Catalytic cracking catalyst, process for its preparation and use

Abstract

The application provides a catalytic cracking catalyst and a preparation method and application thereof. The catalytic cracking catalyst comprises a catalyst A component and a catalyst B component in a weight ratio of 98:2-20:80; raw materials of the catalyst A component comprise 15-55% of modified ZSM-5 molecular sieve, 10-55% of clay, 3-20% of an aluminum source and 5-20% of phosphorus from a second modifier; the modified ZSM-5 molecular sieve is obtained by modifying raw ZSM-5 molecular sieve by using a first modifier; the first modifier comprises a titanium source and a phosphorus source; and raw materials of the catalyst B component comprise 15-50% of Y-type molecular sieve, 10-55% of clay, 5-30% of pseudo-boehmite, 3-20% of a binder and 0-5% of modified metal elements. The application further provides a preparation method of the catalytic cracking catalyst and application thereof in a catalytic cracking process.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oil refining catalysts and adjuvants, and particularly relates to a catalytic cracking catalyst and a preparation method and application thereof. BACKGROUND

[0002] In the production process of polyolefin industry, the widely used catalyst is mainly Ziegler-Natta catalyst, which is a titanium-based catalyst. For the preparation of titanium-based polyolefin catalyst, for example, Chinese patent CN 102336851A discloses a propylene polymerization catalyst, which comprises magnesium, titanium, halogen and a mixture of internal electron donor compounds diisobutyl phthalate, diethyl phthalate or di-n-butyl phthalate and succinate; Chinese patent CN 107434832B discloses a propylene polymerization catalyst, which mainly consists of alcohol magnesium compound, titanium compound and phosphate ester electron donor compound. The common method for preparing titanium-based catalyst at present is: first, the preparation of halogenated magnesium alcoholate, for example, after the halogenated magnesium and alcohol are co-heated and dissolved, high-pressure spraying or high-speed stirring is carried out, and the method of solidifying into microspherical particles in the cooling medium is adopted, see the relevant description in CN1110281A for specific steps; then, the halogenated magnesium alcoholate particles are reacted with halogen-containing compounds such as titanium tetrachloride to prepare a magnesium-supported catalyst, during which various promoters can be added for modification. In the above catalyst preparation process, a large amount of titanium tetrachloride is needed, and the excess ratio is large, and at the same time, the obtained solid catalyst component needs to be washed with hydrocarbon solvent (such as hexane) to remove the un-loaded titanium tetrachloride therein. Therefore, in the production process of polyolefin catalyst, after the catalyst solid is separated and precipitated, a large amount of catalyst mother liquor containing at least one of titanium tetrachloride, unreacted hydrocarbons, unreacted halogenated alkoxy titanium, alkoxy magnesium, and unreacted esters will be produced. A large amount of waste liquid containing titanium tetrachloride is produced in the preparation process of titanium-based polypropylene catalyst, and the content of titanium tetrachloride is about 80%-95% (by weight), which will inevitably cause environmental pollution and resource waste if discharged into the environment. At present, there is a lack of simple and effective method for recycling and treating waste liquid containing titanium tetrachloride to reduce environmental pollution. Moreover, the thermal stability of the existing ZSM-5 molecular sieve is not high, even after modification by known methods, the thermal stability of the ZSM-5 molecular sieve is still not ideal, which is not conducive to the use of the molecular sieve, especially the application of the molecular sieve as a cracking catalyst. In the prior art, for example, Chinese patent CN102114429B discloses a method for increasing the B acid amount of ZSM-5 molecular sieve and realizing the yield increase of low carbon olefins, which is by simultaneously modifying the ZSM-5 molecular sieve with iron and titanium, the mass ratio of iron to titanium in the modified molecular sieve is 0.3-3:1, so that the catalytic reactivity of the molecular sieve is improved, the conversion of long-chain alkanes and aromatic hydrocarbons with long-chain alkyl side chains such as cumene is promoted, and the effect of increasing the yield of low carbon olefins is achieved. US5171921 discloses a method for modifying ZSM-5 molecular sieve, which comprises ammonium exchange, drying and calcination of the synthesized ZSM-5 molecular sieve, and then modification with phosphoric acid, drying and calcination to obtain ZSM-5 molecular sieve containing phosphorus.

[0003] Moreover, the existing technology also needs to overcome the adverse effects of high heavy oil yield, high coke formation, and low light olefin yield of the catalytic cracking catalyst prepared by the existing technology. In the existing technology, for example, Chinese patent CN 101898146 B discloses a catalytic thermal cracking catalyst and a preparation method thereof. The catalyst contains 5-75 wt% of an aluminum binder based on alumina, 0.5-70 wt% of a zeolite with an MFI structure, and 3-25 wt% of a zirconium oxide matrix, wherein the silicon-aluminum ratio of the zeolite with the MFI structure is 15-300, and the primary particle diameter is 5-55 μm. The preparation method of the catalyst comprises the steps of mixing and slushing the zeolite with the MFI structure, the aluminum binder, and the zirconium oxide matrix, and drying, wherein the zirconium oxide matrix is introduced in two steps during the slushing process. The catalyst of the invention is used for catalytic thermal cracking of heavy oil, has high feedstock conversion rate, and good selectivity of light olefins.

[0004] In the existing technology, the treatment of the waste liquid containing titanium tetrachloride generated in the preparation process of the titanium-based polypropylene catalyst is not involved, and the modified ZSM-5 molecular sieve and the corresponding catalytic cracking catalyst also do not involve the need to provide a new technology for preparing a catalytic cracking catalyst with a simple and feasible preparation process and excellent performance in reducing the coke formation tendency and reducing the heavy oil yield. SUMMARY

[0005] In order to solve the above problems, the present application provides a catalytic cracking catalyst and a preparation method and application thereof.

[0006] In order to achieve the above purpose, the present application provides a catalytic cracking catalyst, which comprises a catalyst A component and a catalyst B component in a weight ratio of 98:2-20:80.

[0007] The raw material of the catalyst A component comprises 15%-55% of a modified ZSM-5 molecular sieve, 10%-55% of clay, 3%-20% of an aluminum source, and 5%-20% of phosphorus from a second modifier, based on 100% of the weight of the raw material of the catalyst A component, wherein the weight of the modified ZSM-5 molecular sieve, the clay, and the aluminum source is calculated on a dry basis, and the weight of the phosphorus is calculated as an oxide.

[0008] The modified ZSM-5 molecular sieve is obtained by modifying a raw ZSM-5 molecular sieve with a first modifier; the first modifier comprises a titanium source for providing titanium in the modified ZSM-5 molecular sieve and a phosphorus source for providing phosphorus in the modified ZSM-5 molecular sieve.

[0009] The raw materials of the catalyst B component include, based on 100% by weight of the raw materials of the catalyst B component: 15%-50% of the Y-type molecular sieve, 10%-55% of the clay, 5%-30% of the aluminum source, and 3%-20% of the binder; wherein the weight of the Y-type molecular sieve, the clay, and the aluminum source is on a dry basis, and the weight of the binder is on an oxide basis.

[0010] According to a specific embodiment of the present application, the weight ratio of the catalyst A component to the catalyst B component can be 98:2-20:80, for example, can be 97:3-30:70. In some specific embodiments, the weight ratio of the catalyst A component to the catalyst B component can be 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 85:15, 80:20, 75:25, 70:30, and the like specific values and ranges with any two of the above specific values as endpoints.

[0011] In the modified ZSM-5 molecular sieve, the titanium source and the phosphorus source in the first modifier can jointly modify the ZSM-5 molecular sieve, synergistically improve the acid distribution and hydrothermal stability in the ZSM-5 molecular sieve, thereby promoting the conversion of heavy oil in the catalytic process involving the catalytic cracking catalyst and reducing the amount of coke.

[0012] In the above-mentioned modified ZSM-5 molecular sieve, the modified ZSM-5 molecular sieve includes 0.2%-25% of titanium from the first modifier and 0.2%-6% of phosphorus from the first modifier, based on 100% by weight of the total weight of the modified ZSM-5 molecular sieve; wherein the weight of the titanium and the phosphorus is on an oxide basis, respectively.

[0013] In the above-mentioned modified ZSM-5 molecular sieve, the weight content of the titanium from the first modifier in the modified ZSM-5 molecular sieve is 0.2%-25% on an oxide basis of titanium, and further can be 0.5%-15%. Specifically, the weight content of the titanium from the first modifier in the modified ZSM-5 molecular sieve can be 0.2%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, and the like specific values and ranges with any two of the above specific values as endpoints.

[0014] In the above-mentioned modified ZSM-5 molecular sieve, the weight content of the phosphorus from the first modifier in the modified ZSM-5 molecular sieve is 0.2%-6% on an oxide basis of phosphorus, and further can be 0.5%-6%. Specifically, the weight content of the phosphorus from the first modifier in the modified ZSM-5 molecular sieve can be 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, and the like specific values and ranges with any two of the above specific values as endpoints.

[0015] In the modified ZSM-5 molecular sieve, the modified ZSM-5 molecular sieve can further comprise a modified metal element, and accordingly, the first modifier further comprises a modified metal source for providing the modified metal element. The modified metal element can modify the ZSM-5 molecular sieve to improve the hydrothermal stability, acidity and catalytic reaction performance of the ZSM-5 molecular sieve, etc.

[0016] In some embodiments, the modified metal element from the first modifier accounts for 0-5% by weight in the modified ZSM-5 molecular sieve, such as greater than 0% and less than or equal to 5%, further can be 0.5-5%, 0-3%, etc. Specifically, the modified metal element from the first modifier can account for 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, etc. specific values and ranges with any two of the above specific values as endpoints.

[0017] In the catalytic cracking catalyst, the preparation method of the modified ZSM-5 molecular sieve comprises: mixing the raw ZSM-5 and a titanium source to form a mixed solution, performing first calcination, or, using an impregnation solution containing a titanium source to sufficiently impregnate the raw ZSM-5 molecular sieve, drying, and performing first calcination; mixing the product of the first calcination with a phosphorus source, performing second calcination, to obtain the modified ZSM-5 molecular sieve.

[0018] The preparation method of the modified ZSM-5 molecular sieve does not have special restrictions on the mixing conditions of the titanium source and the raw ZSM-5 molecular sieve, the mixing conditions of the product of the first calcination and the phosphorus source, as long as the components are sufficiently mixed. In some embodiments, the mixing temperature of the titanium source and the raw ZSM-5 molecular sieve can be 4-150°C, and the mixing time can be 10 min-2 h. The mixing temperature of the product of the first calcination and the phosphorus source can be 4-150°C, and the mixing time can be 10 min-2 h.

[0019] In the preparation method of the modified ZSM-5 molecular sieve, the temperature of the first calcination is 450-650°C, and the time of the first calcination is 1-4 h. Specifically, the temperature of the first calcination can be 450°C, 500°C, 550°C, 600°C, 650°C, etc. specific values and ranges with any two of the above specific values as endpoints. The time of the first calcination is 1 h, 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, etc. specific values and ranges with any two of the above specific values as endpoints.

