 wt% of the alumina matrix and 3-14 wt% of the titanium dioxide; the sphericity of the titanium-containing reactive microspheres is 85-100%, and the particle size is 20-150 μm, preferably the sphericity is 90-100%.

[0074] In one embodiment of the present application, the specific surface area of the Y-type molecular sieve catalytic material is 200-700 m 2 / g, the total pore volume is 0.20-0.5 mL / g, the attrition index is 0.1-3% per hour, and the volume of the mesopore and macropore with a pore size of 2-50 nm accounts for 20-50% of the total pore volume, preferably the specific surface area is 500-600 m 2 / g, the total pore volume is 0.22-0.35 mL / g, the attrition index is 0.1-2.5% per hour, and the volume of the mesopore and macropore with a pore size of 2-50 nm accounts for 23-50% of the total pore volume.

[0075] According to the present application, the titanium-containing reactive microspheres are prepared by a method comprising the following steps: mixing the alumina matrix raw material, the titanium sol and water to obtain a slurry, and spray drying the slurry to obtain the titanium-containing reactive microsphere precursor;

[0076] The titanium-containing reactive microsphere precursor is further subjected to calcination treatment to obtain the titanium-containing reactive microspheres. The calcination treatment conditions can include a temperature of 300-1000 °C and a time of 1-10 hours; preferably, the temperature is 400-750 °C and the time is 1.5-8 hours.

[0077] According to the present application, the solid content of the slurry can vary within a large range. In one embodiment of the present application, the solid content of the slurry is 20-60 wt%.

[0078] According to the present application, the spray drying is well known to those skilled in the art, and will not be described here. The spray drying conditions can include an inlet temperature of 50-700 °C and an outlet temperature of 50-700 °C. In one embodiment of the present application, the particle size of the titanium-containing reactive microspheres obtained by spray drying is 20-150 μm.

[0079] In one embodiment of the present application, the alumina matrix raw material contains hydrous kaolin, and / or metakaolin, optionally hydrated alumina, optionally high clay. The hydrous kaolin is a product of dispersing kaolin in water and removing associated sandy minerals; the metakaolin is obtained by calcining the hydrous kaolin at 500-900℃ to remove water; the high clay is obtained by calcining the hydrous kaolin at 900-1050℃ to remove water. The hydrated alumina can include, but is not limited to, one or more of boehmite, bayerite and gibbsite, and more preferably, the hydrated alumina is calcined hydrated alumina or acidified hydrated alumina, the calcined hydrated alumina is obtained by calcining the hydrated alumina at 400-700℃, and the acidified hydrated alumina is obtained by acidifying the hydrated alumina at a pH value less than 3.5.

[0080] In one embodiment of the present application, the alumina matrix raw material contains 0-100 wt%, preferably 10-95 wt%, for example 15-80 wt% of the hydrous kaolin, 0-100 wt%, 5-50 wt%, for example 10-45 wt% of the metakaolin, 0-20 wt%, for example 5-15 wt% of the hydrated alumina, and 0-70 wt%, preferably 0-30 wt%, for example 5-25 wt% of the high clay, based on the total weight of the alumina matrix raw material.

[0081] More preferably, the alumina matrix raw material contains 20-80 wt% of the hydrous kaolin, 15-45 wt% of the metakaolin, 5-15 wt% of the hydrated alumina, and 10-25 wt% of the high clay as the inert component raw material of the Y-type molecular sieve catalytic material, the metakaolin can provide soluble alumina for the growth of the molecular sieve, and the high clay will be used to prepare an aluminum-rich matrix.

[0082] The titanium-containing reactive microspheres of the present application can be used for crystallization to prepare porous zeolites, or modified as catalytic cracking catalysts, catalytic cracking aids, dehydrogenation catalysts, oxidation catalysts.

[0083] The third aspect of the present application provides a method for preparing the Y-type molecular sieve catalytic material provided in the second aspect of the present application, the method comprising: mixing the titanium-containing reactive microspheres, a silicon source, a directing agent, sodium hydroxide and water, and then subjecting the obtained mixture to hydrothermal crystallization treatment.

[0084] According to the present application, the conditions of the hydrothermal crystallization treatment can include a temperature of 88-105℃ and a time of 10-78 hours, and more preferably, a temperature of 90-96℃ and a time of 12-70 hours.

