Modified β-zeolite, catalytic cracking catalyst, and production method and use thereof

Abstract

The present invention relates to a modified beta zeolite, a catalytic cracking catalyst, and a method for producing and using the same. The modified beta zeolite contains 0.5% to 15% by weight of a Group IVB metal element in terms of oxide, based on the dry basis weight of the modified beta zeolite. The number of centers with medium acid strength in the modified beta zeolite accounts for 30% to 60% of the total acid content, the number of strong acid centers accounts for 5% to 25% of the total acid content, and the ratio of B acid to L acid is 0.8 or more. The ratio of the weight content of the Group IVB metal element in the modified beta zeolite body phase to the weight content of the Group IVB metal element on the surface is 0.1 to 0.8. The catalytic cracking catalyst containing the modified beta zeolite of the present invention has good selectivity and yield of C4 olefins.

Description

Detailed Description of the Invention

[0001] 〔Technical Field〕 The present invention relates to modified β-zeolite, catalytic cracking catalyst, and methods for their production and use. 〔Background Art〕 With the increasing environmental awareness, the quality standards of automotive gasoline have been continuously raised. The new standards for automotive gasoline and GB17930-2016 clearly stipulate that the National VI standard gasoline will be implemented nationwide from 2019. Compared with the National V standard, the National VI standard reduces the contents of benzene, aromatics, and olefins in gasoline. Currently, in the gasoline blending component system in China, it can hardly meet the necessary requirements. Since alkylated gasoline has a high octane number and zero contents of olefins, aromatic compounds, and benzene, it is a good gasoline blending component compared with conventional catalytic gasoline and reformed gasoline under the National VI standard, and the proportion of alkylated gasoline in the gasoline blending components will increase significantly. The main raw materials of the alkylation unit are isobutane and C4 olefins. Nearly 70% of the world's C4 olefins are obtained from catalytic cracking units, and the technology for producing C4 olefin fractions from catalytic cracking units has the advantages of less investment and low cost. Many enterprises are trying to obtain higher yields of C4 olefins from catalytic cracking processes.

[0002] To increase the production of light olefins, shape-selective molecular sieves are usually added to the catalyst. In 1993, Engelhard CORP. of the United States first disclosed a catalytic cracking catalyst for increasing the production of isobutylene and isoamylene in US Patent USP5243121. By reducing the unit cell diameter of Y zeolite in the cracking catalyst through hydrothermal treatment, a catalyst can be obtained that can enhance the olefin selectivity in the product during hydrocarbon cracking. The addition of a specific amount of ZSM-5 zeolite as an auxiliary to the catalyst can result in a decrease in coke yield and an increase in activity. US3758403 discloses a catalyst having ZSM-5 and large-pore zeolites (mainly Y-type zeolites) as active components. The catalyst brings about an increase in octane number and an increase in the yield of C3 and C4 olefins, and the large-pore zeolite decomposes the raw material to produce gasoline and diesel. The ZSM-5 shape-selective molecular sieve further decomposes it into light olefins.

[0003] β-zeolite was first synthesized in 1967 by Wadlinger et al. of Mobil. By 1988, Higgins et al. had clarified its unique three-dimensional structural characteristics. This is the only high-silica zeolite having a channel system with intersecting 12-membered rings. The one-dimensional 12-membered ring channels parallel to the (001) crystal plane have a diameter of 0.75 - 0.57 nm, and the other two-dimensional 12-membered ring channels parallel to the (100) crystal plane have a diameter of 0.65 - 0.56 nm. Due to its unique structure, it has both acid catalytic properties and structural selectivity, and has been rapidly developing as a new catalyst material in recent years. The main problems in the use of β-zeolite are, on the one hand, that the structure of β-zeolite is easily damaged in the process of removing the template agent, and on the other hand, it is easily dealuminated in the reaction process, which deteriorates the activity stability. Therefore, there are many research reports on the modification of β-zeolite.

[0004] CN103771437A discloses a modified β molecular sieve containing phosphorus. The phosphorus content accounts for 3 wt% to 10 wt% calculated as P2O5. The 27 In the Al MAS NMR of the molecular sieve, the ratio of the peak area of the resonance signal with a chemical shift of 40 ± 3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm ± 3 ppm is 1 or more. In the molecular sieve, phosphorus is completely coordinated with the framework aluminum, and the framework aluminum is completely protected, having excellent hydrothermal stability and better product selectivity.

[0005] CN1179994A discloses a method for modifying β zeolite. Na β zeolite undergoes ammonium ion exchange to reduce the Na2O content on the zeolite to less than 0.1 wt%; then, the above-mentioned ammonium-exchanged β zeolite is treated with an acid to remove part of the framework aluminum and increase its silica-alumina ratio to more than 50; the above-mentioned dealuminated β zeolite is uniformly mixed with phosphoric acid or phosphate and dried to make the P2O5 content on the obtained zeolite 2 wt% to 5 wt%; finally, in a steam atmosphere, the obtained product is hydrothermally calcined at 450 °C to 650 °C for 0.5 hour to 4 hours. When the β zeolite modified according to this method is used in the hydrocarbon cracking reaction, olefins, especially isoolefins, can be obtained in a higher yield, and coke can be obtained in a lower yield.

[0006] CN105621432A discloses a modified β molecular sieve and its manufacturing method. The β molecular sieve obtained after ammonium exchange is subjected to pretreatment and drying; a carbon deposition reaction is carried out; a high-temperature calcination treatment is carried out; then, it is subjected to dealumination treatment, drying and carbon calcination treatment to obtain a modified β molecular sieve. The silicon-aluminum ratio of the main body phase of the modified β molecular sieve is 30 to 80, the silica-alumina ratio of the surface layer is 50 to 130, and the silica-alumina ratio of the surface layer is 30 to 70 higher than that of the main body phase. The specific surface area is 400 m 2 / g to 800 m 2 / g, with a pore volume of 0.2 ml / g to 0.60 ml / g; an infrared acid amount of 0.1 mmol / g to 0.6 mmol / g; and a relative crystallinity of 100% to 150%. The silica-alumina ratio of the molecular sieve surface layer of this invention is higher than that of the bulk phase, and has broad applicability in the hydrocracking reaction process.

[0007] CN107899607A provides a modified β molecular sieve, a method for manufacturing a molecular sieve, and its use. The method for manufacturing the catalyst includes using β molecular sieve as a substrate; using a metal element as a modifier; and manufacturing a modified β molecular sieve using an aqueous salt solution of the metal element and an ion exchange method. The metal element is selected from one of Cu, Al, Zn, Fe, and Sn, or a mixture of two or more of them, and accounts for 0.5% to 4% of the mass of the manufactured modified β molecular sieve.

[0008] There are also many reports on the use of β zeolite in a catalytic cracking catalyst for producing low-carbon olefins. US Patent US4837396 discloses a catalyst containing β zeolite and Y zeolite. The metal ion-containing compound is used as a stabilizer to improve the hydrothermal stability and mechanical strength of the catalyst. The stabilizer can act directly on the β zeolite or can be introduced in the manufacturing process.

[0009] CN1055105C discloses a cracking catalyst for obtaining isobutene and isopentene in high yields. The catalyst includes a high-Si zeolite having 6 wt% to 30 wt% of five-membered rings and containing phosphorus and rare earth elements, 5 wt% to 20 wt% of USY zeolite, 1 wt% to 5 wt% of β zeolite, 30 wt% to 60 wt% of clay, and 15 wt% to 30 wt% of inorganic oxide. The catalyst has the characteristic of bringing isobutene and isopentene in high yields under the processing conditions of catalytic cracking, and at the same time, can co-produce high-octane gasoline.