[0020] In the method for preparing the modified ZSM-5 molecular sieve, the temperature of the second calcination is 450-650°C, and the time of the second calcination is 1-4h. Specifically, the temperature of the second calcination can be 450°C, 500°C, 550°C, 600°C, 650°C, and the like, and ranges defined by any two of the above specific values as the end points. The time of the second calcination is 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, and the like, and ranges defined by any two of the above specific values as the end points.

[0021] In the method for preparing the ZSM-5 molecular sieve, when the first modifier comprises a modified metal source, the modified metal source is usually mixed with the titanium source and the raw ZSM-5 molecular sieve together, so as to avoid precipitation between the phosphorus source and the metal.

[0022] In the method for preparing the ZSM-5 molecular sieve, the raw ZSM-5 molecular sieve can have a silicon-aluminum ratio of 15-450. In some specific embodiments, the raw ZSM-5 molecular sieve can be a ZSM-5 molecular sieve with a high silicon-aluminum ratio. Specifically, the raw ZSM-5 molecular sieve can have a silicon-aluminum ratio of 20-450, 30-450, and the like.

[0023] In the method for preparing the ZSM-5 molecular sieve, the raw ZSM-5 molecular sieve can comprise a micro-mesoporous ZSM-5 molecular sieve, i.e., a molecular sieve containing micropores and mesopores; in some specific embodiments, the micro-mesoporous ZSM-5 molecular sieve can have a mesopore volume of not less than 0.10 mL / g, for example, 0.10-0.70 mL / g, 0.10-30 mL / g, 0.30-0.70 mL / g, and the like.

[0024] In the method for preparing the ZSM-5 molecular sieve, the raw ZSM-5 molecular sieve can be added in the form of a slurry, which can be formed by dispersing the raw ZSM-5 molecular sieve into water.

[0025] In the method for preparing the ZSM-5 molecular sieve, the pH value of the mixed solution and / or the impregnation solution can be controlled to be 0.5-8, for example, 0.5-3. By controlling the pH value range of the mixed solution and / or the impregnation solution, the present application is advantageous in controlling the distribution of titanium in the ZSM-5 molecular sieve. In some specific embodiments, the pH value of the mixed solution and / or the impregnation solution can be 0.5, 1, 1.5, 1.8, 2, 3, 4, 5, 6, 7, 8, and the like, and ranges defined by any two of the above specific values as the end points.

[0026] According to a specific embodiment of the present application, the preparation method of the modified ZSM-5 molecular sieve can further comprise the operation of adjusting the pH value of the titanium source and the modified metal source of the first modifier to 0.5-8, for example, 0.5-3, and then mixing the titanium source, the modified metal source and the raw ZSM-5 molecular sieve. By pre-adjusting the pH value of the titanium source and the modified metal source, the dealumination of the molecular sieve caused by the excessively high acidity of the system when the titanium source, the modified metal source and the ZSM-5 molecular sieve are mixed can be avoided. Moreover, by controlling the pH value range, the distribution of the modified elements such as titanium in the modified ZSM-5 molecular sieve can be regulated.

[0027] In some specific embodiments, the pH value of the mixed solution, the impregnation solution, the titanium source and the modified metal source can be adjusted by a pH adjuster, which comprises a basic substance. The basic substance can comprise one or a combination of two or more of ammonia, ammonium carbonate, ammonium bicarbonate, water glass, magnesium oxide, magnesium hydroxide and magnesium carbonate.

[0028] According to a specific embodiment of the present application, the preparation method of the modified ZSM-5 molecular sieve can comprise the operations of adjusting the pH value of the titanium source and the modified metal source of the first modifier to 0.5-8, filtering, and then mixing the filter cake obtained by filtering with the raw ZSM-5 molecular sieve.

[0029] In the above preparation method of the modified ZSM-5 molecular sieve, the mixed solution and / or the impregnation solution further comprises a dispersant. The dispersant can promote the sufficient dispersion of the metal elements in the modified metal source and titanium, which is beneficial to improving the hydrothermal stability of the modified ZSM-5 molecular sieve.

[0030] In some specific embodiments, the mass of the dispersant can be 0-20%, for example, 0.2-20%, 0-10% of the weight of the raw ZSM-5 molecular sieve, and can be further controlled to be 0.3%-6%. In some specific embodiments, the weight ratio of the dispersant to the raw ZSM-5 molecular sieve can be 0.1%, 0.3%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20% and the like, and a range with any two of the above specific values as the end points.

[0031] In the above preparation method, the dispersant comprises one or a combination of two or more of 1,3,5-trimethylbenzene, 1,3,5-triisopropylbenzene, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol and polyethylene glycol.

[0032] In the preparation of the modified ZSM-5 molecular sieve, the dispersant can be added at one time or in several times. Specifically, when the dispersant is added at one time, the dispersant can be added into the mixed solution and / or the impregnation solution, that is, the dispersant is added together with the titanium source, the modified metal source and the raw ZSM-5 molecular sieve, which helps to improve the dispersity of titanium elements and modified metal elements; or, the dispersant can be added together with the phosphorus source, which can improve the dispersity of phosphorus elements. When the dispersant is added in several times, part of the dispersant can be added into the mixed solution containing the titanium source, the modified metal and the raw ZSM-5 molecular sieve or the impregnation solution containing the titanium source and the modified metal source, and the remaining dispersant can be added together with the phosphorus source, so as to improve the dispersity of titanium, phosphorus and modified metal elements in the molecular sieve.

[0033] According to a specific embodiment of the present application, the raw material of the catalyst A component comprises a second modifier, and the second modifier comprises a phosphorus source, and 5%-20% of the phosphorus contained in the raw material of the catalyst A component comes from the second modifier.

[0034] In some specific embodiments, the weight content of the phosphorus in the raw material of the catalyst A component can be 6%-19% in terms of oxide of phosphorus, and the phosphorus comes from the second modifier.

[0035] In some specific embodiments, the weight content of the phosphorus in the raw material of the catalyst A component can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% and the like specific values and ranges with any two of the above specific values as endpoints.

[0036] According to a specific embodiment of the present application, the second modifier can further comprise a titanium source, and the raw material of the catalyst A component contains 0-10%, for example 0.2%-10%, 0.5%-8% of titanium from the second modifier in terms of oxide. In some specific embodiments, the weight content of the titanium from the second modifier in the raw material of the catalyst A component can be 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% and the like specific values and ranges with any two of the above specific values as endpoints.

[0037] According to a specific embodiment of the present application, the titanium contained in the catalyst A component can exist in the form of ions in the interior and surface of the modified ZSM-5 molecular sieve, or can exist in the form of oxide as a carrier in the catalyst.

[0038] According to particular embodiments of the present application, the weight of the titanium source in the second modifier can be 0-9.9%, for example greater than 0 and less than 9.9%, of the weight of the catalyst A component feedstock, calculated as titanium oxide. In some particular embodiments, the weight of the titanium source in the second modifier can be 0.1%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.9%, and the like, as well as ranges having any two of the foregoing particular values as endpoints, of the weight of the catalyst A component feedstock.

[0039] According to particular embodiments of the present application, the second modifier can further include a modifying metal source, the catalyst A component feedstock comprising 0-5%, for example 0-3%, 0.2%-5%, of the modifying metal element from the second modifier, calculated as oxide.

[0040] In some particular embodiments, the weight of the phosphorus in the catalyst A component feedstock can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, and the like, as well as ranges having any two of the foregoing particular values as endpoints, of the weight of the catalyst A component feedstock, calculated as oxide.

[0041] In the catalytic cracking catalyst described above, the catalyst A component can further include a binder.

[0042] In the catalytic cracking catalyst described above, the weight of the binder, calculated as oxide, can be 0-10%, further can be 0-6%, of the weight of the catalyst A component. In some particular embodiments, the weight of the binder, calculated as oxide, can be 0.1%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, and the like, as well as ranges having any two of the foregoing particular values as endpoints, of the weight of the catalyst A component feedstock.

[0043] In the catalytic cracking catalyst described above, the catalyst A component feedstock can include 15%-55%, for example 20%-50%, of the modified ZSM-5 molecular sieve, calculated on a dry basis, of the weight of the catalyst A component feedstock. In some particular embodiments, the weight of the modified ZSM-5 molecular sieve, calculated on a dry basis, can be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, and the like, as well as ranges having any two of the foregoing particular values as endpoints, of the weight of the catalyst A component feedstock.

[0044] In the catalytic cracking catalyst described above, the raw material of the catalyst A component includes 10%-55%, for example, 10%-50% of clay on a dry basis, based on 100% of the weight of the raw material of the catalyst A component. In some specific embodiments, the weight percentage of the clay in the raw material of the catalyst A component can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, and the like specific values and ranges with any two of the above specific values as endpoints, on a dry basis.

[0045] In the catalytic cracking catalyst described above, the raw material of the catalyst A component includes 3%-20%, for example, 3%-15% of an aluminum source on a dry basis, based on 100% of the weight of the raw material of the catalyst A component. In some specific embodiments, the weight percentage of the aluminum source in the raw material of the catalyst A component can be 3%, 5%, 10%, 15%, 20%, and the like specific values and ranges with any two of the above specific values as endpoints, on a dry basis.

[0046] In the catalytic cracking catalyst described above, the clay and the aluminum source in the catalyst A component can synergize with the phosphorus source in the first modifier to improve the adhesion between the components in the catalyst A component, thereby improving the wear resistance of the catalyst A component.

[0047] In the catalytic cracking catalyst described above, the raw material of the catalyst A component includes 20%-50% of modified ZSM-5 molecular sieve, 10%-50% of clay, 3%-15% of pseudoboehmite, 6%-19% of phosphorus in oxide form, 0-6% of binder in oxide form, 0.5%-8% of titanium in oxide form, and 0-3% of modified metal compound on a dry basis, based on 100% of the total weight of the catalyst A component.

[0048] In the catalytic cracking catalyst described above, the raw material of the catalyst B component further includes a third modifier, and the third modifier further includes a modified metal source for providing a modified metal element. The raw material of the catalyst B component further includes 0-5%, for example, 0.5%-3% of the modified metal element in oxide form from the third modifier. In some specific embodiments, the weight percentage of the modified metal element in oxide form from the third modifier in the raw material of the catalyst B component can be 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, and the like specific values and ranges with any two of the above specific values as endpoints.

[0049] In the catalytic cracking catalyst described above, the raw material of the catalyst B component further comprises 0-10% of ZSM-5 molecular sieve on a dry basis, based on 100% of the weight of the raw material of the catalyst B component; preferably, the raw material of the catalyst B component further comprises 0-8% of the ZSM-5 molecular sieve on a dry basis, based on 100% of the weight of the raw material of the catalyst B component. In some specific embodiments, the ZSM-5 molecular sieve is at a specific value of 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, or a range with any two of the above specific values as endpoints.