[0085] In one embodiment of the present application, the method further comprises filtering, washing and drying the product obtained from the hydrothermal crystallization process, preferably, the solid product obtained from the filtering is washed to a pH value of the washing solution less than 10. The drying can be performed in a constant temperature drying oven, and the drying conditions can include a temperature of 100-150°C and a time of 100-150°C.

[0086] According to the present application, the weight ratio of the amount of the first silicon source, the first directing agent, sodium hydroxide and water can vary in a wide range, for example, can be (2-9) : 1 : (1-3) : (40-200), 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 alkali source is calculated as Na2O. The weight ratio of the amount of the first directing agent calculated as Al2O3 and the reactive microspheres containing titanium can also vary in a wide range, for example, can be (0.001-1) : 1, preferably (0.01-1.5).

[0087] In one embodiment of the present application, the directing agent can be synthesized according to conventional methods, such as the preparation methods described in USP 3574538, USP 3639099, USP 3671191, USP 4166099, EUP 0435625. The molar composition of the directing agent is (10-17) SiO2: (0.7-1.3) Al2O3: (11-18) Na2O: (200-350) H2O. The raw materials are aged at 4-35°C, preferably 4-20°C, to obtain the directing agent during the synthesis. According to the present application, the silicon source can be selected from sodium silicate, silica gel and one or several organosilicon compounds, preferably sodium silicate.

[0088] The fourth aspect of the present application provides a reactive microsphere containing titanium suitable for the hydrothermal crystallization of a catalytic material containing titanium Y-type molecular sieve, wherein the reactive microsphere containing titanium contains 85-98% by weight of an alumina matrix and 2-15% by weight of titanium dioxide, and the titanium dioxide contains anatase-type titanium dioxide, based on the dry basis weight of the reactive microsphere containing titanium.

[0089] In one embodiment of the present application, the reactive microsphere containing titanium contains 86-97% by weight of an alumina matrix and 3-14% by weight of titanium oxide; the sphericity of the reactive microsphere containing titanium and zirconium is 85-100%, and the particle size is 20-150 μm.

[0090] In one embodiment of the present application, the titanium-containing reactive microspheres contain, based on the dry basis weight of the titanium-containing reactive microspheres, 10-95 wt%, preferably 15-80 wt%, preferably 20-50 wt% of hydrous kaolin, 5-50 wt%, preferably 10-45 wt% of metakaolin (also known as deviated kaolin), 0-20 wt%, preferably 2-15 wt% of alumina, 0-30 wt%, preferably 5-28 wt%, preferably 10-25 wt% of high clay, and 3-15 wt%, preferably 3-12 wt%, preferably 3-10 wt% of titanium oxide.

[0091] In one embodiment of the present application, the titanium oxide is derived from the dispersant-containing titanium sol, which contains a hydrolysis inhibitor, titanium oxide, an acidic substance, a dispersant, and water.

[0092] The fifth aspect of the present application provides a method for preparing the titanium-containing reactive microspheres provided by the fourth aspect of the present application, which comprises the following steps: (1) mixing hydrous kaolin, metakaolin, optionally high clay, a stabilizer-containing titanium sol, optionally alumina, and water to form a slurry; the solid content of the slurry is 15-45 wt%, preferably 25-40 wt%; (2) spray drying and optionally calcining the slurry obtained in step (1); the calcination temperature is 300-1000°C, preferably 400-750°C, and the calcination time is 1-4 h.

[0093] In the present application, the alumina can include, but is not limited to, one or more of hydrated alumina, γ-alumina, η-alumina, and κ-alumina.

[0094] The sixth aspect of the present application provides a Y-type molecular sieve catalytic material, which is obtained by hydrothermal crystallization of a mixture containing the titanium-containing reactive microspheres provided by the fourth aspect of the present application, a second silicon source, a second directing agent, sodium hydroxide, and water; preferably, the weight ratio of the amount 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 amount of the second directing agent calculated as Al2O3 to the titanium-containing reactive microspheres is (0.001-2) : 1; the second silicon source is selected from one or more of sodium silicate, silica gel, and organosilicon.