[0010] CN107971003A discloses a catalytic cracking aid containing a β - molecular sieve containing phosphorus and an added metal, and a method for producing the same. The aid contains, on a dry basis, 10 wt% - 75 wt% of a β - molecular sieve containing phosphorus and an added metal, 0 wt% - 60 wt% of clay, 15 wt% - 60 wt% of an inorganic oxide binder, 0 wt% - 25 wt% of a phosphorus additive based on P2O5, and 0 wt% - 15 wt% of a Group VIII metal additive based on the oxide. The distribution parameter D of Al in the molecular sieve satisfies 0.4 ≤ D ≤ 0.8; the micropore specific surface area of the molecular sieve is 420 m 2 / g - 520 m 2 / g; the mesopore volume of the molecular sieve accounts for 30% - 70% of the total pore volume; the amount of strong acid in the molecular sieve accounts for 65% - 80% of the total acid amount; the ratio of the amount of acid B to the amount of acid L is 25 - 90. When the aid is applied to catalytic cracking, it can improve the yields of isobutene and propylene, as well as the octane number of gasoline. However, the increase in the total butene concentration in the liquefied gas is not significant.

[0011] CN104998681A discloses a catalytic cracking aid for improving the concentration of low - carbon olefins and a method for producing the same. The aid contains a boron - modified β - molecular sieve containing phosphorus and a metal, an inorganic oxide adhesive, a Group VIII metal additive, a phosphorus additive, and optionally clay. The catalytic cracking aid is applied to the catalytic cracking of petroleum hydrocarbons, can increase the concentration of isobutene in the catalytic cracking liquefied gas, and can reduce the coke yield.

[0012] CN107971000A discloses a catalytic cracking aid containing a phosphorus-containing β molecular sieve and a method for producing the same. The aid contains 10 wt% - 75 wt% of a phosphorus-containing β molecular sieve on a dry basis, 0 wt% - 60 wt% of clay on a dry basis, 15 wt% - 60 wt% of an inorganic oxide binder on a dry basis, 0 wt% - 25 wt% of a phosphorus additive based on P2O5, and 0 wt% - 15 wt% of a Group VIII metal additive based on oxides. When applying the aid in catalytic cracking, the yields of isobutylene and propylene can be improved, and the octane number of gasoline can be improved.

[0013] The purpose of increasing the yield of light olefins can be achieved to a certain extent by using various catalysts / auxiliaries produced according to the above-mentioned technology in catalytic cracking. However, with the increase in propylene and butylene, the yield of liquefied gas also increases, so there is also a problem that the change in the concentration of propylene or butylene in the liquefied gas is almost eliminated; on the other hand, with the increase in butylene, the yield of propylene also increases, and there is also a problem that the selectivity for butylene deteriorates.

[0014] According to the analysis of the formation and conversion mechanism of C4 olefins in the catalytic cracking process, the formation of C4 olefins in the catalytic cracking process mainly comes from two aspects: one is the product resulting from the decomposition of active intermediates generated from hydrocarbon polymers in the raw material by unimolecular decomposition reaction or bimolecular decomposition reaction, and the other is the product of the secondary reaction of light olefins formed in the decomposition reaction. The C4 olefins generated during catalytic cracking can further undergo decomposition reaction, isomerization reaction, dimerization reaction, and hydrogen transfer reaction.

[0015] 〔Summary of the Invention〕 The object of the present invention is to provide a modified β zeolite, a catalytic cracking catalyst, and methods for producing and using them. The catalytic cracking catalyst of the present invention has good selectivity and yield for C4 olefins.

[0016] In order to achieve the above object, in a first aspect, the present invention provides a modified β-zeolite containing 0.5% to 15% by weight of a Group IVB metal element in terms of the oxide based on the dry standard weight of the modified β-zeolite. The number of centers with a medium acid strength in the modified β-zeolite accounts for 30% to 60% of the total acid amount, the number of strong acid centers accounts for 5% to 25% of the total acid amount, and the ratio of B acid to L acid is 0.8 or more. The ratio of the weight content of the Group IVB metal element in the main body phase of the modified β-zeolite to the weight content of the Group IVB metal element on the surface is 0.1 to 0.8.

[0017] Optionally, the ratio of the B acid to the L acid is 1.0 to 1.5.

[0018] Optionally, the number of centers with a medium acid strength accounts for 35% to 55% of the total acid amount.

[0019] Optionally, the number of strong acid centers accounts for 5% to 20% of the total acid amount.

[0020] Optionally, the modified β-zeolite contains 1% to 12% by weight of the Group IVB metal element in terms of the oxide based on the dry standard weight of the modified β-zeolite.

[0021] Optionally, the Group IVB metal element is Zr and / or Ti, preferably Zr. The weight of the Zr element is based on ZrO2, and the weight of the Ti element is based on TiO2.

[0022] Optionally, the ratio of the weight content of the Group IVB metal element in the main body phase of the modified β-zeolite to the weight content of the Group IVB metal element on the surface is 0.1 to 0.6.

[0023] In a second aspect, the present invention provides a catalytic cracking catalyst comprising, based on the dry reference weight of the catalytic cracking catalyst, 10 wt% to 50 wt%, preferably 20 wt% to 50 wt% of Y-type zeolite, 2 wt% to 40 wt% of modified β-zeolite, 10 wt% to 70 wt% of clay, and 5 wt% to 60 wt% of heat-resistant inorganic oxide, wherein the modified β-zeolite is the modified β-zeolite provided in the first aspect of the present invention.

[0024] Optionally, the Y-type zeolite is selected from one or more of Y-type zeolite containing phosphorus and / or rare earths, ultrastable Y zeolite, and ultrastable Y zeolite containing phosphorus and / or rare earths; Optionally, the clay is selected from one or more of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite, and sepiolite; Optionally, the heat-resistant inorganic oxide is selected from one or more of aluminum oxide, silicon oxide, and amorphous silica-alumina.

[0025] Optionally, the catalytic cracking catalyst comprises 15 wt% to 45 wt%, preferably 30 wt% to 45 wt% of the Y-type zeolite, 5 wt% to 30 wt% of the modified β-zeolite, 10 wt% to 50 wt% of the clay, and 5 wt% to 40 wt% of the heat-resistant inorganic oxide.

[0026] In a third aspect, the present invention provides a method for producing the modified β-zeolite provided in the first aspect of the present invention. The method includes: Step (1): Mixing a compound containing a Group IVB metal, a carbon source, and a first solvent, Adjusting the pH value of the mixture to 4 to 9 to obtain a first slurry, wherein the carbon source includes a natural polymer organic compound and / or a semi-synthetic polymer organic compound; Step (2): Mixing the first slurry and β-zeolite by stirring at 20°C to 100°C for 10 minutes to 180 minutes, taking out the solid matter, and performing a first calcination at 350°C to 650°C for 0.5 hour to 5 hours.

[0027] Optionally, in step (2), the pH value of the first slurry is adjusted to 5 to 8.

[0028] Optionally, the weight ratio of the amount of the compound containing a Group IVB metal to the amount of the β-zeolite is (0.005 to 0.15):1, and the weight ratio of the amount of the β-zeolite to the amount of the carbon source is 1:(0.001 to 0.15). The compound containing a Group IVB metal is based on the oxide of the Group IVB metal, and the β-zeolite is based on the dry basis weight.

[0029] Optionally, the β-zeolite is selected from one or more of a hydrogen-type β-zeolite, a sodium-type β-zeolite, a β-zeolite containing phosphorus, a β-zeolite containing a rare earth metal, and a β-zeolite containing phosphorus and a rare earth metal.

[0030] Optionally, the carbon source is selected from one or more of starch, lignin, viscose fiber, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose.

[0031] Optionally, the compound containing a Group IVB metal is selected from one or more of zirconium tetrachloride, zirconium acetate, zirconium isopropoxide, titanium tetrachloride, titanium oxysulfate, ammonium fluorotitanate, zirconium sulfate, zirconium nitrate, zirconium oxychloride, titanium(IV) sulfate, tetrabutyl titanate, titanium trichloride, and titanium(III) sulfate.

[0032] Optionally, the first solvent is selected from one or more of deionized water, ethanol, acetone, and n-hexane.

[0033] As a fourth aspect, the present invention provides a method for producing the catalytic cracking catalyst provided in the second aspect of the present invention. The method includes a step of mixing the Y-type zeolite, the modified β-zeolite provided in the first aspect of the present invention, the clay, the heat-resistant inorganic oxide, and a second solvent to obtain a second slurry, a step of granulating the obtained second slurry, and a step of performing drying and / or a second calcination.