[0050] The ZSM-5 molecular sieve comprises a raw ZSM-5 molecular sieve and / or a modified ZSM-5 molecular sieve. The preparation method and component composition of the modified ZSM-5 molecular sieve can refer to those of the modified ZSM-5 molecular sieve in the catalyst A component; the raw ZSM-5 molecular sieve is an unmodified ZSM-5 molecular sieve.

[0051] In the catalytic cracking catalyst described above, the raw material of the catalyst B component comprises 15%-50%, for example, 20%-45% of Y-type molecular sieve on a dry basis, based on 100% of the weight of the raw material of the catalyst B component. In some specific embodiments, the Y-type molecular sieve on a dry basis accounts for 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or the like of the weight of the raw material of the catalyst B component, or a range with any two of the above specific values as endpoints.

[0052] In the catalytic cracking catalyst described above, the raw material of the catalyst B component comprises 10%-55% of clay on a dry basis, based on 100% of the weight of the raw material of the catalyst B component. In some specific embodiments, the clay on a dry basis accounts for 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or the like of the weight of the raw material of the catalyst B component, or a range with any two of the above specific values as endpoints.

[0053] In the catalytic cracking catalyst described above, the raw material of the catalyst B component comprises 5-30%, for example, 5%-25% of an aluminum source on a dry basis, based on 100% of the weight of the raw material of the catalyst B component. In some specific embodiments, the aluminum source on a dry basis accounts for 5%, 10%, 15%, 20%, 25%, 30% or the like of the weight of the raw material of the catalyst B component, or a range with any two of the above specific values as endpoints.

[0054] In the catalytic cracking catalyst described above, the feedstock of the catalyst B component includes 3-20%, for example 3-15%, of a binder on a dry basis, based on 100% by weight of the feedstock of the catalyst B component. In some embodiments, the binder, on an oxide basis, can be present in the feedstock of the catalyst B component in an amount of 3%, 5%, 10%, 15%, and the like, as well as ranges having any two of the foregoing values as endpoints.

[0055] In the catalytic cracking catalyst described above, the feedstock of the catalyst B component includes 0-8% of ZSM-5 molecular sieve on a dry basis, 20-45% of Y-type molecular sieve on a dry basis, 10-55% of clay on a dry basis, 5-25% of an aluminum source on a dry basis, 3-15% of a binder on an oxide basis, 2-15% of an inorganic oxide support material on an oxide basis, and 0.5-3% of a modifying metal, based on 100% by weight of the total weight of the feedstock of the catalyst B component.

[0056] In the catalytic cracking catalyst described above, the catalyst B component can further include an inorganic oxide support, the feedstock of the catalyst B component including 0-30%, for example 2-15%, of an inorganic oxide support material on an oxide basis, based on 100% by weight of the feedstock of the catalyst B component. In some embodiments, the inorganic oxide support material, on an oxide basis, can be present in the feedstock of the catalyst B component in an amount of 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, and the like, as well as ranges having any two of the foregoing values as endpoints.

[0057] In some embodiments, the inorganic oxide support includes one or a combination of two or more of fumed silica, an alumina material containing B acid sites, and a silica-alumina material containing B acid sites. The alumina material containing B acid sites and the silica-alumina material containing B acid sites described above have high pore volume, large specific surface area, bimodal pore distribution, high thermal stability, and high acid content, and contain B acid sites.

[0058] In the preparation of the catalytic cracking catalyst described above, the modifying metal element can include one or a combination of two or more of iron, zinc, magnesium, calcium, zirconium, lanthanum, cerium, and yttrium in the first modifier, the second modifier, and the third modifier. In some embodiments, the modifying metal source includes a metal salt and / or a metal oxide. The metal salt can include one or a combination of two or more of chloride, nitrate, carbonate, sulfate, oxalate, and acetate.

[0059] In the modified ZSM-5 molecular sieve, the phosphorus source in the first modifier and the second modifier includes one or more than two combinations of phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphoric acid, pyrophosphate, polyphosphoric acid, polyphosphate, metaphosphoric acid, metaphosphate; preferably, the phosphorus source includes one or more than two combinations of phosphoric acid, ammonium phosphate, dihydrogen ammonium phosphate, dihydrogen ammonium phosphate, magnesium phosphate, aluminum phosphate, phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate.

[0060] In the first modifier and the second modifier, the titanium source refers to a substance containing titanium element, and specifically can include titanium tetrachloride. Further, the titanium source includes a combination of titanium tetrachloride and hexane; in some specific embodiments, the weight ratio of the titanium tetrachloride and the hexane can be (4-34):1, such as 4:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 34:1, and the like specific values and ranges with any two of the above specific values as the end points.

[0061] According to specific embodiments of the present application, the titanium source in the first modifier and / or the second modifier includes a titanium tetrachloride-containing waste liquid, which contains titanium tetrachloride and further can contain hydrocarbons such as hexane.

[0062] The titanium tetrachloride-containing waste liquid can be a titanium tetrachloride-containing waste liquid obtained in the production process of a titanium-based polyolefin (such as polypropylene) catalyst. The titanium tetrachloride-containing waste liquid includes 80%-95% of titanium tetrachloride, 2%-5% of titanium alkoxy complex, and the balance of hydrocarbons, based on 100% of the total weight of the titanium tetrachloride-containing waste liquid; wherein the hydrocarbons are liquid at room temperature and contain hexane and esters, most of which are hexane.

[0063] In the above-mentioned titanium tetrachloride-containing waste liquid, the titanium tetrachloride can be used to modify the ZSM-5 molecular sieve; the hexane can promote the uniform distribution of titanium in the ZSM-5 molecular sieve, increase the pore volume of the modified ZSM-5 molecular sieve, and thus improve the diffusion effect of molecules in the modified ZSM-5 molecular sieve and improve the selectivity of the modified ZSM-5 molecular sieve in catalytic reactions. Moreover, the hydrocarbons such as hexane in the titanium tetrachloride-containing solution can form micropores, mesopores, and the like after calcination, which is conducive to improving the pore structure of the catalyst and improving the catalytic activity.

[0064] In some specific embodiments, the titanium tetrachloride-containing waste liquid can be generated in the preparation process of a titanium-based polypropylene catalyst. The above-mentioned preparation method can solve the problem of waste liquid treatment, save treatment costs, and avoid environmental pollution by using a large amount of titanium tetrachloride-containing waste liquid generated in the preparation process of a titanium-based polypropylene catalyst as raw material.

[0065] The titanium source used in the first modifier and the second modifier can be the same or different.

[0066] In the catalytic cracking catalyst described above, in the catalyst A component and / or the catalyst B component, the clay includes one or a combination of two or more of kaolin, montmorillonite, diatomite, halloysite (also known as metakaolin), sepiolite, and bentonite. Specifically, the clay can include one of kaolin, diatomite, halloysite, or sepiolite. The clay used in the catalyst A component and the catalyst B component can be the same or different.

[0067] In the catalytic cracking catalyst described above, in the catalyst A component and / or the catalyst B component, the aluminum source can include one or a combination of two or more of pseudoboehmite, amorphous alumina, boehmite, aluminum nitrate, and aluminum chloride. In some specific embodiments, the aluminum source can be pseudoboehmite. The aluminum source used in the catalyst A component and the catalyst B component can be the same or different.

[0068] In the catalytic cracking catalyst described above, in the catalyst A component and / or the catalyst B component, the binder includes one or a combination of two or more of aluminum sol, silica sol, silica-alumina sol, and phosphorus-alumina sol. The binder used in the catalyst A component and the catalyst B component can be the same or different.

[0069] In the catalytic cracking catalyst described above, in the catalyst B component, the Y-type molecular sieve includes one or a combination of two or more of HY molecular sieve, NH4Y molecular sieve, hydrothermally stabilized Y-type molecular sieve, silicon tetrachloride vapor phase stabilized Y-type molecular sieve, rare earth-containing Y-type molecular sieve, and phosphorus-modified stabilized Y-type molecular sieve. Specifically, the rare earth-containing Y-type molecular sieve includes a rare earth-modified stabilized Y-type molecular sieve and / or a phosphorus and rare earth-modified stabilized Y-type molecular sieve.

[0070] The present application also provides a preparation method of the catalytic cracking catalyst described above, comprising:

[0071] Preparation of the catalyst A component: mixing the modified ZSM-5 molecular sieve, the clay, the aluminum source, and the second modifier to form a first slurry; spray drying and calcining the first slurry to obtain the catalyst A component;

[0072] Preparation of the catalyst B component: mixing the Y-type molecular sieve, the clay, the aluminum source, and the binder to form a second slurry; spray drying and calcining the second slurry to obtain the catalyst B component; the third modifier includes a modified metal source;

[0073] Mixing the catalyst A component and the catalyst B component to obtain the catalytic cracking catalyst.

[0074] In the preparation of the catalytic cracking catalyst, the second modifier at least comprises a phosphorus source, and further optionally comprises a modified metal source and a titanium source.

[0075] In the preparation of the catalytic cracking catalyst, the second slurry can further comprise a third modifier, and the third modifier at least comprises a modified metal source.

[0076] In the preparation of the catalytic cracking catalyst, by introducing the second modifier into the catalyst A component and introducing the third modifier into the catalyst B component, the content of the modified elements (titanium, modified metal elements, etc.) in the catalytic cracking catalyst can be further increased.

[0077] According to the specific embodiments of the present application, the pH value of the titanium source in the second modifier can be 0.5-8. In the preparation of the catalyst A component, the pH value of the titanium source can be first adjusted to 0.5-8, and then the titanium source is mixed with the modified ZSM-5 molecular sieve. When the second modifier comprises a modified metal source with high acidity (such as an iron source, etc.), the pH value of the modified metal source can also be first adjusted to 0.5-8, and then the modified metal source is mixed with the modified ZSM-5 molecular sieve.

[0078] In some specific embodiments, the pH value of the titanium source and the modified metal source of the second modifier can be adjusted by using alkaline substances. The alkaline substances can comprise one or a combination of two or more of ammonia, ammonium carbonate, ammonium bicarbonate, water glass, magnesium oxide, magnesium hydroxide, and magnesium carbonate.

[0079] According to the specific embodiments of the present application, in the above preparation method, the pH value of the titanium source and the modified metal source of the second modifier can be first adjusted to 0.5-8, and then filtered, and the obtained filter cake is added to the first slurry as the second modifier.

[0080] According to the specific embodiments of the present application, by adjusting the pH value of the second modifier in advance, the dealumination of the modified ZSM-5 molecular sieve due to the excessively high acidity of the system when the modified ZSM-5 molecular sieve is mixed with the second modifier can be avoided. Moreover, by controlling the pH value range, the distribution of the modified elements such as titanium in the ZSM-5 molecular sieve can be controlled.

[0081] In the above preparation method of the catalytic cracking catalyst, the modified ZSM-5 molecular sieve can be added in the form of a slurry, and the volume median particle size (D(v, 0.5)) of the slurry of the modified ZSM-5 molecular sieve can be less than or equal to 4 μm (i.e., the particle size of 50% volume fraction of particles can be less than or equal to 4 μm). In some specific embodiments, the modified ZSM-5 molecular sieve can be pre-treated by sand milling.