[0095] In a seventh aspect, the present application provides a catalyst comprising the Y-type molecular sieve catalytic material according to the second aspect of the present application and a modifying component. In a specific embodiment of the present application, the modifying component is selected from rare earth metals, preferably one or more of lanthanum, cerium, praseodymium, neodymium and phosphorus. The content of the modifying component is 5.2-6.5 wt% based on the dry weight of the catalyst.

[0096] The present application is further illustrated by the following examples, but the present application is not limited in any way by the examples.

[0097] The content of the molecular sieve in the molecular sieve catalytic material of the examples and comparative examples was determined according to the standard method RIPP 146-90 (see “Analysis Methods for Petroleum and Chemical Industry (RIPP Test Methods)”, edited by Yang Cuiding et al., published by Science Press in 1990, hereinafter referred to as the RIPP standard method) and was derived from the relative crystallinity.

[0098] The content of each component in the titanium-containing reactive microspheres and the titanium oxide matrix was determined by XRF analysis. The crystal form of titanium oxide contained in the titanium-containing reactive microspheres after calcination was determined by XRD analysis.

[0099] In the present application, the sphericity is represented by the sphericity index SPHT, which is the ratio of the surface area of a sphere having the same volume as the object to the surface area of the object. The sphericity calculation formula is as follows: sphericity index SPHT = 4πA 2 / P 2 wherein A is the projected area of the particle and P is the projected perimeter of the particle. The Camsizer XT dynamic digital imaging particle analyzer of Leica Company in Germany was used, two digital camera lenses, a base lens CCD-B and a focusing lens CCD-Z, were used to take pictures of the falling sample particles at a speed of 300 pictures per second. Through software analysis, the particle images captured by the two lenses were statistically calculated to obtain the sphericity index SPHT of the sample.

[0100] The attrition index of the molecular sieve catalytic material and the titanium-containing reactive microspheres was determined by the method of NB / SH / T 0943-2017. The specific surface area of the molecular sieve catalytic material was determined by the nitrogen adsorption method (GB / T 5816-1995), the total pore volume (Vtotal pore) and the pore volume of the pores with a pore size of 2-50 nm (Vpore size of 2-50 nm) were determined by the nitrogen adsorption method (RIPP 151-90), and the meso-macropore rate was calculated according to the following formula: meso-macropore rate = (Vtotal pore-Vpore size of 2-50 nm) / Vtotal pore x 100%.

[0101] In the examples and comparative examples, the preparation of the directing agent: take 250 kg of sodium silicate solution (containing 20.05% by weight of SiO2, 6.41% by weight of Na2O), slowly add 120 kg of sodium metaaluminate solution (containing 3.15% by weight of Al2O3, 21.1% by weight of Na2O) under rapid stirring at 30°C, stir for 1 hour, age at 20°C for 48 hours, and obtain the directing agent.

[0102] Preparation Example 1 of titanium sol

[0103] S1, first dissolve 17.02 mL of Ti(OC4H9)4 in 68.28 mL of anhydrous ethanol to obtain a mixed solution;

[0104] S2, then add 4.80 mL of diethanolamine to the mixed solution, stir for 10 min, adjust the pH to about 3 with glacial acetic acid, finally add 0.5 g of polyethylene glycol, stir for 2 h at 20°C on a constant temperature magnetic stirrer, and then age to obtain a uniform, transparent light yellow sol, which is titanium sol C1.

[0105] Preparation Example 2 of titanium sol

[0106] S1, 17.02 mL of Ti(OC4H9)4 is dissolved in 68.28 mL of anhydrous ethanol to obtain a mixed solution;

[0107] S2, then add 4.80 mL of acetylacetone to the mixed solution, stir for 10 min, adjust the pH to about 2.8 with citric acid, finally add 1 g of polyethylene glycol, stir for 2 h at 20°C on a constant temperature magnetic stirrer, and then age to obtain a uniform, transparent light yellow sol, which is titanium sol C2.

[0108] Preparation Example 3 of titanium sol

[0109] Add 50 g of titanium chloride aqueous solution (Ti concentration 18 mass%) to a beaker, slowly add 38 g of oxalic acid, stir for 30 min to obtain a mixed solution; then slowly add triethanolamine to the mixed solution with a pump, the addition time is 30 min, adjust the pH to 4, and obtain a clear and transparent titanium sol C3 after aging.