[0034] Optionally, the drying temperature is 80°C to 200°C, and the drying time is 0.5 hour to 24 hours; the temperature of the second calcination is 350°C to 700°C, and the time of the second calcination is 0.5 hour to 5 hours.

[0035] In a fifth aspect, the present invention provides the use of the modified β-zeolite provided in the first aspect of the present invention or the catalytic cracking catalyst provided in the second aspect of the present invention in the catalytic cracking of heavy oil.

[0036] By the above technical solution, the modified β-zeolite of the present invention has an excellent acid distribution and Group IVB metal distribution, and the catalytic cracking catalyst containing this modified β-zeolite has good catalytic performance. When used in the catalytic cracking process of heavy oil, it has excellent heavy oil cracking performance. The catalytic cracking catalyst can increase the concentration of C4 olefins in liquefied gas, and increase the yield and selectivity of C4 olefins without reducing the yields of gasoline and liquefied gas.

[0037] The method of the present invention is simple, can improve the state and amount of Group IVB metal oxides distributed on β-zeolite, adjust the channel distribution of β-zeolite, and enables the production of modified β-zeolite with good physicochemical properties.

[0038] Other features and effects of the present invention are detailed in part of the following specific embodiments.

[0039] 〔Specific Embodiments〕 Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described herein are not intended to limit the present invention, but only to illustrate and explain the present invention.

[0040] In a first aspect, the present invention provides a modified β-zeolite containing 0.5 wt% to 15 wt%, for example 2 wt% to 13.5 wt% of a Group IVB metal element in terms of the oxide based on the dry basis weight of the modified β-zeolite. The number of centers with a medium acid strength in the modified β-zeolite accounts for 30% to 60%, for example 30% to 50% of the total acid amount, and the number of strong acid centers accounts for 5% to 25%, for example 10% to 25% of the total acid amount. The ratio of B acid to L acid is 0.8 or more, for example, 0.9 to 1.5. The ratio of the weight content of the Group IVB metal element in the main body phase of the modified β-zeolite to the weight content of the Group IVB metal element on the surface is 0.1 to 0.8, for example, 0.15 to 0.45.

[0041] Compared with the conventional β-zeolite, the modified β-zeolite of the present invention has an excellent acid distribution and a ratio of B acid to L acid, and the number of centers with a medium acid strength increases, which optimizes the ratio of the isomerization reaction to the decomposition reaction of the carbenium ion in the catalytic cracking reaction process, contributes to the isomerization reaction of C6 - C10 olefins generated in the catalytic cracking process prior to the β-position cleavage reaction, and increases the selectivity of C4 olefins; on the other hand, the modified β-zeolite has an excellent ability to decompose heavy oil.

[0042] According to the present invention, the Group IVB metal element is Zr and / or Ti, preferably Zr. The weight of the Zr element is based on ZrO2, and the weight of the Ti element is based on TiO2. According to the present invention, the Group IVB metal element on the surface of the β-zeolite may exist in the form of an oxide of the Group IVB metal. In a preferred embodiment, the Group IVB metal oxide is ZrO2 and / or TiO2, more preferably ZrO2.

[0043] In a preferred embodiment, the modified β-zeolite contains, in terms of oxides, 1 wt% to 12 wt%, for example 2 wt% to 12 wt%, of a Group IVB metal element based on the dry basis weight of the modified β-zeolite. The number of central acid sites with medium acid strength accounts for 35% to 55%, for example 35% to 50% or 35% to 45%, of the total acid amount, and the number of strong acid sites accounts for 5% to 20%, for example 10% to 20%, of the total acid amount. The ratio of Bronsted acid to Lewis acid is 0.8 or more, for example 1.0 to 1.5 or 1.1 to 1.5. The ratio of the weight content of the Group IVB metal element in the main phase of the modified β-zeolite to the weight content of the Group IVB metal element on the surface is 0.1 to 0.6, for example 0.15 to 0.45.

[0044] In a second aspect of the present invention, there is provided a catalytic cracking catalyst containing, based on the dry basis weight of the catalytic cracking catalyst, 20 wt% to 50 wt% of Y-type zeolite, 2 wt% to 40 wt% of modified β-zeolite, 10 wt% to 70 wt% of clay, and 5 wt% to 60 wt% of a heat-resistant inorganic oxide, wherein the modified β-zeolite is the modified β-zeolite provided in the first aspect of the present invention.

[0045] The inventor of the present invention has found that the combination of Y-zeolite and modified β-zeolite can not only further increase the selectivity of C4 olefins, but also promote the cracking treatment of heavy oil polymers, reduce the yields of oil slurry and diesel oil, increase the yield of gasoline, and provide more potential components for increasing the production amount of C4 olefins. When the catalytic cracking catalyst of the present invention is used in the catalytic cracking process of heavy oil, the concentration of C4 olefins in the liquefied gas can be increased, and the yield and selectivity of C4 olefins can be increased without reducing the yields of gasoline and liquefied gas.

[0046] In a preferred embodiment, the catalytic cracking catalyst contains 30 wt% to 45 wt% of the Y-type zeolite, 5 wt% to 30 wt% of the modified β-zeolite, 10 wt% to 50 wt% of the clay, and 5 wt% to 40 wt% of the heat-resistant inorganic oxide.

[0047] According to the present invention, the heat-resistant inorganic oxide can be selected from heat-resistant inorganic oxides such as one or more of aluminum oxide, silicon oxide, and amorphous silica-alumina, which are used as the matrix and / or binder component of the catalytic cracking catalyst. These heat-resistant inorganic oxides themselves and their production methods are well known to those skilled in the art.

[0048] According to the present invention, the Y-type zeolite and the clay are well known to those skilled in the art. For example, the Y-type zeolite can be selected from one or more of Y-type zeolites containing phosphorus and / or rare earths, ultrastable Y zeolites, and ultrastable Y zeolites containing phosphorus and / or rare earths; the clay can be selected from one or more of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite, and sepiolite.

[0049] In a third aspect, the present invention provides a method for producing the modified β-zeolite provided in the first aspect of the present invention. The method includes Step (1): Mixing a compound containing a Group IVB metal, a carbon source, and a first solvent, and adjusting the pH value of the mixture to 4 to 9 to obtain a first slurry, wherein the carbon source includes a natural polymer organic compound and / or a semi-synthetic polymer organic compound; Step (2): Mixing the first slurry and β-zeolite by stirring at 20°C to 100°C for 10 minutes to 180 minutes, taking out the solid matter, and performing a first calcination at 350°C to 650°C for 0.5 hour to 5 hours.

[0050] The atmosphere of the first calcination is not particularly limited. For example, it can be an air atmosphere and / or an inert atmosphere, and the inert gas in the inert atmosphere is selected from one or more of nitrogen, helium, and argon. The temperature and time of mixing performed in step (1) are not particularly limited. For example, mixing can be performed at 40°C to 90°C for 30 minutes to 120 minutes. The method of taking out the solid matter is not particularly limited, but for example, a filtration method or a heat drying method can be used, and the filtration method is preferred.

[0051] According to the present invention, the weight ratio of the amount of the compound containing a Group IVB metal to the amount of the β-zeolite can be (0.005 to 0.15):1, and the weight ratio of the amount of the β-zeolite to the amount of the carbon source can be 1:(0.001 to 0.15). The compound containing a Group IVB metal is based on the oxide of the Group IVB metal, and the β-zeolite is based on the dry basis weight. Preferably, the weight ratio of the amount of the compound containing a Group IVB metal to the amount of the β-zeolite is (0.01 to 0.12):1, and the weight ratio of the amount of the β-zeolite to the amount of the carbon source is 1:(0.005 to 0.10). More preferably, the compound containing a Group IVB metal is a compound containing Zr and / or a compound containing Ti.

[0052] According to the present invention, the carbon source can be a polymer organic compound such as a natural polymer compound and / or a semi-synthetic polymer compound. In a specific embodiment, the carbon source can be selected from one or more of starch, lignin, viscose fiber, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose. The weight content of the Group IVB metal element on the surface of the modified β-zeolite produced from the polymer organic compound and / or the semi-synthetic polymer organic compound is higher than the content of the Group IVB metal element in the bulk phase. The modified β-zeolite has relatively excellent catalytic performance. When used in the catalytic cracking process of heavy oil, the modified β-zeolite can increase the concentration of C4 olefins in the liquefied gas, and increase the yield and selectivity of C4 olefins without reducing the yields of gasoline and liquefied gas.