[0082] In the preparation method of the catalytic cracking catalyst, the volume median particle size D(v, 0.5) of the first slurry and / or the second slurry is less than or equal to 4 μm. The slurry can be subjected to sand milling before being subjected to spray drying.

[0083] In the preparation method of the catalytic cracking catalyst, the first slurry and / or the second slurry can further comprise a pore structure modifier capable of improving the pore structure, specific surface area and other structural properties of the catalyst. The pore structure modifier is added to the first slurry and the second slurry, and the weight of the pore structure modifier is 0.1% to 10% of the total weight of the catalytic cracking catalyst, preferably 0.3% to 5%.

[0084] In the preparation method of the catalytic cracking catalyst, the weight of the pore structure modifier contained in the first slurry is 0.3% to 6% of the weight of the raw material of the catalyst A component.

[0085] In the preparation method of the catalytic cracking catalyst, the pore structure modifier comprises one or a combination of two or more of 1,3,5-trimethylbenzene, 1,3,5-triisopropylbenzene, methyl cellulose, carboxymethyl cellulose, polyvinyl alcohol and polyethylene glycol.

[0086] According to a specific embodiment of the present application, the process of preparing the catalyst A component can further comprise subjecting at least one of the modified ZSM-5 molecular sieve, clay and aluminum source to acid treatment, and the process of preparing the catalyst B component can further comprise subjecting at least one of the binder, clay, second modifier and at least part of the modified metal source to acid treatment. The acid treatment in the preparation of the catalyst A component and the catalyst B component can acidize and disperse the aluminum source such as pseudo-boehmite, and make the aluminum source such as pseudo-boehmite have a certain binder effect, thereby improving the wear resistance of the catalytic cracking catalyst.

[0087] According to a specific embodiment of the present application, the acid used in the acid treatment can comprise an inorganic acid. The inorganic acid can comprise one or a combination of two or more of hydrochloric acid, sulfuric acid and nitric acid.

[0088] According to a specific embodiment of the present application, the temperature of the acid treatment can be 40-90 ℃, and the time of the acid treatment can be 0.5-3 h.

[0089] The present application further provides the use of the catalytic cracking catalyst in a catalytic cracking process. The catalytic cracking catalyst is used in a catalytic cracking process, which can promote the conversion of heavy oil, reduce the yield of heavy oil, reduce the tendency of coke formation, and at the same time, the yield of low-carbon olefins and aromatic hydrocarbons is high. For relatively heavy raw oil, the Y molecular sieve in the catalytic cracking catalyst can first crack heavy oil macromolecules, and then make the cracked products enter the ZSM-5 molecular sieve to be further converted into low-carbon olefins and aromatic hydrocarbons and other chemical products.

[0090] In some embodiments, the reaction temperature of the catalytic cracking process can be 530-650℃, and the catalyst-oil ratio can be 8-20.

[0091] The beneficial effects of the present application include:

[0092] 1. The A component and the B component of the catalytic cracking catalyst provided by the present application are used by mixing, and have the following synergistic effect: the catalyst B can convert heavy oil macromolecules into relatively small molecules, in which straight-chain hydrocarbons or straight-chain hydrocarbons containing methyl groups can enter the catalyst A for further reaction and cracking into smaller molecules, especially low-carbon olefins (ethylene, propylene, butene). However, the reaction effect cannot be achieved by using the catalyst A component or the catalyst B component alone. Furthermore, compared with a catalyst containing both Y-type molecular sieve and ZSM-5 molecular sieve, the catalyst system formed by mixing the catalyst A component and the catalyst B component has higher yield and better selectivity of low-carbon olefins.

[0093] 2. The catalytic cracking catalyst using the modified ZSM-5 molecular sieve as the active component is used in the catalytic cracking process, which can promote the conversion of heavy oil in the catalytic cracking process, reduce the yield of heavy oil, and reduce the tendency of coke formation while increasing the yield of ethylene / propylene and other low-carbon olefins, and has excellent reaction selectivity and use performance. Further, the preparation raw material of the catalytic cracking catalyst provided by the present application can contain titanium tetrachloride-containing waste liquid generated in the preparation process of a titanium-based polypropylene catalyst, which not only solves the problem of the treatment of the waste liquid and avoids environmental pollution, but also reduces the high treatment cost of the waste liquid. BRIEF DESCRIPTION OF DRAWINGS

[0094] Figure 1 BJH pore distribution curve of the support material APM-7 and the industrial pseudo-boehmite. DETAILED DESCRIPTION

[0095] In order to have a clearer understanding of the technical features, objectives and beneficial effects of the present application, the technical solutions of the present application are described in detail as follows, but it should not be understood as limiting the scope of the present application.

[0096] In the following examples and comparative examples, the contents of titanium, phosphorus, modified metals and other elements in the modified ZSM-5 molecular sieve are determined by X-ray fluorescence analysis. The crystallinity of ZSM-5 is the relative crystallinity, which is measured by XRD method. The specific surface area retention rate is the ratio of the specific surface area of the modified molecular sieve before aging to the specific surface area after aging multiplied by 100%. The pore volume of the molecular sieve is determined by N2 isothermal adsorption-desorption using a Micromeritics ASAP3000 type automatic physical adsorption instrument.

[0097] In the present application, the dry base refers to the state of the material after being calcined at 800℃ for 1h.

[0098] The raw materials used in the embodiments of the present application are from the following places and have the following specifications:

[0099] (1) Waste liquid containing titanium tetrachloride produced in the preparation process of titanium-based polypropylene catalyst (hereinafter referred to as waste liquid containing titanium tetrachloride): the waste liquid contains 90% of titanium (calculated as TiCl4), 2-5% of titanium alkoxy complex, and the balance of hydrocarbons in liquid state at room temperature, based on the total weight of the waste liquid; the hydrocarbons mainly include hexane, and the balance includes esters. The waste liquid is provided by Lanzhou Chemical Research Center of Petrochemical Research Institute of China Petroleum.

[0100] Kaolin (loss on ignition 29 wt%), halloysite (loss on ignition 16.6 wt%), pseudoboehmite (loss on ignition 36 wt%), aluminum sol (containing alumina 21.6 wt%), silica sol (silica concentration 30 wt%), ordinary ZSM-5 molecular sieve (silicon-aluminum ratio 31, mesopore volume 0.04 mL / g), high-silicon ZSM-5 molecular sieve (silicon-aluminum ratio 384), USY molecular sieve (Na2O content 1.2 wt%, not containing rare earth, loss on ignition 4 wt%), GUSY-1 molecular sieve (silicon tetrachloride gas phase ultrastable molecular sieve, Na2O content 1.3 wt%, RE2O3 content 2.7 wt%, relative crystallinity 55%, unit cell constant 24.46 Å, loss on ignition 4 wt%), REHY molecular sieve (Na2O content 1.5 wt%, RE2O3 content 8.2 wt%, loss on ignition 5 wt%), rare earth chloride solution (content 289.3 g / L as RE2O3): all are industrial products, and are obtained from the Catalyst Factory of Lanzhou Petrochemical Company.

[0101] (2) Micro-mesoporous ZSM-5 molecular sieve: silicon-aluminum ratio 30, mesopore volume 0.29 mL / g, purchased from Dalian;

[0102] (3) Diatomite (loss on ignition 2.6 wt%): industrial product, purchased from Inner Mongolia;

[0103] (4) Titanium tetrachloride, magnesium oxide, magnesium chloride, phosphoric acid (concentration 85%), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lanthanum oxide, yttrium nitrate, iron nitrate (Fe(NO3)3·9H2O), zirconium oxide, zirconium sulfate, 1,3,5-trimethylbenzene, polyethylene glycol, carboxymethyl cellulose: all are chemical reagents; n-hexane: analytical pure reagent.

[0104] (5) Hydrochloric acid: concentration 36%, chemical reagent; nitric acid: concentration 65-68%, chemical reagent; ammonia water: concentration 18%, chemical reagent.

[0105] (6) The carrier material APM-7 used in the following examples and comparative examples is an active silicon-aluminum material produced by the Catalyst Factory of PetroChina Lanzhou Petrochemical Company. The carrier material APM-7 has B acid centers. The carrier material is a multi-level pore silicon-aluminum material rich in B acid characteristics prepared from inexpensive silicon and aluminum sources, using hydrochloric acid and ammonia to adjust the pH value of the system, through steps such as gelation and temperature aging, and is obtained according to the preparation method of the B acid-rich multi-level pore material APM-7 described in “Application of B Acid-Rich Multi-Level Pore Material in Catalytic Cracking Catalyst” (Fine Petrochemical Industry, 2019, 36(3): 24-27.), the entire contents of the above document are incorporated herein by reference as part of the specification.

[0106] Figure 1 The BJH pore distribution curves of the carrier material APM-7 and the comparative material (industrial pseudo-boehmite, also known as industrial alumina) are shown in FIG. 1. Figure 1 As can be seen, APM-7 has both mesopore and macropore distributions, while the industrial pseudo-boehmite material only has a single pore distribution between 2-4 nm, with a pore diameter of 3.4 nm.

[0107] Table 1 shows the infrared acidity characterization data of the carrier material APM-7 and the industrial pseudo-boehmite (comparative material).

[0108] Table 1

[0109]

[0110] As can be seen from Table 1, the total amount of L acid and B acid of APM-7 is 91.50 and 197.36 μmol / g, respectively, and the B / L acid ratio is as high as 2.2. The comparative material only contains L acid centers, and the total amount of L acid is 213.61 μmol / g, which is lower than that of APM-7.

[0111] In the following examples and comparative examples, the furnace temperature of the spray drying is 450°C, and the spray tail gas temperature is 200°C.

[0112] Example 1

[0113] The present embodiment provides a catalytic cracking catalyst, and a preparation method thereof, which comprises:

[0114] 1. Preparation of modified ZSM-5 molecular sieve:

[0115] (1) 1.402 kg of microporous ZSM-5 molecular sieve (dry basis) is added to 4 L of deionized water, stirred uniformly, and then 139 g of waste liquid containing titanium tetrachloride is added, stirred for 0.5 h, to form a slurry containing the molecular sieve, dried at 120°C, and calcined at 500°C for 1 h; wherein the pH value of the slurry containing the molecular sieve is 1.01;

[0116] (2) The molecular sieve after step (1) is mixed with 4 L of deionized water, 73 g of phosphoric acid is added, stirred uniformly, dried at 120°C, and calcined at 500°C for 1 h to obtain the titanium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve Z-1.

[0117] According to the amount of raw material added, the titanium-phosphorus modified ZSM-5 molecular sieve Z-1 contains 3.5% titanium (calculated as an oxide) and 3.0% phosphorus (calculated as an oxide), with the balance being ZSM-5 molecular sieve.