[0110] Preparation Examples 1-3 and 6 of titanium-containing reactive microspheres

[0111] The hydrous kaolin is calcined in a muffle furnace at 1000°C for 3 hours to obtain high kaolin through characteristic heat release. The hydrous kaolin is calcined in a muffle furnace at 870°C for 1 hour to obtain metakaolin. The pseudoboehmite is calcined in a muffle furnace at 600°C for 2 hours to obtain γ-Al2O3, i.e. calcined hydrated alumina.

[0112] The kaolin, metakaolin, high clay, calcined hydrated alumina, titanium sol and water were mixed and slurried according to the amount ratio shown in Table 1. The slurry having a solid content of 40 wt% was spray dried to obtain a titanium-containing reactive microsphere precursor. The titanium-containing reactive microsphere precursor was calcined at 800°C for 3 hours to obtain a titanium-containing reactive microsphere ZQ-1 having a particle size of 20-150 μm. The data in the raw material amount section of Table 1 represent the weight ratio of the amounts of the kaolin, metakaolin, high clay, calcined hydrated alumina and titanium sol.

[0113] Preparation Example 4-5 of the titanium-containing reactive microsphere

[0114] The kaolin was calcined at 1000°C for 3 hours in a muffle furnace to obtain a high clay. The kaolin was calcined at 870°C for 1 hour in a muffle furnace to obtain a metakaolin. The boehmite was acidified with hydrochloric acid to obtain an acidified hydrated alumina having a pH of 1-3.

[0115] The kaolin, metakaolin, high clay, acidified hydrated alumina, titanium sol and water were mixed and slurried according to the amount ratio shown in Table 1. The slurry having a solid content of 40 wt% was spray dried to obtain a titanium-containing reactive microsphere precursor. The titanium-containing reactive microsphere precursor was calcined at 800°C for 3 hours to obtain a titanium-containing reactive microsphere having a particle size of 20-150 μm. The composition of the titanium-containing reactive microsphere obtained is shown in Table 2, as follows.

[0116] Preparation Example 7 of the titanium-containing reactive microsphere

[0117] The same method as in Preparation Example 1 of the titanium-containing reactive microsphere was used, except that the slurry was prepared using titanium tetrachloride instead of the titanium sol.

[0118] Preparation Comparative Example 1 of the reactive microsphere not containing titanium

[0119] The kaolin was calcined at 1000°C for 3 hours in a muffle furnace to obtain a high clay. The kaolin was calcined at 870°C for 1 hour in a muffle furnace to obtain a metakaolin. The boehmite was calcined at 600°C for 2 hours in a muffle furnace to obtain γ-Al2O3, i.e. calcined hydrated alumina.

[0120] The kaolin, metakaolin, high clay, calcined hydrated alumina and water were mixed and slurried according to the amount ratio shown in Table 1. The slurry having a solid content of 40 wt% was spray dried to obtain a reactive microsphere precursor. The reactive microsphere precursor was calcined at 800°C for 3 hours to obtain a reactive microsphere DB-1 having a particle size of 20-150 μm.

[0121] The XRD patterns of the titanium-containing reactive microspheres ZQ-1, ZQ-2 and the reactive microspheres DB-1 are shown in Figure 1 It can be seen from Figure 1 that the titanium-containing reactive microspheres ZQ-1 and ZQ-2 have obvious diffraction peaks at 25±0.5°, 48±0.5° and 55±0.5°, and the Ti in the microspheres mainly exists in the form of anatase titanium dioxide with a small amount of rutile titanium dioxide.

[0122] Table 1

[0123]

[0124] Table 2

[0125]

[0126]

[0127] Example 1 for preparing a molecular sieve catalytic material

[0128] One kilogram of the titanium-containing reactive microspheres ZQ-1 was mixed with 6 kilograms of a sodium silicate solution (containing 20.05% by weight of SiO2 and 6.41% by weight of Na2O), 1.5 kilograms of a directing agent and 2 kilograms of a sodium hydroxide solution with a concentration of 15% by weight, and then the mixture was subjected to hydrothermal crystallization treatment at 94°C and a rotation speed of 400 rpm for 24 hours. After the hydrothermal crystallization treatment, the crystallization tank was rapidly cooled and filtered, and the solid product obtained by the filtration was washed with deionized water until the pH value of the washing liquid was less than 10. Then, the product was dried at 120°C for 2 hours to obtain a Y-type molecular sieve catalytic material TY-1, and the XRD pattern of the TY-1 is shown in Figure 2 The XRD pattern does not contain characteristic peaks of titanium, indicating that the titanium is highly dispersed in the reactive microspheres during the crystallization process.