[0053] According to the present invention, the Group IVB metal in the compound containing a Group IVB metal can be titanium and / or zirconium. In certain embodiments, the compound containing a Group IVB metal can be selected from one or more of zirconium tetrachloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, zirconium acetate, zirconium isopropoxide, titanium tetrachloride, titanium oxysulfate, ammonium fluorotitanate, titanium sulfate, tetrabutyl titanate, titanium trichloride, and titanium(III) sulfate. The type of the first solvent is not particularly limited as long as the compound containing a Group IVB metal can be dissolved and the β-zeolite can be dispersed therein. For example, the first solvent can be selected from one or more of deionized water, ethanol, acetone, and n-hexane.

[0054] According to the present invention, the β-zeolite is well-known to those skilled in the art. For example, the β-zeolite can be selected from one or more of a hydrogen form β-zeolite, a sodium form β-zeolite, a β-zeolite containing phosphorus, a β-zeolite containing a rare earth metal, and a β-zeolite containing phosphorus and a rare earth metal, and preferably, a hydrogen form β-zeolite and a β-zeolite containing phosphorus.

[0055] According to the present invention, in step (1), the pH value of the first slurry can be adjusted to 5 to 8. Preferably, the pH value of the first slurry is adjusted to 6 to 8. The method for adjusting the pH value is not particularly limited. For example, the pH value of the first slurry can be adjusted by adding an alkaline solution which can be one or more of aqueous ammonia, an aqueous solution of water glass, an aqueous solution of sodium metaaluminate, and an aqueous solution of sodium hydroxide, preferably aqueous ammonia, and preferably can be aqueous ammonia. The concentration of the alkaline solution can vary within a wide range. In certain embodiments, OH -The concentration of the alkaline solution based on [substance] can be 2 wt% to 20 wt%, and preferably can be 3 wt% to 15 wt%. In another specific embodiment, the alkaline solution is diluted aqueous ammonia with a concentration of 2 wt% to 20 wt%, preferably 3 wt% to 15 wt% based on NH₃. By adjusting the pH value of the mixture, the Group IVB metal ions can form hydroxide precipitates, which helps the precipitates containing Group IVB metals to be uniformly dispersed in the surface of the β-zeolite.

[0056] In a third aspect, the present invention provides a method for manufacturing the catalytic cracking catalyst manufactured in the second aspect of the present invention. The method includes a step of mixing the Y-zeolite, the modified β-zeolite manufactured in the first aspect of the present invention, the clay, the heat-resistant inorganic oxide, and a second solvent to obtain a second slurry, a step of granulating the obtained second slurry, and a step of performing drying and / or a second calcination.

[0057] According to the present invention, the heat-resistant inorganic oxide includes the heat-resistant inorganic oxide itself and / or a precursor of the heat-resistant inorganic oxide. The heat-resistant inorganic oxide itself can be selected from one or more of heat-resistant inorganic oxides used as a matrix and / or binder component of the catalytic cracking catalyst, such as, for example, one or more of aluminum oxide, silicon oxide, and amorphous silica-alumina. The precursor of the heat-resistant inorganic oxide refers to a substance that can form the heat-resistant inorganic oxide in the step of manufacturing the catalyst of the present invention. For example, the precursor of aluminum oxide can be selected from one or more of aluminum sol, boehmite, bayerite, aluminum trihydroxide, and amorphous aluminum hydroxide; for example, the precursor of silicon oxide can be selected from one or more of silica sol, silica gel, and water glass. These heat-resistant inorganic oxides themselves and / or precursors of heat-resistant inorganic oxides and their manufacturing methods are well known to those skilled in the art.

[0058] In a preferred specific embodiment, the clay, the heat-resistant inorganic oxide and the first solvent are subjected to strong beating. The obtained slurry, the modified β-zeolite and the Y-type zeolite are mixed and stirred. By spray granulation, firing, optionally washing and drying, the catalytic cracking catalyst of the present invention is obtained. Preferably, the acid is added during or after strong beating. The pH value of the slurry is adjusted to 1 to 5, preferably 2 to 4, and the slurry is aged at 30°C to 90°C for 0.5 hour to 5 hours. The acid can be a water-soluble inorganic acid or an organic acid, and preferably can be one or more of hydrochloric acid, nitric acid and phosphoric acid. Here, the methods and conditions of spray drying are well known to those skilled in the art and will not be described herein.

[0059] In the present invention, the solid content of the second slurry can vary within a wide range. For example, the solid content of the second slurry is 15% by weight to 50% by weight, preferably 20% by weight to 45% by weight.

[0060] According to the present invention, the drying temperature is 80°C to 200°C, and the drying time is 0.5 hour to 24 hours. Preferably, the drying temperature is 80°C to 120°C, and the drying time is 0.5 hour to 12 hours. The temperature of the second firing can be 350°C to 700°C, and the time of the second firing can be 0.5 hour to 5 hours. Preferably, the temperature of the second firing is 400°C to 650°C, and the time of the second firing is 1 hour to 4 hours. The firing can be carried out under any atmosphere, such as an air atmosphere.

[0061] In a fourth aspect of the present invention, there is provided the use of the modified β-zeolite produced in the first aspect of the present invention or the catalytic cracking catalyst produced in the second aspect of the present invention in the catalytic cracking of heavy oil.

[0062] The present invention will be further described in the following examples, but the present invention is not limited thereby.

[0063] Kaolin is manufactured by Suzhou Kaolin Company, and the solid content is 76% by weight.

[0064] The content of aluminum oxide in the aluminum sol is 21.5% by weight.

[0065] Pseudoboehmite is manufactured in an aluminum factory in Shandong, and the solid content is 62.0% by weight.

[0066] The solid content of the acidified pseudoboehmite is 12.0% by weight and it is acidified with hydrochloric acid. When acidified, the molar ratio of the acid (HCl) to aluminum oxide is 0.15.

[0067] The ultra-stable Y zeolite (USY) adopted has a solid content of 94.7%, a unit cell constant of 24.48 Å, and in weight percentage, the Na2O content is 1.3% and the RE2O3 content is 2.5%.

[0068] The rare earth ultra-stable Y zeolite (REUSY) has a solid content of 84.8%, a unit cell constant of 24.51 Å, and in weight percentage, the Na2O content is 1.6% and the RE2O3 content is 12.0%.

[0069] The Y zeolite containing phosphorus (PREHY) has a solid content of 92.4%, a unit cell constant of 24.59 Å, and in weight percentage, the Na2O content is 1.5%, the P2O5 content is 7.5%, and the RE2O3 content is 8.5%.

[0070] The hydrogen form β zeolite has a solid content of 75%, SiO2 / Al2O3 (molar ratio) = 25, and a Na2O content of 0.15%.

[0071] The phosphorus-modified β zeolite has a solid content of 82.5%, SiO2 / Al2O3 (molar ratio) = 25, a Na2O content of 0.15%, and a P2O5 content of 7.0%.

[0072] All of the above Y zeolite and β zeolite are manufactured by Sinopec Catalyst Co., Ltd., and other reagents are manufactured by Sinopharm Chemical Reagent Co., Ltd. The grade of all reagents is analytical purity. Among the above contents, those not specifically indicated are in weight percentage.

[0073] The concentration of diluted aqueous ammonia based on NH3 is 12 wt%.

[0074] (Method for testing the properties of modified β zeolite) (1) Measurement of acid amount and acid strength: Using the thermogravimetric programmed temperature desorption (TG-TPD) method, with NH3 as the alkali adsorption gas, saturate the zeolite sample at room temperature. Then, measure the weight loss of NH3 during programmed temperature increase and desorption by thermogravimetric differential thermogravimetry (PCT-2). The desorption amount of NH3 is the acid amount of the sample. The temperature ranges of the weak acid centers, medium acid strength centers, and strong acid centers of the zeolite are 120 °C to 270 °C, 270 °C to 390 °C, and 390 °C to 560 °C, respectively. The molar amount of NH3 desorbed in the corresponding temperature range corresponds to the acid amount of the zeolite.