[0118] 2. Preparation of catalyst A component:

[0119] 1.08 kg of kaolin (dry basis), 0.36 kg of pseudo-boehmite (dry basis), and 4.05 L of deionized water are added to a beater tank for beating, stirred for 1 h, then 48 mL of hydrochloric acid is added, stirred for 0.5 h, and then acidified at 50°C for 2 h to obtain a first intermediate system;

[0120] 1.08 kg of titanium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve Z-1 (dry basis), 0.799 kg of phosphoric acid, and 30 g of carboxymethyl cellulose are further added to the first intermediate system, mixed and beaten for 1 h, then the obtained first slurry is subjected to sand milling treatment to make the average particle size D(v, 0.5) of the slurry less than 4 μm, spray dried, and calcined at 550°C for 2 h to obtain the catalytic cracking catalyst A component CAT-A1.

[0121] The raw material composition of the catalytic cracking catalyst A component CAT-A1 is: titanium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve Z-1 is 36 wt% (dry basis), kaolin is 36 wt% (dry basis), pseudo-boehmite is 12 wt% (dry basis), and the phosphorus pentoxide from the added phosphoric acid in step 2 is 16 wt%.

[0122] 3. Preparation of catalyst B component:

[0123] 1.413 kg of kaolin (dry basis), 0.972 kg of aluminum sol, and 1.52 kg of deionized water are added to a beater tank for beating, then 0.24 kg of pseudo-boehmite (dry basis) and 15 g of lanthanum oxide are added, stirred for 0.5 h, then 36 mL of hydrochloric acid is added, stirred for 2 h, and then acidified at 70°C for 1.5 h to obtain a second intermediate system.

[0124] 1.05 kg of USY molecular sieve (dry basis), 183 g of yttrium nitrate, 91.5 g of magnesium chloride, and 1.58 kg of deionized water are mixed and beaten for 1.5 h, then added to the second intermediate system in the first beater tank, and then 30 g of carboxymethyl cellulose is added, beaten for 2 h, and the obtained second slurry is subjected to sand milling treatment to make the average particle size D(v, 0.5) of the slurry less than 4 μm, and then spray dried to obtain the catalyst B component microspheres.

[0125] The spray-dried catalyst B component microspheres were calcined, washed to reduce sodium, and dried to obtain a catalytic cracking catalyst B component CAT-B1.

[0126] The raw material composition of the catalytic cracking catalyst B component CAT-B1 was: kaolin 47.1 wt% (dry basis), pseudo-boehmite 8 wt% (dry basis), alumina from aluminum sol 7 wt%, USY molecular sieve 35 wt% (dry basis), yttrium oxide from yttrium nitrate 1.8 wt%, magnesium oxide from magnesium chloride 0.6 wt%, lanthanum oxide 0.5 wt%, and catalyst gel solid content 38%. The catalyst gel solid content is the solid content in the raw material slurry, that is, the ratio of the mass of the solid obtained after spray drying (dry basis) to the mass of the raw material slurry before spray drying.

[0127] The catalyst A component CAT-A1 and the catalyst B component CAT-B1 were mixed in a weight ratio of 98:2 to obtain the catalytic cracking catalyst CAT-1 of the present example.

[0128] Example 2

[0129] The present example provides a catalytic cracking catalyst, and a preparation method thereof, which comprises:

[0130] 1. Preparation of modified ZSM-5 molecular sieve:

[0131] (1) 1.388 kg of micro-mesoporous ZSM-5 molecular sieve (dry basis), 15 g of polyethylene glycol, 3.5 L of deionized water, 20 g of waste liquid containing titanium tetrachloride, and 103 g of zirconium sulfate were added and stirred uniformly to form a molecular sieve-containing slurry, which was dried at 100°C and calcined at 550°C for 1.5 h; wherein the pH value of the molecular sieve-containing slurry was 1.52.

[0132] (2) The calcined molecular sieve of step (1) was mixed with 15 g of polyethylene glycol, 3.5 L of deionized water, and 97 g of phosphoric acid, stirred uniformly, dried at 100°C, and calcined at 550°C for 1.5 h to obtain a titanium-zirconium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve Z-2. According to the calculation of the amount of raw materials added, the titanium-zirconium-phosphorus modified ZSM-5 molecular sieve Z-2 contains 0.5% titanium (calculated as oxide), 3.0% zirconium (calculated as oxide), and 4.0% phosphorus (calculated as oxide), and the balance is ZSM-5 molecular sieve.

[0133] 2. Preparation of catalyst A component:

[0134] A first intermediate system was prepared by adding 1.14 kg of kaolin (dry basis), 0.12 kg of pseudo-boehmite (dry basis) and 4.18 L of deionized water into a beater tank for beating, stirring for 0.5 h, then adding 12.1 mL of hydrochloric acid, stirring for 15 min, and acidifying at 50 °C for 1 h;

[0135] Then, 0.972 kg of aluminum sol, 1.14 kg of titanium-zirconium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve Z-2 (dry basis), 30 g of lanthanum oxide, 0.585 kg of phosphoric acid, and 15 g of polyethylene glycol were added into the first intermediate system, and the mixture was beaten for 0.5 h. The obtained first slurry was subjected to sand milling treatment to make the average particle size D(v, 0.5) of the slurry less than 4 μm, spray dried, and calcined at 500 °C for 1 h to obtain a catalytic cracking catalyst A component CAT-A2.

[0136] The raw material composition of the catalytic cracking catalyst A component CAT-A2 was as follows: titanium-zirconium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve Z-2 was 38 wt% (dry basis), kaolin was 38 wt% (dry basis), pseudo-boehmite was 4 wt% (dry basis), aluminum oxide from aluminum sol was 7 wt%, lanthanum oxide was 1 wt%, and phosphorus pentoxide from the added phosphoric acid in step 2 was 12 wt%.

[0137] 3. Preparation of a catalyst B component:

[0138] A second intermediate system was prepared by adding 1.08 kg of kaolin (dry basis), 0.972 kg of aluminum sol, and 1.7 kg of deionized water into a beater tank for beating, then adding 0.54 kg of pseudo-boehmite (dry basis) and 155 mL of a rare earth chloride solution, stirring for 1.5 h, adding 91 mL of hydrochloric acid, stirring for 0.5 h, and acidifying at 50 °C for 1 h.

[0139] The second intermediate system in the first beater tank was added with 0.9 kg of GUSY-1 molecular sieve (dry basis), 60 g of titanium-phosphorus-zirconium modified micro-mesoporous ZSM-5 molecular sieve Z-2 (dry basis) in the A component described above, 45 g of yttrium chloride (calculated as yttrium oxide), and 1.6 kg of deionized water, and the mixture was beaten for 0.5 h. Then, 120 g (dry basis) of carrier material APM-7 and 15 g of polyethylene glycol were added, and the mixture was beaten for 1 h. The obtained second slurry was subjected to sand milling treatment to make the average particle size D(v, 0.5) of the slurry less than 4 μm, and spray dried to obtain catalyst B component microspheres.

[0140] The spray-dried catalyst B component microspheres were calcined, washed to reduce sodium, and dried to obtain a catalytic cracking catalyst B component CAT-B2.

[0141] The raw material composition of the catalytic cracking catalyst B component CAT-B2 is: 36 wt% (dry basis) kaolin, 18 wt% (dry basis) pseudo-boehmite, 7 wt% alumina from aluminum sol, 30 wt% (dry basis) GUSY-1 molecular sieve, 2 wt% (dry basis) titanium-phosphorus-zirconium modified micro-mesoporous ZSM-5 molecular sieve Z-2, 1.5 wt% yttrium oxide from yttrium chloride, 1.5 wt% rare earth oxide from rare earth chloride solution, 4 wt% inorganic oxide carrier material APM-7 (dry basis), and catalyst gel content 36%.

[0142] The catalyst A component CAT-A2 and the catalyst B component CAT-B2 are mixed in a weight ratio of 95:5 to obtain the catalytic cracking catalyst CAT-2 of the present example.

[0143] Example 3

[0144] The present example provides a catalytic cracking catalyst, and a preparation method thereof, which comprises:

[0145] 1. Preparation of modified ZSM-5 molecular sieve:

[0146] (1) Under stirring, 792 g of waste liquid containing titanium tetrachloride, 113.6 g of ferric nitrate, and 110 g of carboxymethyl cellulose are added to 3.6 L of deionized water, respectively, stirred for 10 min, the pH value is adjusted to 6.51 with ammonia water, and then 1.102 kg of ordinary ZSM-5 molecular sieve (dry basis) is added, stirred for 1 h, a slurry containing the molecular sieve is formed, dried at 100°C, and calcined at 520°C for 1 h; wherein the pH value of the slurry of the molecular sieve is 5.66.

[0147] (2) The calcined molecular sieve of step (1), 110 g of carboxymethyl cellulose, and 3.6 L of deionized water are mixed, 139 g of diammonium hydrogen phosphate is added, stirred uniformly, dried at 100°C, and calcined at 520°C for 1 h to obtain a titanium-iron-phosphorus modified ZSM-5 molecular sieve Z-3.

[0148] According to the calculation of the raw material addition amount, the titanium-iron-phosphorus modified ZSM-5 molecular sieve contains 20.0% titanium (calculated as oxide), 1.5% iron (calculated as oxide), and 5.0% phosphorus (calculated as oxide), and the balance is ZSM-5 molecular sieve.

[0149] 2. Preparation of catalyst A component:

[0150] 1.5 kg of ZSM-5 molecular sieve Z-3 (dry basis) is added to 4 L of deionized water, stirred, and subjected to sand milling treatment to make the average particle size D(v, 0.5) of the molecular sieve Z-3 slurry less than 4 μm.

[0151] The slurry of the molecular sieve Z-3 with an average particle size D(v,0.5) of less than 4 μm, 0.93 kg halloysite (dry basis), 0.18 kg pseudoboehmite (dry basis) and 0.7 L deionized water were added into a beater to be beaten, stirred for 2 h, then 22.7 mL hydrochloric acid was added, stirred for 25 min, acidified at 70 °C for 1 h, cooled to 35 °C to obtain a first intermediate system; 694 g aluminum sol, 0.390 kg phosphoric acid and 150 g carboxymethyl cellulose were added into the first intermediate system, mixed and beaten for 0.5 h, then the first slurry was homogenized, spray dried and calcined at 600 °C for 3 h to obtain the catalytic cracking catalyst A component CAT-A3.

[0152] The raw material composition of the catalytic cracking catalyst A component CAT-A3 was: the titanium iron phosphorus modified ZSM-5 molecular sieve Z-3 was 50 wt% (dry basis), halloysite was 31 wt% (dry basis), pseudoboehmite was 6 wt% (dry basis), the alumina from the aluminum sol was 5 wt%, the phosphorus pentoxide from the phosphoric acid added in step 2 was 8 wt%.

[0153] 3. Preparation of the catalyst B component:

[0154] 1.236 kg kaolin (dry basis), 1.11 kg aluminum sol, 15 g cerium oxide and 1.74 kg deionized water were added into a beater to be beaten, then 0.24 kg pseudoboehmite (dry basis) was added, stirred for 1 h, then 20 mL nitric acid was added, stirred for 1 h, acidified at 50 °C for 1.2 h to obtain a second intermediate system.