[0129] Example 2 for preparing a molecular sieve catalytic material

[0130] The Y-type molecular sieve catalytic material TY-2 was prepared by the same method as in Example 1, except that the titanium-containing reactive microspheres ZQ-2 were used instead of ZQ-1.

[0131] Example 3 for preparing a molecular sieve catalytic material

[0132] The Y-type molecular sieve catalytic material TY-3 was prepared by the same method as in Example 1, except that 7 kilograms of sodium silicate was used and the titanium-containing reactive microspheres ZQ-3 were used instead of ZQ-1.

[0133] Example 4 for preparing a molecular sieve catalytic material

[0134] The Y-type molecular sieve catalytic material TY-4 was prepared by the same method as in Example 1, except that 7 kg of sodium silicate was added and reactive microspheres ZQ-4 containing titanium were used instead of ZQ-1.

[0135] Example 5 for preparing a molecular sieve catalytic material

[0136] The Y-type molecular sieve catalytic material TY-5 was prepared by the same method as in Example 1, except that 7 kg of sodium silicate was added and reactive microspheres ZQ-5 containing titanium were used instead of ZQ-1.

[0137] Example 6 for preparing a molecular sieve catalytic material

[0138] The Y-type molecular sieve catalytic material TY-6 was prepared by the same method as in Example 1, except that reactive microspheres ZQ-6 containing titanium were used instead of ZQ-1.

[0139] Example 7 for preparing a molecular sieve catalytic material

[0140] The Y-type molecular sieve catalytic material TY-7 was prepared by the same method as in Example 1, except that reactive microspheres ZQ-7 containing titanium were used instead of ZQ-1.

[0141] Comparative Example 1 for preparing a molecular sieve catalytic material

[0142] The Y-type molecular sieve catalytic material DY-1 was prepared by the same method as in Example 1, except that reactive microspheres DB-1 were used instead of ZQ-1. The XRD spectrum of the molecular sieve catalytic material DY-1 is shown in Figure 3 .

[0143] Comparative Example 2 for preparing a molecular sieve catalytic material

[0144] DY-1 was added to deionized water to adjust the concentration to 50% by weight, and 5% by weight of titanium sol Cl equal to the weight of DY-1 was added and impregnated for 6 hours, and then dried at 120 degrees to obtain the molecular sieve catalytic material DY-2.

[0145] Table 3

[0146]

[0147] The meso-macropore rate refers to the proportion of the volume of meso-macropores with a pore size of 2-50 nm to the total pore volume.

[0148] Example 1 for preparing a catalyst

[0149] The molecular sieve catalytic material TY-1 was added into deionized water to form a slurry with a solid content of 10% by weight; lanthanum chloride was taken and added into water to form a lanthanum chloride solution with a La2O3 concentration of 6% by weight; the lanthanum chloride solution was added into the slurry, the weight ratio of lanthanum chloride (calculated as La2O3) to the molecular sieve (calculated as dry basis) was 1:19, stirring at 70°C for 1 h, filtration, washing, drying at 150°C for 8 h, and calcining at 500°C for 4 h; then the obtained catalyst was washed with an ammonium sulfate solution, the weight ratio of ammonium sulfate to the molecular sieve catalytic material (dry basis) was 1:20, stirring at 70°C for 1 h, filtration, washing, drying at 150°C for 8 h, and calcining at 500°C for 2 h; the obtained catalyst was recorded as REGY-1.

[0150] Examples 2-7 for preparing catalysts

[0151] The catalysts REGY-1 to REGY-7 were prepared by the same method as that in Example 1 for preparing catalysts, except that the molecular sieve catalytic materials TY-2 to TY-7 prepared in Examples 2-7 for preparing molecular sieve catalytic materials were used to prepare the catalysts, respectively.