[0075] (2) Bronsted acid and Lewis acid: The surface acidity of the catalyst is characterized by a Nicolet 560 infrared spectrometer manufactured by US Nicolet, and the wave number is 1400 cm -1 ~1700 cm -1 . The Bronsted acid in the catalyst is characterized by a characteristic peak at 1540 cm -1 , and the Lewis acid in the catalyst is characterized by a characteristic peak at 1450 cm -1 . Based on the integral calculation of the corresponding peak areas, the ratio of Bronsted acid to Lewis acid refers to the ratio of the peak area of the characteristic peak of Bronsted acid to the peak area of the characteristic peak of Lewis acid.

[0076] (3) Weight content of Group IVB metal elements on the surface of the modified β-zeolite and weight content of Group IVB metal elements in the bulk phase: The weight content of Group IVB metal elements on the surface of the zeolite refers to the weight content of Group IVB metal elements in the range of 2 nm to 5 nm on the surface of the zeolite, analyzed using X-ray photoelectron spectroscopy (XPS).

[0077] The weight content of Group IVB metal elements in the bulk phase of the modified β-zeolite is the weight content of Group IVB metal elements in the zeolite, analyzed by chemical elemental analysis and quantification method (ICP (Jarrell-Ash, ICAP 9000)).

[0078] In this application, the Group IVB metal elements contained in the modified β-zeolite refer to the Group IVB metal elements contained in the bulk phase of the modified β-zeolite. The weight content of Group IVB metal elements based on the oxides contained in the modified β-zeolite can be obtained by converting the weight content of Group IVB metal elements measured in the bulk phase of the modified β-zeolite. The conversion method is well-known to those skilled in the art and will not be described here. The characteristics of the modified β-zeolites produced in the examples and comparative examples are shown in Table 1.

[0079] Analysis of the composition of the catalyst: X-ray fluorescence spectroscopy (XRF) is used.

[0080] The analysis results of the composition of the catalyst are shown in Tables 2 to 4.

[0081] Examples 1 to 8 are production examples of the modified β-zeolite. Comparative Examples 1 to 4 are comparative examples of the production of the modified β-zeolite.

[0082] (Example 1) (1) 2250 g of deionized water, 39.23 g of zirconium oxychloride (ZrOCl2·8H2O), and 7.5 g of hydroxypropyl methylcellulose were mixed. The pH of the mixture was adjusted to 7.0 using diluted aqueous ammonia. The mixture was stirred for 40 minutes to obtain the first slurry; (2) The first slurry and 150 g of hydrogen-type β-zeolite were mixed and stirred at 40 °C for 90 minutes. The mixture was filtered. The obtained filter cake was calcined at 550 °C for 2 hours in an air atmosphere to obtain the modified β-zeolite of the present invention, which was recorded as B1.

[0083] Here, the weight ratio of the amount of zirconium oxychloride, the amount of β-zeolite, and the amount of hydroxypropyl methylcellulose is 0.1:1:0.05. The zirconium oxychloride is based on zirconia, and the β-zeolite is based on the dry basis weight.

[0084] (Example 2) (1) 1500 g of deionized water, 28.34 g of zirconium isopropoxide, and 3 g of methylcellulose were mixed. The pH of the mixture was adjusted to 5.0 using diluted ammonia water. The mixture was stirred for 60 minutes to obtain the first slurry; (2) The first slurry and 150 g of hydrogen-type β-zeolite were mixed and stirred at 60 °C for 120 minutes. The mixture was filtered. The obtained filter cake was calcined at 500 °C for 3 hours in an air atmosphere to obtain the modified β-zeolite of the present invention, which was recorded as B2.

[0085] Here, the weight ratio of the amount of zirconium isopropoxide, the amount of β-zeolite, and the amount of methylcellulose is 0.06:1:0.02. The zirconium isopropoxide is based on zirconia, and the β-zeolite is based on the dry basis weight.

[0086] (Example 3) (1) 750 g of deionized water, 10.45 g of zirconium nitrate (Zr(NO3)4·5H2O), and 0.8 g of lignin were mixed. The pH of the mixture was adjusted to 5 using diluted ammonia water. The mixture was stirred for 30 minutes to obtain the first slurry; (2) The first slurry and 150 g of hydrogen-type β-zeolite were mixed and stirred at 80 °C for 180 minutes. The mixture was filtered. The obtained filter cake was calcined at 550 °C for 1 hour in an air atmosphere to obtain the modified β-zeolite of the present invention, which was recorded as B3.

[0087] Here, the weight ratio of the amount of zirconium nitrate, the amount of β-zeolite, and the amount of lignin is 0.02:1:0.005. The zirconium nitrate is based on zirconia, and the β-zeolite is based on the dry basis weight.

[0088] (Example 4) (1) 3000 g of deionized water, 47.08 g of zirconium oxychloride (ZrOCl2·8H2O), and 15 g of viscose fiber were mixed. The pH of the mixture was adjusted to 7.5 using diluted aqueous ammonia. The mixture was stirred for 60 minutes to obtain the first slurry; (2) The first slurry and 150 g of hydrogen-type β-zeolite were mixed and stirred at 45 °C for 85 minutes. The mixture was filtered. The obtained filter cake was calcined at 450 °C for 3 hours in an air atmosphere to obtain the modified β-zeolite of the present invention, which was recorded as B4.

[0089] Here, the weight ratio of the amount of zirconium oxychloride, the amount of β-zeolite, and the amount of viscose fiber is 0.12:1:0.1. The zirconium oxychloride is based on zirconia, and the β-zeolite is based on the dry basis weight.

[0090] (Example 5) (1) 1500 g of deionized water, 18.9 g of zirconium isopropoxide, and 6 g of hydroxyethyl cellulose were mixed. The pH of the mixture was adjusted to 5.5 using diluted aqueous ammonia. The mixture was stirred for 30 minutes to obtain the first slurry; (2) The first slurry and 150 g of phosphorus-modified β-zeolite were mixed and stirred at 80 °C for 60 minutes. The mixture was filtered. The obtained filter cake was calcined at 550 °C for 2 hours in an air atmosphere to obtain the modified β-zeolite of the present invention, which was recorded as B5.

[0091] Here, the weight ratio of the amount of zirconium isopropoxide, the amount of β-zeolite, and the amount of hydroxyethyl cellulose is 0.04:1:0.04. The zirconium isopropoxide is based on zirconia, and the β-zeolite is based on the dry basis weight.

[0092] (Example 6) In step (1), 2250 g of deionized water, 39.23 g of zirconium oxychloride (ZrOCl₂·8H₂O), and 0.12 g of hydroxypropyl methylcellulose were mixed, and the pH of the mixture was adjusted to 7.0 using diluted aqueous ammonia, and the mixture was stirred for 40 minutes to give a first slurry. Modified β-zeolite B6 was produced in the same manner as in Example 1, except for the above.

[0093] Here, the weight ratio of the amount of zirconium oxychloride, the amount of β-zeolite, and the amount of hydroxypropyl methylcellulose is 0.10:1:0.0008. Zirconium oxychloride is based on zirconia, and β-zeolite is based on the dry basis weight.

[0094] (Example 7) In step (1), 2250 g of deionized water, 62.78 g of zirconium oxychloride (ZrOCl₂·8H₂O), and 7.5 g of hydroxypropyl methylcellulose were mixed, and the pH of the mixture was adjusted to 7.0 using diluted aqueous ammonia, and the mixture was stirred for 40 minutes to give a first slurry. Modified β-zeolite B7 was produced in the same manner as in Example 1, except for the above.

[0095] Here, the weight ratio of the amount of zirconium oxychloride, the amount of β-zeolite, and the amount of hydroxypropyl methylcellulose is 0.16:1:0.05. Zirconium oxychloride is based on zirconia.