[0155] 0.72 kg GUSY-1 molecular sieve (dry basis), 0.24 kg REHY molecular sieve (dry basis), 60 g titanium phosphorus zirconium modified micro-mesoporous ZSM-5 molecular sieve Z-2 in the A component of Example 2 (dry basis), 0.18 kg unmodified high-silicon ZSM-5 molecular sieve (dry basis), 54 g yttrium oxide, 15 g magnesium oxide and 1.98 kg deionized water were mixed and beaten for 0.5 h, then added into the second intermediate system in the first beater, then 150 g carboxymethyl cellulose was added, beaten for 1.8 h, the obtained second slurry was subjected to sand milling treatment to make the average particle size D(v,0.5) of the slurry less than 4 μm, then spray dried to obtain the catalyst B component microspheres.

[0156] The spray dried catalyst B component microspheres were calcined, washed to reduce sodium, dried to obtain the catalytic cracking catalyst B component CAT-B3.

[0157] The raw material composition of the catalytic cracking catalyst B component CAT-B3 is: kaolin 41.2 wt% (dry basis), pseudo-boehmite 8 wt% (dry basis), alumina from aluminum sol 8 wt%, GUSY-1 molecular sieve 24 wt% (dry basis), REHY molecular sieve 8 wt% (dry basis), 2 wt% (dry basis) micro-mesoporous ZSM-5 molecular sieve Z-2, 6 wt% (dry basis) high-silicon ZSM-5 molecular sieve, yttrium oxide 1.8 wt%, cerium oxide 0.5 wt%, magnesium oxide 0.5 wt%, and the catalyst gelation solid content is 36%.

[0158] The catalyst A component CAT-A3 and the catalyst B component CAT-B3 are mixed at a weight ratio of 70:30 to obtain the catalytic cracking catalyst CAT-3 of the present example.

[0159] Example 4

[0160] The present example provides a catalytic cracking catalyst, and a preparation method thereof comprises:

[0161] 1. Preparation of the catalyst A component:

[0162] 0.96 kg of the titanium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve Z-1 of the A component of Example 1 (dry basis) is added into 2.2 L of deionized water, stirred, and subjected to sand milling treatment to make the average particle size D(v, 0.5) of the molecular sieve Z-1 slurry less than 4 μm.

[0163] 30 g of magnesium oxide is added into 1.8 L of deionized water, stirred, 475 g of waste liquid containing titanium tetrachloride is added, the pH value is adjusted to 7 by using ammonia water, and filtration is performed to obtain a titanium-magnesium-containing filter cake A.

[0164] 1.065 kg of kaolin (dry basis), 0.24 kg of pseudo-boehmite (dry basis), and 1.5 L of deionized water are added into a beater tank for beating, stirred for 40 min, then 28.2 mL of hydrochloric acid is added, stirred for 15 min, and then acidified at 45°C for 1.5 h to obtain a first intermediate system; 600 g of silica sol, the molecular sieve Z-1 slurry with the average particle size D(v, 0.5) less than 4 μm, the filter cake A, 0.487 kg of phosphoric acid, 45 g of zirconium oxide, and 9 g of 1,3,5-trimethylbenzene are further added into the first intermediate system, mixed and beaten for 1 h, then the obtained first slurry is subjected to homogenization, spray dried, and calcined at 570°C for 1.5 h to obtain the catalytic cracking catalyst A component CAT-A4.

[0165] The raw material composition of the catalyst A component CAT-A4 of the catalytic cracking catalyst is: 32 wt% (dry basis) of modified micro-mesoporous ZSM-5 zeolite Z-1, 35.5 wt% (dry basis) of kaolin, 8 wt% of pseudo-boehmite, 6 wt% of silicon oxide from silica sol, 1.5 wt% of zirconium oxide, 6 wt% (calculated as oxide) of titanium from filter cake A, 1 wt% (calculated as oxide) of magnesium from filter cake A, and 10 wt% of phosphorus pentoxide from phosphoric acid.

[0166] 2、Preparation of the catalyst B component:

[0167] 0.45 kg of kaolin (dry basis), 0.3 kg of halloysite (dry basis), 0.833 kg of aluminum sol, and 1.76 kg of deionized water were added into a beater tank for beating, then 0.75 kg of pseudo-boehmite (dry basis) was added, stirred for 1 h, 101 mL of hydrochloric acid was added, stirred for 0.5 h, and then acidified at 55°C for 2 h to obtain a second intermediate system.

[0168] After 1.26 kg of GUSY-1 zeolite (dry basis), 60 g of yttrium oxide, and 2.1 kg of deionized water were mixed and beaten for 0.5 h, they were added into the second intermediate system of the first beating tank, 9 g of 1,3,5-trimethylbenzene was added, and beating was performed for 1.5 h. The obtained second slurry was subjected to sand milling treatment to make the average particle size D(v, 0.5) of the slurry less than 4 μm, spray drying was performed to obtain the catalyst B component microspheres.

[0169] The catalyst B component microspheres obtained by spray drying were calcined, washed to reduce sodium, and dried to obtain the catalyst B component CAT-B4 of the catalytic cracking catalyst.

[0170] The raw material composition of the catalyst B component CAT-B4 of the catalytic cracking catalyst is: 15 wt% (dry basis) of kaolin, 10 wt% (dry basis) of halloysite, 25 wt% (dry basis) of pseudo-boehmite, 6 wt% of aluminum oxide from aluminum sol, 42 wt% (dry basis) of GUSY-1 zeolite, 2 wt% of yttrium oxide, and a catalyst gelation solid content of 36%. The catalyst gelation solid content is the solid content in the slurry, that is, the ratio of the mass of the solid obtained after spray drying to the mass of the slurry before spray drying.

[0171] The catalyst A component CAT-A4 and the catalyst B component CAT-B4 were mixed at a weight ratio of 30:70 to obtain the catalytic cracking catalyst CAT-4 of the present example.

[0172] Example 5

[0173] The present example provides a catalytic cracking catalyst, and a preparation method thereof.

[0174] 1、Preparation of modified ZSM-5 zeolite:

[0175] (1) Take 170.6 g of Fe(NO3)3·9H2O, 107 g of waste liquid containing titanium tetrachloride, and dissolve them in an appropriate amount of distilled water to prepare a mixed iron nitrate / titanium tetrachloride impregnation solution. The pH value of the mixed iron nitrate / titanium tetrachloride impregnation solution is 0.56. Slowly pour the mixed impregnation solution into 1.381 kg of ordinary ZSM-5 molecular sieve (dry basis), and continuously stir to achieve equal volume impregnation. After standing for 12 h, dry in a 120°C oven for 6 h. Calcine in a 540°C muffle furnace for 4 h to obtain the modified molecular sieve Fe-Ti / ZSM-5.

[0176] (2) Mix the modified molecular sieve Fe-Ti / ZSM-5 from step (1) with 3.6 L of deionized water, add 73 g of ammonium dihydrogen phosphate, stir until uniform, dry at 120°C, and calcine at 520°C for 1 h to obtain the titanium-iron-phosphorus modified ZSM-5 molecular sieve Z-4.

[0177] According to the calculation of the amount of raw materials added, the titanium-iron-phosphorus modified ZSM-5 molecular sieve contains 2.7% titanium (as oxide), 2.25% iron (as oxide), and 3.0% phosphorus (as oxide), with the balance being ZSM-5 molecular sieve.

[0178] 2. Preparation of catalyst A component:

[0179] Add 0.78 kg of kaolin (dry basis), 0.18 kg of diatomite (dry basis), 0.3 kg of pseudo-boehmite (dry basis), and 4.18 L of deionized water to a beater tank and beat, stir for 0.5 h, then add 25 mL of nitric acid, stir for 45 min, and then acidify at 55°C for 2 h to obtain a first intermediate system. Add 1.26 kg of ZSM-5 molecular sieve Z-4 (dry basis), 0.799 kg of phosphoric acid, and 30 g of polyethylene glycol to the first intermediate system, mix and beat for 1 h, then subject the obtained first slurry to sand milling treatment to make the average particle size D(v,0.5) of the slurry less than 4 μm, spray dry, and calcine at 500°C for 2 h to obtain the catalytic cracking catalyst A component CAT-A5.

[0180] The raw material composition of the catalytic cracking catalyst A component CAT-A5 is: titanium-iron-phosphorus modified ZSM-5 molecular sieve Z-4 42 wt% (dry basis), kaolin 26 wt% (dry basis), diatomite 6 wt% (dry basis), pseudo-boehmite 10 wt% (dry basis), and phosphorus pentoxide from the added phosphoric acid in step 2 16 wt%.

[0181] Mix the catalyst A component CAT-A5 and the catalyst B component CAT-B4 prepared in Example 4 in a weight ratio of 90:10 to obtain the catalytic cracking catalyst CAT-5 of this example.

[0182] Example 6

[0183] This example provides a catalytic cracking catalyst, and the preparation method thereof comprises:

[0184] 1. Preparation of modified ZSM-5 molecular sieve:

[0185] (1) 1.402 kg of microporous ZSM-5 molecular sieve (dry basis) was added into 4 L of deionized water and stirred uniformly, then 125 g of titanium tetrachloride was added, stirred for 0.5 h, to form a slurry containing the molecular sieve (as a mixed solution), dried at 120°C, and calcined at 500°C for 1 h; wherein the pH value of the slurry containing the molecular sieve was 1.03;

[0186] (2) The calcined product of step (1) was mixed with 4 L of deionized water, 73 g of phosphoric acid was added, stirred uniformly, dried at 120°C, and calcined at 500°C for 1 h to obtain a titanium-phosphorus modified microporous ZSM-5 molecular sieve, denoted as Z-5.

[0187] According to the calculation of the amount of raw materials added, the composition of the titanium-phosphorus modified microporous ZSM-5 molecular sieve was: titanium (as an oxide) 3.5%, phosphorus (as an oxide) 3.0%, and the balance was ZSM-5 molecular sieve.

[0188] 2. Preparation of catalyst A component: the preparation method was similar to that of the catalyst A component of Example 1, and the only difference was that the modified ZSM-5 molecular sieve used in this example was the titanium-phosphorus modified microporous ZSM-5 molecular sieve of step 1 of this example.

[0189] 3. Preparation of catalyst B component: the preparation method was the same as that of the catalyst B component of Example 1.

[0190] The catalyst A component CAT-A6 and the catalyst B component CAT-B1 were mixed in a weight ratio of 98:2 to obtain the catalytic cracking catalyst CAT-6 of this example.