[0152] Comparative Examples 1-2 for preparing catalysts

[0153] The catalysts were prepared by the same method as that in Example 1 for preparing catalysts, except that the molecular sieve catalytic materials prepared in Comparative Examples 1-2 for preparing molecular sieve catalytic materials were used to prepare the catalysts, respectively.

[0154] Test Example

[0155] The catalysts prepared in the Examples and Comparative Examples for preparing catalysts were treated in an aging device at 800°C / 100% steam for 17 hours, and were evaluated in a fixed fluidized bed micro-reactor ACE, the raw oil was a Wuhan mixed three raw oil (the composition and properties are shown in Table 4), and the evaluation conditions were as follows: the reaction temperature was 500°C, the catalyst / oil ratio (by weight) was 6, and the WHSV was 16 h-1. -1 The results are shown in Table 5.

[0156] wherein the conversion rate = the gasoline yield + the liquefied gas yield + the dry gas yield + the coke yield;

[0157] The gasoline selectivity = the gasoline yield / the conversion rate x 100%.

[0158] Table 4

[0159]

[0160] Table 5

[0161]

[0162] As shown in Table 5, under the same modification conditions, the catalyst prepared by using the Y-type molecular sieve catalytic material of the present application has better cracking effect, and can improve the conversion rate and total liquid yield of the raw oil catalytic cracking. Preferably, the catalyst has higher (LPG) liquefied gas yield.

[0163] The preferred embodiments of the present application are described in detail above with reference to the drawings, but the present application is not limited to the specific details of the above-described embodiments. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, and these simple modifications all belong to the protection scope of the present application.

[0164] In addition, it should be noted that each specific technical feature described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present application will not further describe various possible combinations.

[0165] In addition, various different embodiments of the present application can also be combined in any manner, as long as they do not deviate from the idea of the present application, and they should also be considered as disclosed by the present application.

Claims

1. A Y-type molecular sieve catalytic material for improving total liquid yield of FCC, said Y-type molecular sieve catalytic material being obtained by hydrothermally crystallizing titanium-containing reactive microspheres, said titanium-containing reactive microspheres containing 85-98 wt% of alumina matrix and 2-15 wt% of titanium dioxide, based on dry basis weight of the titanium-containing reactive microspheres, said titanium dioxide including titanium dioxide containing anatase type; said titanium-containing reactive microspheres being prepared by a method comprising the steps of: mixing an alumina matrix raw material, a titanium sol and water to obtain a slurry, and spray drying the slurry to obtain a precursor of the titanium-containing reactive microspheres; and calcining the precursor of the titanium-containing microspheres to obtain the titanium-containing reactive microspheres; said calcining process being performed at a temperature of 300-1000°C for 1-10 hours; said titanium sol containing TiO2 colloidal particles, a hydrolysis inhibitor, an acidic substance, a dispersing agent and water, and containing titanium dioxide of anatase type after being dried and calcined at 500°C for 1-10 hours; said titanium sol containing 5-25 wt% of TiO2 colloidal particles, 0.1-5 wt% of the dispersing agent, and 0.2-10 wt% of the hydrolysis inhibitor, and having a pH value of 2.5-4.2; said titanium-containing reactive microspheres containing 86-97 wt% of alumina matrix and 3-14 wt% of titanium dioxide; said titanium-containing reactive microspheres having a sphericity of 85-100% and a particle size of 20-150 μm; and said titanium dioxide being contained in an amount of 1.5-14 wt%, based on dry basis weight of the Y-type molecular sieve catalytic material. The Y-type molecular sieve catalytic material has a specific surface area of 200-700 m 2 / g, a total pore volume of 0.20-0.5 mL / g, an attrition index of 0.1-3% / h, and a mesopore volume with a pore diameter of 2-50 nm accounting for 20-50% of the total pore volume.

2. The Y-type molecular sieve catalytic material according to claim 1, wherein said titanium sol is prepared by a method comprising the steps of: S1. mixing a titanium source and a hydrolysis inhibitor to obtain a mixed solution, said mixed solution having a concentration of 0.5-30 wt% in terms of TiO2; and S2. mixing said mixed solution, an acid and a dispersing agent, and allowing the mixture to react at 20-90°C for 0.5-3 hours to obtain the titanium sol; said titanium sol having a pH value of 0-7 in step S2; and said titanium sol having a pH value of 0.5-5 in step S2.