[0096] (Example 8) In step (1), 2250 g of deionized water, 35.61 g of titanium tetrachloride, and 7.5 g of hydroxypropyl methylcellulose were mixed, and the pH of the mixture was adjusted to 7.0 using diluted aqueous ammonia, and the mixture was stirred for 40 minutes to give a first slurry. Modified β-zeolite B8 was produced in the same manner as in Example 1, except for the above.

[0097] Here, the weight ratios of the amounts of titanium tetrachloride, β-zeolite, and hydroxypropyl methylcellulose are 0.1:1:0.05. The titanium tetrachloride is based on titanium oxide, and the β-zeolite is based on the dry basis weight.

[0098] (Comparative Example 1) Modified β-zeolite was produced in the same manner as in Example 1, except that the pH of the first slurry was not adjusted. (1) 2250 g of deionized water, 39.2 g of zirconium oxychloride ZrOCl₂·8H₂O, and 7.5 g of hydroxypropyl methylcellulose were mixed. The mixture was stirred for 40 minutes to obtain a first slurry. The pH of the obtained slurry was 1.4. (2) The first slurry and 200 g of hydrogen-type β-zeolite were mixed and stirred at 40 °C for 90 minutes. The mixture was filtered. The obtained filter cake was calcined at 550 °C for 2 hours in an air atmosphere to obtain a comparative β-zeolite, which was recorded as DB1.

[0099] (Comparative Example 1’) Modified β-zeolite was produced in the same manner as in Example 1, except that the pH of the first slurry was not adjusted. (1) 2250 g of deionized water, 39.23 g of zirconium oxychloride ZrOCl₂·8H₂O, and 7.5 g of hydroxypropyl methylcellulose were mixed. The mixture was stirred for 40 minutes to obtain a first slurry. The pH of the obtained slurry was 1.4. (2) The first slurry and 150 g of hydrogen-type β-zeolite were mixed and stirred at 40 °C for 90 minutes. The mixture was filtered. The obtained filter cake was calcined at 550 °C for 2 hours in an air atmosphere to obtain a comparative β-zeolite, which was recorded as DB1-1.

[0100] (Comparative Example 2) Modified β-zeolite was produced in the same manner as in Example 2, except that a carbon source was not added. (1) 1500 g of deionized water and 28.3 g of zirconium isopropoxide were uniformly mixed. The pH of the mixture was adjusted to 5.0 using diluted aqueous ammonia. The mixture was stirred for 60 minutes to obtain a first slurry; (2) The first slurry and 200 g of hydrogen-type β-zeolite were mixed, heated to 60 °C, and stirred for 120 minutes. The mixture was filtered. The obtained filter cake was calcined at 500 °C for 3 hours in an air atmosphere to obtain a comparative β-zeolite, which was recorded as DB2.

[0101] (Comparative Example 2’) A modified β-zeolite was produced in the same manner as in Example 2, except that no carbon source was added. (1) 1500 g of deionized water and 28.34 g of zirconium isopropoxide were uniformly mixed. The pH of the mixture was adjusted to 5.0 using diluted aqueous ammonia. The mixture was stirred for 60 minutes to obtain a first slurry; (2) The first slurry and 150 g of hydrogen-type β-zeolite were mixed, heated to 60 °C, and stirred for 120 minutes. The mixture was filtered. The obtained filter cake was calcined at 500 °C for 3 hours in an air atmosphere to obtain a comparative β-zeolite, which was recorded as DB2-1.

[0102] (Comparative Example 3) The modified β-zeolite was prepared by a conventional aqueous solution impregnation method.

[0103] At room temperature, 200 g of Hβ-zeolite was pulped with 1500 g of deionized water. Then, 45 g of (NH4)2SO4 was added and uniformly mixed. Then, the mixture was heated at 90 °C for 1 hour for exchange, filtered, and washed with deionized water. The filter cake was calcined at 600 °C for 2 hours to obtain a hydrogen-type β-zeolite.

[0104] 47.1 g of zirconium oxychloride (ZrOCl₂·8H₂O) was dissolved in 200 g of deionized water to form an impregnation solution, and the obtained impregnation solution was uniformly mixed with the treated Hβ zeolite. The mixture was left at room temperature for 1 hour and then calcined at 500 °C for 4 hours to obtain a modified β zeolite, which was recorded as DB3.

[0105] (Comparative Example 4) The modified β zeolite was produced by the organic solvent solution impregnation method and recorded as DB4.

[0106] At room temperature, 200 g of Hβ zeolite was pulped with 1500 g of deionized water. Then, 45 g of (NH₄)₂SO₄ was added and uniformly mixed. Then, the mixture was heated at 90 °C for 1 hour for exchange, filtered, and washed with deionized water. The filter cake was calcined at 600 °C for 2 hours to obtain a hydrogen-type β zeolite.

[0107] 47.1 g of zirconium oxychloride (ZrOCl₂·8H₂O) was dissolved in 200 g of ethanol to form an impregnation solution, and the obtained impregnation solution was uniformly mixed with the treated β zeolite. The mixture was left at room temperature for 1 hour and then calcined at 500 °C for 4 hours to obtain a modified β zeolite, which was recorded as DB4.

[0108] Examples 9 to 22 are examples of catalytic cracking catalysts containing the modified β zeolite of the present invention. Comparative Examples 5 to 8 and Comparative Examples 9 to 10 are comparative examples of catalytic cracking catalysts containing comparative modified β zeolites.

[0109] (Example 9) 447 g of kaolin, 372 g of aluminum sol, and 513 g of deionized water were put into a beating tank and beaten. Subsequently, 1666 g of acidified pseudo-boehmite was added. After stirring for 60 minutes, 271 g of REUSY zeolite and 150 g of modified beta zeolite B1 (dry basis) were further added, and it was beaten together with 578 g of deionized water and dispersed (stirred) uniformly for 30 minutes to form a slurry. Subsequently, the obtained slurry was spray-dried for forming. This was calcined at 500 °C for 2 hours to obtain the catalytic cracking catalyst C1 provided by the present invention.

[0110] (Examples 10 to 16) Catalytic cracking catalysts C2 to C8 were produced in the same manner as in Example 9, except that the modified beta zeolites for producing the catalytic cracking catalysts were the modified beta zeolites B2 to B8 produced in Examples 2 to 8, respectively.

[0111] (Comparative Examples 5, 5', 6, 6', 7, and 8) Catalytic cracking catalysts DC1, DC1-1, DC2, DC2-1, DC3, and DC4 were produced in the same manner as in Example 9, except that the modified beta zeolites for producing the catalytic cracking catalysts were the modified beta zeolites DB1, DB1-1, DB2, DB2-1, DB3, and DB4 produced in Comparative Examples 1, 1', 2, 2', 3, and 4, respectively.

[0112] (Example 17) 421 g of kaolin, 372 g of aluminum sol, and 487 g of deionized water were put into a beating tank and beaten. Subsequently, 1666 g of acidified pseudo-boehmite was added. After stirring for 60 minutes, 105 g of USY zeolite, 236 g of REUSY, and 100 g of modified beta zeolite B1 (dry basis) were further added, and it was beaten together with 847 g of deionized water and dispersed (stirred) uniformly for 30 minutes to form a slurry. Subsequently, the obtained slurry was spray-dried for forming. This was calcined at 500 °C for 2 hours to obtain the catalytic cracking catalyst C9 provided by the present invention.

[0113] (Example 18) 421 g of kaolin, 372 g of aluminum sol, and 537 g of deionized water were placed in a beating tank and beaten. Subsequently, 1666 g of acidified pseudo-boehmite was added. After stirring for 60 minutes, 294 g of REUSY zeolite and 150 g of modified β-zeolite B2 (dry basis) were further added, and it was beaten together with 560 g of deionized water and uniformly dispersed (stirred) for 30 minutes to form a slurry. Then, the obtained slurry was spray-dried for shaping. This was calcined at 500 °C for 2 hours to obtain the catalytic cracking catalyst C10 provided by the present invention.

[0114] (Example 19) 421 g of kaolin, 372 g of aluminum sol, and 540 g of deionized water were placed in a beating tank and beaten. Thereafter, 1666 g of acidified pseudo-boehmite was added. After stirring for 60 minutes, 105 g of USY zeolite, 294 g of REUSY zeolite, and 50 g of modified β-zeolite B3 (dry basis) were further added, and it was beaten together with 844 g of deionized water and uniformly dispersed (stirred) for 30 minutes to form a slurry. Then, the obtained slurry was spray-dried for shaping. This was calcined at 500 °C for 2 hours to obtain the catalytic cracking catalyst C11 provided by the present invention.