[0191] Example 7

[0192] This example provides a catalytic cracking catalyst, and the preparation method thereof comprises:

[0193] 1. Preparation of modified ZSM-5 molecular sieve:

[0194] (1) 712 g of titanium tetrachloride, 113.6 g of ferric nitrate, 21 g of n-hexane, and 110 g of carboxymethyl cellulose were added into 3.6 L of deionized water under stirring, stirred for 10 min, the pH value was adjusted to 6.51 with ammonia water, then 1.102 kg of ordinary ZSM-5 molecular sieve (dry basis) was added, stirred for 1 h, to form a slurry containing the molecular sieve, dried at 100°C, and calcined at 520°C for 1 h; wherein the pH value of the slurry containing the molecular sieve was 5.70.

[0195] (2) The calcination product of step (1), 110 g of carboxymethyl cellulose and 3.6 L of deionized water were mixed, 139 g of diammonium hydrogen phosphate was added, stirred uniformly, dried at 100°C, and calcined at 520°C for 1 h to obtain a titanium-iron-phosphorus modified ZSM-5 molecular sieve, denoted as Z-6.

[0196] According to the amount of raw material added, the titanium-iron-phosphorus modified ZSM-5 molecular sieve Z-6 contained 20.0% titanium (calculated as an oxide), 1.5% iron (calculated as an oxide), and 5.0% phosphorus (calculated as an oxide).

[0197] 2, Preparation of catalyst A component: the preparation method is similar to that of catalyst A component of Example 3, and the only difference is that the modified ZSM-5 molecular sieve used in this example is the titanium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve of step 1 of this example.

[0198] 3, Preparation of catalyst B component: the preparation method is the same as that of catalyst B component of Example 3.

[0199] The catalyst A component CAT-A7 and the catalyst B component CAT-B3 were mixed in a weight ratio of 70:30 to obtain the catalytic cracking catalyst CAT-7 of this example.

[0200] Comparative Example 1

[0201] This comparative example provides a catalytic cracking catalyst, and the preparation method thereof comprises:

[0202] 1, Preparation of modified ZSM-5 molecular sieve:

[0203] (1) 1.455 kg of micro-mesoporous ZSM-5 molecular sieve (dry basis) was added to 4 L of deionized water, stirred for 0.5 h to form a slurry containing the molecular sieve, dried at 120°C, and calcined at 500°C for 1 h; wherein the pH value of the slurry containing the molecular sieve was 2.51;

[0204] (2) The calcined molecular sieve of step (1) was mixed with 4 L of deionized water, 73 g of phosphoric acid was added, stirred uniformly, dried at 120°C, and calcined at 500°C for 1 h to obtain a phosphorus modified micro-mesoporous ZSM-5 molecular sieve DZ-1.

[0205] According to the amount of raw material added, the phosphorus modified ZSM-5 molecular sieve contained 3.0% phosphorus (calculated as an oxide), and the balance was ZSM-5 molecular sieve.

[0206] 2, Preparation of catalyst A component:

[0207] A slurry tank was charged with 1.08 kg of kaolin (dry basis), 0.36 kg of pseudo-boehmite (dry basis) and 4.05 L of deionized water, slurried for 1 h, then 48 mL of hydrochloric acid was added, stirred for 0.5 h, and then acidified at 50 °C for 2 h; then 1.08 kg of micro-mesoporous ZSM-5 molecular sieve DZ-1 (dry basis), 0.799 kg of phosphoric acid were added, mixed and slurried for 1 h, then homogenized, spray dried, and calcined at 550 °C for 2 h to obtain the comparative catalytic cracking catalyst A component DCAT-A1.

[0208] The raw material composition of the comparative catalytic cracking catalyst A component DCAT-A1 was: 36 wt% (dry basis) of modified micro-mesoporous ZSM-5 molecular sieve DZ-1, 36 wt% (dry basis) of kaolin, 12 wt% (dry basis) of pseudo-boehmite, and 16 wt% of phosphorus pentoxide from the phosphoric acid added in step 2.

[0209] 3. Preparation of catalyst B component:

[0210] A slurry tank was charged with 1.413 kg of kaolin (dry basis), 0.972 kg of aluminum sol and 1.52 kg of deionized water, slurried, then 0.24 kg of pseudo-boehmite (dry basis) and 15 g of lanthanum oxide were added, stirred for 0.5 h, then 36 mL of hydrochloric acid was added, stirred for 2 h, and then acidified at 70 °C for 1.5 h.

[0211] The slurry tank of the first step was charged with 1.05 kg of USY molecular sieve (dry basis), 183 g of yttrium nitrate, 91.5 g of magnesium chloride, and 1.58 kg of deionized water, mixed and slurried for 1.5 h, then slurried for 2 h, homogenized, and spray dried to obtain the catalyst B component microspheres.

[0212] The spray-dried catalyst B component microspheres were calcined, washed to reduce sodium, and dried to obtain the catalytic cracking catalyst B component DCAT-B1.

[0213] The raw material composition of the catalytic cracking catalyst B component DCAT-B1 was: 47.1 wt% (dry basis) of kaolin, 8 wt% (dry basis) of pseudo-boehmite, 7 wt% of aluminum oxide from the aluminum sol, 35 wt% (dry basis) of USY molecular sieve, 1.8 wt% of yttrium oxide from the yttrium nitrate, 0.6 wt% of magnesium oxide from the magnesium chloride, and 0.5 wt% of lanthanum oxide, with a catalyst gel solid content of 38%.

[0214] The catalyst A component DCAT-A1 and the catalyst B component DCAT-B1 were mixed in a weight ratio of 98:2 to obtain the catalytic cracking catalyst DCAT-1 of the present comparative example.

[0215] Comparative Example 2

[0216] This comparative example provides a catalytic cracking catalyst, the preparation method of which includes:

[0217] 1. Preparation of modified ZSM-5 molecular sieves:

[0218] (1) Add 1.455 kg of ordinary ZSM-5 molecular sieve (dry basis) to 4 L of deionized water, stir for 0.5 h to form a slurry containing molecular sieve, dry at 120 °C and calcine at 500 °C for 1 h;

[0219] (2) The molecular sieve after calcination in step (1) was mixed with 4L of deionized water, 73g of phosphoric acid was added, stirred evenly, dried at 120℃, and calcined at 500℃ for 1h to obtain phosphorus-modified ZSM-5 molecular sieve DZ-2.

[0220] Based on the amount of raw materials added, the phosphorus-modified ZSM-5 molecular sieve contains 3.0% phosphorus (calculated as oxides), with the remainder being ZSM-5 molecular sieve.

[0221] 2. Preparation of catalyst component A:

[0222] 1.08 kg of kaolin (dry basis), 0.36 kg of pseudoboehmite (dry basis), and 4.05 L of deionized water were added to a pulping tank and pulped for 1 h. Then, 48 mL of hydrochloric acid was added and stirred for 0.5 h, followed by acidification at 50 °C for 2 h. Then, 1.08 kg of ZSM-5 molecular sieve DZ-2 (dry basis), 0.799 kg of phosphoric acid, and 30 g of carboxymethyl cellulose were added, mixed and pulped for 1 h, homogenized, spray-dried, and calcined at 550 °C for 2 h to obtain the comparative catalytic cracking catalyst component A, DCAT-A2.

[0223] The raw material composition of the comparative catalytic cracking catalyst A component DCAT-A2 is as follows: 36 wt% (dry basis) of modified ZSM-5 molecular sieve DZ-2, 36 wt% (dry basis) of kaolin, 12 wt% (dry basis) of boehmite, and 16 wt% of phosphorus pentoxide from the phosphoric acid added in step 2.

[0224] This comparative example provides a catalytic cracking catalyst, wherein catalyst component B is catalyst component B CAT-B1 prepared in Example 1. Catalyst component A DCAT-A2 and catalyst component B CAT-B1 are mixed at a weight ratio of 98:2 to obtain the catalytic cracking catalyst DCAT-2 of this comparative example.

[0225] Comparative Example 3

[0226] This comparative example provides a catalytic cracking catalyst, the preparation method of which includes:

[0227] 1. Preparation of modified ZSM-5 molecular sieves:

[0228] (1) Take 170.6 g of Fe(NO3)3·9H2O and 96 g of titanium tetrachloride, dissolve them in a suitable amount of distilled water to prepare a mixed iron nitrate / titanium tetrachloride impregnation solution, slowly pour the mixed impregnation solution into 1.426 kg of ordinary ZSM-5 molecular sieve (dry basis), continuously stir to achieve equal volume impregnation; after standing for 12 h, put it into a 120°C oven for drying for 6 h; calcine in a 540°C muffle furnace for 4 h to obtain the modified molecular sieve DZ-3;

[0229] According to the calculation of the amount of raw materials added, the titanium-iron modified ZSM-5 molecular sieve contains 2.7% titanium (calculated as oxide) and 2.25% iron (calculated as oxide), and the balance is ZSM-5 molecular sieve.

[0230] 2. Preparation of catalyst A component:

[0231] Put 0.78 kg of kaolin (dry basis), 0.18 kg of diatomite (dry basis), 0.3 kg of pseudo-boehmite (dry basis), and 4.18 L of deionized water into a beater tank for beating, stir for 0.5 h, then add 25 mL of nitric acid, stir for 45 min, and then acidify at 55°C for 2 h; then add 1.26 kg of ZSM-5 molecular sieve DZ-3 (dry basis), 0.799 kg of phosphoric acid, and 30 g of polyethylene glycol, mix and beat for 1 h, then homogenize, spray dry, and calcine at 500°C for 2 h to obtain the comparative catalytic cracking catalyst A component DCAT-A3.

[0232] The raw material composition of the comparative catalytic cracking catalyst A component DCAT-A3 is: modified ZSM-5 molecular sieve DZ-3 42 wt% (dry basis), kaolin 26 wt% (dry basis), diatomite 6 wt% (dry basis), pseudo-boehmite 10 wt% (dry basis), and phosphorus pentoxide from the added phosphoric acid in step 2 16 wt%.

[0233] Mix the catalyst A component DCAT-A3 and the catalyst B component (CAT-B4 prepared in Example 4) in a weight ratio of 90:10 to obtain the comparative catalytic cracking catalyst DCAT-3.

[0234] Comparative Example 4

[0235] This comparative example provides a catalytic cracking catalyst, which is prepared as follows:

[0236] Put 0.504 kg of kaolin (dry basis), 0.3 kg of halloysite (dry basis), 0.833 kg of aluminum sol, and 1.83 kg of deionized water into a beater tank for beating, then add 0.75 kg of pseudo-boehmite (dry basis), stir for 1 h, then add 101 mL of hydrochloric acid, stir for 0.5 h, and then acidify at 55°C for 2 h.

[0237] Mix 0.126 kg of GUSY-1 molecular sieve (dry basis), 1.134 kg of ZSM-5 molecular sieve DZ-3 prepared in Comparative Example 3 (dry basis), 6 g of yttrium oxide and 1.96 kg of deionized water in a beater for 0.5 h, then add into the beater of the first step, beat for 1.5 h, homogenize, spray dry to obtain catalyst microspheres.

[0238] The catalyst microspheres obtained by spray drying are calcined, washed to reduce sodium, dried to obtain the catalytic cracking catalyst DCAT-4 of the present comparative example.