3. The Y-type molecular sieve catalytic material according to claim 1 or 2, wherein said titanium source is selected from one or more of titanium alkoxides including tetraethoxytitanium, tetraisopropoxytitanium and tetrabutoxytitanium, titanium tetrachloride, titanium sulfate and titanium oxysulfate; said 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; said 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; and said dispersing agent 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 glyceride, fatty acid sorbitan, polysorbate, triethanolamine sucrose ester, polyhydric alcohol sucrose ester, sodium dodecyl sulfate, methyl bromide ammonium and cetyltrimethylammonium chloride. ​ ​ ​ ​ 2. The Y-type molecular sieve catalytic material of claim 1, wherein, ​ ​ 3. The Y-type molecular sieve catalytic material of claim 1, wherein, ​ 4. The Y-type molecular sieve catalytic material of claim 1, wherein, The specific surface area is 500-600 m 2 / g, the total pore volume is 0.22-0.35 mL / g, the attrition index is 0.1-2.5% / h, and the meso-macro pore volume with a pore diameter of 2-50 nm accounts for 23-50% of the total pore volume.

5. The Y-type molecular sieve catalytic material of claim 1, wherein, ​ ​ ​ 6. The Y-type molecular sieve catalytic material of claim 5, wherein, ​ 7. The Y-type molecular sieve catalytic material of claim 6, wherein, ​ 8. The Y-type molecular sieve catalytic material of claim 5, wherein, ​ ​ ​ ​ 9. The Y-type molecular sieve catalytic material of claim 5, wherein, The hydrolysis inhibitor is selected from one or more of ethanol, propanol, isopropanol, butanol, isobutanol, ethanolamine and acetylacetone; The acid is selected from acetic acid or citric acid.

10. The Y-type molecular sieve catalytic material of claim 1, wherein, The alumina matrix raw material contains hydrous kaolin and / or metakaolin, hydrated alumina, high clay.

11. The Y-type molecular sieve catalytic material of claim 10, wherein, The hydrated alumina is selected from one or more of boehmite, bayerite and gibbsite.

12. The Y-type molecular sieve catalytic material of claim 10, wherein, The hydrated alumina is calcined hydrated alumina or acidified hydrated alumina.

13. The Y-type molecular sieve catalytic material of claim 10, wherein, The alumina matrix raw material contains 0-100 wt% of the hydrous kaolin, 0-100 wt% of the metakaolin, 0-20 wt% of the hydrated alumina and 0-70 wt% of the high clay, based on the total weight of the alumina matrix raw material.

14. The Y-type molecular sieve catalytic material of claim 13, wherein, The alumina matrix raw material contains 10-95 wt% of the hydrous kaolin, 10-80 wt% of the metakaolin, 0-20 wt% of the hydrated alumina and 0-30 wt% of the high clay, based on the total weight of the alumina matrix raw material.

15. The Y-type molecular sieve catalytic material of claim 13, wherein, The alumina matrix raw material contains 20-80 wt% of the hydrous kaolin, 5-50 wt% of the metakaolin, 0-20 wt% of the hydrated alumina and 10-25 wt% of the high clay, based on the total weight of the alumina matrix raw material.

16. The Y-type molecular sieve catalytic material of claim 13, wherein, The alumina matrix raw material contains 20-80 wt% of the hydrous kaolin, 15-45 wt% of the metakaolin, 0-20 wt% of the hydrated alumina and 10-25 wt% of the high clay, based on the total weight of the alumina matrix raw material.

17. A method of making the Y-type molecular sieve catalytic material of any of claims 1-16, the method comprising: The titanium-containing reactive microspheres, the first silicon source, the first directing agent, sodium hydroxide and water are mixed, and the obtained mixture is subjected to a hydrothermal crystallization treatment; The hydrothermal crystallization treatment is performed at a temperature of 88-105℃ for 10-78 hours.

18. The method of claim 17, wherein, The weight ratio of the first silicon source (calculated as SiO2), the first directing agent (calculated as Al2O3) and sodium hydroxide (calculated as Na2O) is (2-15):1:(1-7). The weight ratio of the first directing agent (calculated as Al2O3) to the titanium-containing reactive microspheres is (0.001-2):

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

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