[0115] (Example 20) 421 g of kaolin, 372 g of aluminum sol, and 487 g of deionized water were placed in a beating tank and beaten. Subsequently, 1666 g of acidified pseudo-boehmite was added. After stirring for 60 minutes, 162 g of PREUSY zeolite and 250 g of modified β-zeolite B4 (dry basis) were further added, and it was beaten together with 640 g of deionized water and uniformly dispersed (stirred) for 30 minutes to form a slurry. Then, the obtained slurry was spray-dried for shaping. This was calcined at 500 °C for 2 hours to obtain the catalytic cracking catalyst C12 provided by the present invention.

[0116] (Example 21) 421 g of kaolin, 372 g of aluminum sol, and 487 g of deionized water were placed in a beating tank and beaten. Subsequently, 1666 g of acidified pseudo-boehmite was added. After stirring for 60 minutes, 105 g of USY zeolite, 259 g of REUSY zeolite, and 80 g of modified β-zeolite B5 (dry basis) were further added, and it was beaten together with 867 g of deionized water and uniformly dispersed (stirred) for 30 minutes to form a slurry. Subsequently, the obtained slurry was spray-dried for forming. This was calcined at 500 °C for 2 hours to obtain the cracking catalyst C13 provided by the present invention.

[0117] (Example 22) 421 g of kaolin, 372 g of aluminum sol, and 487 g of deionized water were placed in a beating tank and beaten. Subsequently, 1666 g of acidified pseudo-boehmite was added. After stirring for 60 minutes, 190 g of USY zeolite, 235 g of REUSY, and 20 g of modified β-zeolite B1 (dry basis) were further added, and it was beaten together with 847 g of deionized water and uniformly dispersed (stirred) for 30 minutes to form a slurry. Subsequently, the obtained slurry was spray-dried for forming. This was calcined at 500 °C for 2 hours to obtain the cracking catalyst C14 provided by the present invention.

[0118] (Comparative Example 9) This comparative example is the production of a cracking catalyst that does not contain β-zeolite.

[0119] According to the method of Example 17, a catalyst was produced. 421 g of kaolin, 372 g of aluminum sol, and 487 g of deionized water were placed in a beating tank and beaten. Subsequently, 1666 g of acidified pseudo-boehmite was added. After stirring for 60 minutes, 211 g of USY zeolite and 236 g of REUSY (dry basis) were further added, and it was beaten together with 841 g of deionized water and uniformly dispersed (stirred) for 30 minutes to form a slurry. Subsequently, the obtained slurry was spray-dried for forming. This was calcined at 500 °C for 2 hours to obtain the comparative cracking catalyst DC5.

[0120] (Comparative Example 10) According to the method of Example 4 of CN104998681A, modified β-zeolite DB5 with phosphorus and iron was produced.

[0121] According to the method of Example 21, a catalyst was produced. 421 g of kaolin, 372 g of aluminum sol, and 487 g of deionized water were put into a beating tank and beaten. Subsequently, 1666 g of acidified pseudo-boehmite was added. After stirring for 60 minutes, 105 g of USY zeolite, 259 g of REUSY zeolite, and 80 g of modified β-zeolite with phosphorus and iron (dry basis) were further added, and it was beaten together with 867 g of deionized water and uniformly dispersed (confused) for 30 minutes to form a slurry. Then, the obtained slurry was spray-dried for forming. This was calcined at 500 °C for 2 hours to obtain a comparative catalytic cracking catalyst DC6.

[0122] (Evaluation of catalytic cracking catalysts) The catalytic cracking catalysts C1 - C8 and DC1 - DC4 were pre-aged in a fixed-bed aging unit at 800 °C for 12 hours using 100% steam, and then evaluated in a small fixed-fluidized bed unit. The characteristics of the reaction feed oil are shown in Table 8. The reaction temperature was 500 °C, and the weight ratio of the catalyst to the oil was 5.92.

[0123] The catalytic cracking catalysts C9 - C14 and DC5 - DC6 were pre-aged in a fixed-bed aging unit at 800 °C for 8 hours using 100% steam, and then evaluated in a small fixed-fluidized bed unit. The characteristics of the reaction feed oil are shown in Table 8. The reaction temperature was 500 °C, and the weight ratio of the catalyst to the oil was 4.0.

[0124] Here, conversion rate = gasoline yield + liquefied gas yield + dry gas yield + coke yield; C4 olefin yield = 1-butene yield + 2-butene yield + isobutylene yield; C4 olefin concentration = C4 olefin yield / liquefied gas yield; C4 olefin selectivity = C4 olefin yield / C4 fraction yield.

[0125] The evaluation results are shown in Tables 5 to 7. In the tables, the strong acid amount / total acid amount refers to the number of strong acid centers in the total acid amount, and the medium acid amount / total acid amount refers to the number of centers with medium acid strength in the total acid amount.

[0126]

Table 1

[0127] From the results in Table 1, it can be seen that if the amount of the added zirconium-containing compound is the same, the modified β-zeolite produced based on Example 1 has a higher zirconia content compared to Comparative Example 1. This indicates that adjusting the pH of the slurry using diluted aqueous ammonia is preferable for fully utilizing the zirconium-containing compound and is useful for depositing the zirconium-containing compound on the surface of β-zeolite, while in Comparative Example 1, the zirconium-containing compound is lost during filtration. Therefore, in Example 1, the ratio of the weight content of the Group IVB metal element in the zeolite bulk phase to the weight content of the Group IVB metal element on the zeolite surface is relatively low, the B acid / L acid ratio is relatively high, and the number of centers with medium acid strength is large. Compared with Comparative Example 3, the modified β-zeolite produced according to the present invention has a higher B acid / L acid and more centers with medium acid strength.

[0128]

Table 2

[0129]

Table 3

[0130]

Table 4

[0131]

Table 5

[0132]

Table 6

[0133]

Table 7

[0134]

Table 8

[0135] The results of Table 5 and Table 7 show that, compared with the catalyst DC1 produced in Comparative Example 5, in the catalyst C1 produced in Example 9 of the present invention, the total yield of gasoline and liquefied gas increased significantly by 1.11%, the yield of heavy oil decreased by 0.16%, the yield of diesel oil decreased by 0.97%, and the yield of C4 olefins increased by 0.65%. In liquefied gas, the concentration of C4 olefins increased by 2.91% and the selectivity of C4 olefins increased by 5.01%. The propylene concentration in liquefied gas hardly changed. Compared with the catalyst DC1-1 produced according to Comparative Example 5', in the catalyst C1 produced in Example 9 of the present invention, the total yield of gasoline and liquefied gas increased significantly by 1.27%, the yield of heavy oil decreased by 0.14%, the yield of diesel oil decreased by 1.14%, and the yield of C4 olefins increased by 0.67%. In liquefied gas, the concentration of C4 olefins increased by 2.95% and the selectivity of C4 olefins increased by 5.17%. The propylene concentration in liquefied gas hardly changed. This indicates that in the present invention, adjusting the pH of the slurry with diluted aqueous ammonia enables the precipitation of the zirconium-containing compound on the surface of β-zeolite, and the produced modified β-zeolite has higher activity and performance for the decomposition of heavy oil and excellent yield and selectivity of C4 olefins.

[0136] Compared with the catalyst DC2 produced in Comparative Example 6, in the catalyst C2 produced in Example 10 of the present invention, the total yield of gasoline and liquefied gas increased significantly by 1.41%, the yield of heavy oil decreased by 0.59%, the yield of diesel oil decreased by 1.31%, and the yield of C4 olefins increased by 0.87%. In the liquefied gas, the concentration of C4 olefins increased by 4.61% and the selectivity of C4 olefins increased by 7.15%. The propylene concentration in the liquefied gas hardly changed. Compared with the catalyst DC2-1 produced according to Comparative Example 6', in the catalyst C2 produced in Example 10 of the present invention, the total yield of gasoline and liquefied gas increased significantly by 1.44%, the yield of heavy oil decreased by 0.64%, the yield of diesel oil decreased by 1.34%, and the yield of C4 olefins increased by 0.86%. In the liquefied gas, the concentration of C4 olefins increased by 4.58% and the selectivity of C4 olefins increased by 7.1%. The propylene concentration in the liquefied gas hardly changed. This shows that in the present invention, the modified β-zeolite produced using a carbon source has higher activity and performance for the decomposition of heavy oil and has excellent yields and selectivities of C4 olefins.

[0137] Compared with the catalyst DC3 produced in Comparative Example 7, in the catalyst C5 produced in Example 13 of the present invention, the total yield of gasoline and liquefied gas increased significantly by 2.13%, the yield of heavy oil decreased by 0.10%, the yield of diesel oil decreased by 2.58%, and the yield of C4 olefins increased by 0.76%. In the liquefied gas, the concentration of C4 olefins increased by 4.8% and the selectivity of C4 olefins increased by 5.81%. The propylene concentration in the liquefied gas hardly changed. This shows that the modified β-zeolite containing phosphorus produced in the present invention has higher activity and performance for the decomposition of heavy oil and has excellent yields and selectivities of C4 olefins.

[0138] When the content of the modified β-zeolite in the catalyst is the same amount, in the catalytic cracking catalysts C1 to C9 produced according to Examples 9 to 16 of the present invention, compared with Comparative Examples 5 to 8, the cracking ability of heavy oil is higher, the yield of diesel oil is lower, and the yield of C4 olefins is higher. The C4 olefin concentration in the liquefied gas increases so as to basically hardly change the yield of the liquefied gas.

[0139] Preferred embodiments of the present invention are described in detail as above. However, the present invention is not limited to the specific details of the above-described embodiments. Within the scope of the technical idea of the present invention, various simple modifications can be made to the technical solution of the present invention, and all of these simple modifications are within the protection scope of the present invention.

[0140] Also, it should be made clear that each specific technical feature described in the above-described specific embodiments can be appropriately combined as long as there is no contradiction. In order to avoid unnecessary repetition, the present invention will no longer explain various possible combination methods.

[0141] Furthermore, various embodiments of the present invention can be arbitrarily combined as long as they do not conflict with the idea of the present invention. It should also be regarded as the content disclosed by the present invention.

Claims

1. A modified β-zeolite, comprising 0.5 wt% to 15 wt% of a Group IVB metal element based on the oxide content of the dried reference weight of the modified β-zeolite, the number of centers with a medium acid strength in the modified β-zeolite accounting for 30% to 60% of the total acid amount, the number of strong acid centers in the modified β-zeolite accounting for 5% to 25% of the total acid amount, the ratio of B acid to L acid being 0.8 or more, and the ratio of the weight content of the Group IVB metal element in the bulk phase of the modified β-zeolite to the weight content of the Group IVB metal element on the surface being 0.1 to 0.

8. Modified β-zeolite.

2. The modified β-zeolite according to claim 1, wherein the ratio of the B acid to the L acid is 1.0 to 1.

5.

3. The modified β-zeolite according to claim 1, wherein the number of centers with a medium acid strength accounts for 35% to 55% of the total acid amount.

4. The modified β-zeolite according to claim 1, wherein the number of the strong acid centers accounts for 5% to 20% of the total acid amount.

5. The modified β-zeolite according to claim 1, comprising 1 wt% to 12 wt% of the Group IVB metal element based on the oxide content of the dried reference weight of the modified β-zeolite.

6. The Group IVB metal element is Zr and / or Ti, The weight of the Zr element is based on ZrO ２ and is The weight of the Ti element is TiO ２ The modified β-zeolite according to claim 1 based on

7. The modified β-zeolite according to claim 1, wherein the ratio of the weight content of the Group IVB metal element in the bulk phase of the modified β-zeolite to the weight content of the Group IVB metal element on the surface is 0.1 to 0.

6.

8. A catalytic cracking catalyst, based on the dried reference weight of the catalytic cracking catalyst, comprising 10 wt% to 50 wt% of Y-type zeolite, 2 wt% to 40 wt% of modified β-zeolite, 10 wt% to 70 wt% of clay, and 5 wt% to 60 wt% of a heat-resistant inorganic oxide, wherein the modified β-zeolite is the modified β-zeolite according to any one of claims 1 to 7. Catalytic cracking catalyst.

9. The catalytic cracking catalyst according to claim 8, satisfying one or more of the following (i) to (iii): (i) The Y-type zeolite is selected from one or more of a Y-type zeolite containing phosphorus and / or rare earths, a ultrastable Y zeolite, and a ultrastable Y zeolite containing phosphorus and / or rare earths; (ii) The clay is selected from one or more of kaolin, rectorite, diatomaceous earth, montmorillonite, bentonite, and sepiolite; and / or (iii) The heat-resistant inorganic oxide is selected from one or more of aluminum oxide, silicon oxide, and amorphous silica-alumina.

10. The catalytic cracking catalyst according to claim 8, comprising 15% to 45% by weight of the Y-type zeolite, 5% to 30% by weight of the modified β-zeolite, 10% to 50% by weight of the clay, and 5% to 40% by weight of the heat-resistant inorganic oxide.

11. A method for producing the modified β-zeolite according to any one of claims 1 to 7, the method comprising the following steps: Step (1) Mixing a compound containing a Group IVB metal, a carbon source, and a first solvent, The step of adjusting the pH value of the mixture to 4 to 9 to obtain a first slurry, The carbon source includes a natural polymer organic compound and / or a semi-synthetic polymer organic compound; Step (2) Mixing the first slurry and β-zeolite by stirring at 20°C to 100°C for 10 minutes to 180 minutes, The step of taking out the solid matter and performing a first firing at 350°C to 650°C for 0.5 hour to 5 hours.

12. The method according to claim 11, wherein the pH value of the first slurry is adjusted to 5 to 8 in step (1).

13. The weight ratio of the amount of the compound containing a Group IVB metal to the amount of the β-zeolite is (0.005 to 0.15):1, The weight ratio of the amount of the β-zeolite to the amount of the carbon source is 1:(0.001 to 0.15), The compound containing a Group IVB metal is based on the oxide of the Group IVB metal, The β-zeolite is based on the dry basis weight, the method according to claim 11.

14. The method according to claim 11, satisfying one or more of the following (i) to (iv): (i) The β-zeolite is selected from one or more of a hydrogen-type β-zeolite, a sodium-type β-zeolite, a β-zeolite containing phosphorus, a β-zeolite containing a rare earth metal, and a β-zeolite containing phosphorus and a rare earth metal; (ii) The carbon source is selected from one or more of starch, lignin, viscose fiber, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, and carboxymethyl cellulose; (iii) The compound containing a Group IVB metal is selected from one or more of zirconium tetrachloride, zirconium acetate, zirconium isopropoxide, titanium tetrachloride, titanium oxysulfate, ammonium fluorotitanate, zirconium sulfate, zirconium nitrate, zirconyl chloride, titanium(IV) sulfate, tetrabutyl titanate, titanium trichloride, and titanium(III) sulfate; and / or (iv) The first solvent is selected from one or more of deionized water, ethanol, acetone, and n-hexane.

15. A method for producing the catalytic cracking catalyst according to any one of Claims 8 to 10, comprising: a step of mixing the Y-type zeolite, the modified β-zeolite, the clay, the heat-resistant inorganic oxide, and a second solvent to obtain a second slurry; a step of granulating the obtained second slurry; and a step of performing drying and / or a second calcination, wherein the modified β-zeolite is the modified β-zeolite according to any one of Claims 1 to 7.

16. The temperature of the drying is 80°C to 200°C, the time of the drying is 0.5 hour to 24 hours, the temperature of the second calcination is 350°C to 700°C, and the time of the second calcination is 0.5 hour to 5 hours. The method according to Claim 15.

17. Use of the modified β-zeolite according to any one of Claims 1 to 7 or the catalytic cracking catalyst according to any one of Claims 8 to 10 in the catalytic cracking of heavy oil.

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