[0239] The raw material composition of the catalytic cracking catalyst DCAT-4 is: 16.8 wt% of kaolin (dry basis), 10 wt% of halloysite (dry basis), 25 wt% of pseudoboehmite (dry basis), 6 wt% of alumina from aluminum sol, 4.2 wt% of GUSY-1 molecular sieve (dry basis), 37.8 wt% of ZSM-5 molecular sieve DZ-3 (dry basis), 0.2 wt% of yttrium oxide, and the catalyst gel content is 36%.

[0240] Comparative Example 5

[0241] The present comparative example provides a catalytic cracking catalyst, and the preparation method thereof comprises:

[0242] 1. Preparation of modified ZSM-5 molecular sieve:

[0243] (1) Add 1.402 kg of micro-mesoporous ZSM-5 molecular sieve (dry basis) into 4 L of deionized water, stir uniformly, then add 73 g of phosphoric acid, stir uniformly, dry at 120°C, and calcine at 500°C for 1 h;

[0244] (2) Mix the calcined product of step (1) with 4 L of deionized water, add 139 g of waste liquid containing titanium tetrachloride, stir for 0.5 h to form a slurry containing molecular sieve, stir uniformly, dry at 120°C, and calcine at 500°C for 1 h to obtain a titanium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve, which is denoted as DZ-4.

[0245] The composition of the titanium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve is: 3.5% of titanium (calculated as oxide), 3.0% of phosphorus (calculated as oxide), and the balance of ZSM-5 molecular sieve.

[0246] 2. Preparation of catalyst A component: the preparation method is similar to that of catalyst A component in Example 1, except that the modified ZSM-5 molecular sieve used in the present example is the titanium-phosphorus modified micro-mesoporous ZSM-5 molecular sieve of step 1 of the present example.

[0247] 3. Preparation of catalyst B component: the preparation method is the same as that of catalyst B component in Example 1.

[0248] The catalyst A component and the catalyst B component were mixed in a weight ratio of 98:2 to obtain the catalytic cracking catalyst DCAT-5 of the present comparative example.

[0249] The median particle sizes of the catalyst A components and the catalyst B components obtained in the above examples and comparative examples were 65-78 μm.

[0250] Test Example 1

[0251] (1) The present test example provides the test results of the hydrothermal stability of the modified ZSM-5 molecular sieves prepared in the above examples and comparative examples.

[0252] The modified ZSM-5 molecular sieves prepared in Examples 1-3 and 5-7 and the modified ZSM-5 molecular sieves prepared in Comparative Examples 1-3 and 5 were respectively taken as the samples to be tested, and the specific surface areas of the samples to be tested were measured; then the specific surface areas of the samples to be tested after aging at 800℃ under 100% steam for 17h were measured, and the specific surface area retention rates were calculated. The results are shown in Table 2.

[0253] Table 2: Test results of the specific surface area retention rates of the ZSM-5 molecular sieves of the examples and comparative examples

[0254]

[0255] The results in Table 2 show that, after aging at 800℃ under 100% steam for 17h, the specific surface area retention rate of the ZSM-5 molecular sieve prepared by the method of the present application is higher than that of the comparative ZSM-5 molecular sieves DZ-1, DZ-2 and DZ-3 prepared in the comparative examples.

[0256] The difference between Example 1 and Comparative Example 1 is only whether the titanium source is added. The specific surface area retention rate of the titanium-phosphorus modified ZSM-5 molecular sieve of Example 1 is 11.7% higher than that of the phosphorus modified ZSM-5 molecular sieve of Comparative Example 1.

[0257] The modified elements used in Example 5 and Comparative Example 3 are different. It can be seen from the comparison that the specific surface area retention rate of the titanium-iron-phosphorus modified ZSM-5 molecular sieve of Example 5 is 10.4% higher than that of the titanium-iron modified ZSM-5 molecular sieve of Comparative Example 3.

[0258] The difference between Comparative Example 5 and the various embodiments (especially Example 6) lies in the different modification order of the phosphorus and titanium sources. As shown in Table 2, compared to modifying ZSM-5 molecular sieves with phosphorus first and then with titanium, the reaction order of modifying ZSM-5 molecular sieves with titanium first and then with phosphorus, as used in this invention, significantly improves the specific surface area retention rate of the molecular sieve, with an increase of more than 8 percentage points. These results demonstrate that this invention can effectively improve the hydrothermal stability of ZSM-5 molecular sieves by controlling the reaction order.

[0259] The types of titanium sources used in Example 1 and Example 6 are different. As can be seen from Table 2, both pure titanium tetrachloride and waste liquid containing titanium tetrachloride can improve the specific surface area retention rate of molecular sieves to a certain extent when used as titanium sources to modify molecular sieves; among them, waste liquid containing titanium tetrachloride has a more significant effect on improving hydrothermal stability than pure titanium tetrachloride.

[0260] The above results demonstrate that the preparation method of the present invention, by using titanium phosphorus as a modifying element and controlling the reaction sequence, can significantly improve the hydrothermal stability of the titanium phosphorus-modified ZSM-5 molecular sieve obtained therefrom. On this basis, using iron, zirconium, zinc, magnesium, calcium, zirconium, lanthanum, cerium, and yttrium as second metals for modification can further enhance the performance of ZSM-5 molecular sieve.

[0261] (2) This test example also provides the elemental composition analysis results of the modified ZSM-5 molecular sieves of the above examples and comparative examples. The content of each element in the samples of the above examples and comparative examples was tested by X-ray fluorescence analysis. The weight content of titanium, phosphorus, iron and zirconium elements is calculated as oxides, and the weight content of chlorine element is calculated as Cl element. The test results are summarized in Table 3.

[0262] Table 3. Elemental content analysis results of modified ZSM-5 molecular sieves in each example and comparative example.

[0263]

[0264] The main difference between Comparative Example 5 and each of the Examples (especially Example 1) is that in Comparative Example 5, the ZSM-5 molecular sieve is first modified with phosphorus and then modified with titanium, while in the Examples, the ZSM-5 molecular sieve is first modified with titanium and then modified with phosphorus. The results show that the Cl content in the modified ZSM-5 molecular sieve of each of the Examples is close to 0, while the Cl content in the modified ZSM-5 molecular sieve of Comparative Example 5 is more than 7%, indicating that the modified ZSM-5 molecular sieve prepared in the Examples of the present application contains less impurities, and further indicating that the reaction sequence of the present application can effectively reduce the impurity content in the modified ZSM-5 molecular sieve and improve the quality of the molecular sieve. In the process of catalytic cracking reaction, if the chlorine content on the molecular sieve and catalyst is too high, it is easy to cause corrosion and salt deposition of the catalytic cracking device, which is not conducive to the long-term stable operation of the device.

[0265] The appearance color of the modified ZSM-5 molecular sieve (first modified with titanium and then modified with phosphorus) of each of the Examples is white, while the appearance color of the modified ZSM-5 molecular sieve (first modified with phosphorus and then modified with titanium) of Comparative Example 5 is gray. This result indicates that the template in the modified ZSM-5 molecular sieve of Comparative Example 5 is not easy to remove, while the template can block the pore channels of the molecular sieve, which has an adverse effect on the catalytic process; while the template in the modified ZSM-5 molecular sieve prepared in the present application is easy to remove through the calcination process, thereby avoiding the situation that the template blocks the pore channels of the molecular sieve, which is conducive to improving the selectivity of the molecular sieve in the catalytic reaction. The results of the determination of the pore volume also show that the pore volume of the modified ZSM-5 molecular sieve prepared in Comparative Example 5 is 0.25 mL / g, and the pore volume of the modified ZSM-5 molecular sieve prepared in Example 1 is 0.31 mL / g, indicating that the modified ZSM-5 molecular sieve prepared in the present application has a relatively unobstructed pore structure.

[0266] The ZSM-5 molecular sieve crystallinity of the modified ZSM-5 molecular sieves of Example 1, Example 2, Example 6, Comparative Example 1 and Comparative Example 5 was analyzed, and the results of the crystallinity of each molecular sieve were as follows: the molecular sieve crystallinity of Example 1 was 65%, the molecular sieve crystallinity of Example 2 was 66%, the molecular sieve crystallinity of Example 6 was 65%, the molecular sieve crystallinity of Comparative Example 1 was 60%, and the molecular sieve crystallinity of Comparative Example 5 was 63%. The main difference between Comparative Example 1 and Examples 1 and 2 was that Comparative Example 1 only used phosphorus-modified ZSM-5 molecular sieves and did not use titanium modification. During the modification of the molecular sieves, high-temperature calcination treatment was performed, which caused dealumination and structural damage to the molecular sieves during the calcination process, resulting in a decrease in the crystallinity of the molecular sieves measured by XRD. Therefore, the crystallinity of the molecular sieves in the modified product can reflect the stability of the molecular sieves. Compared with the modified ZSM-5 molecular sieves prepared in Comparative Example 1, the ZSM-5 molecular sieve crystallinity of the modified ZSM-5 molecular sieves of Examples 1, 2 and 6 was increased by more than 5 percentage points, indicating that the titanium-phosphorus synergistic modification made the modified ZSM-5 molecular sieves prepared in the present application more stable than the modified ZSM-5 molecular sieves of Comparative Example 1. Compared with the modified ZSM-5 molecular sieves of Comparative Example 5, the ZSM-5 molecular sieve crystallinity of the modified ZSM-5 molecular sieves of Example 1 was increased by 2 percentage points, while the ZSM-5 molecular sieve crystallinity of the modified ZSM-5 molecular sieves of Comparative Example 5 was lower, at 63%. This result also indicates that the modified ZSM-5 molecular sieves prepared in the present application are more stable than the modified ZSM-5 molecular sieves of Comparative Example 5. The above results show that the stability of the ZSM-5 molecular sieves can be effectively improved by titanium-phosphorus synergistic modification (further modification with modification metals such as zirconium) and control of the modification sequence.

[0267] Test Example 2

[0268] This test example was used to evaluate the performance of the catalytic cracking catalysts of Examples 1-4.

[0269] The catalytic cracking catalysts CAT-1, CAT-2, CAT-3 and CAT-4 prepared in Examples 1-4 and 6-7 and the comparative catalytic cracking catalysts DCAT-1, DCAT-2 and DCAT-5 prepared in Comparative Examples 1, 2 and 5 were each subjected to aging treatment at 800°C and 100% steam for 17 hours, and then the catalytic cracking reaction performance was evaluated on a heavy oil micro-reaction evaluation device (ACE) using waxy oil from Lanzhou Petrochemical Company as the raw oil.

[0270] The reaction selectivity evaluation results of the catalytic cracking catalysts of Examples 1-4, Examples 6-7, Comparative Examples 1-2 and Comparative Example 5 are shown in Table 4.

[0271] In Table 4, total liquid yield = liquefied gas yield + gasoline yield + diesel yield; coke factor = (100 - conversion rate) x coke yield / conversion rate.

[0272] Table 4

[0273]

[0274] Referring to Table 4, compared with the comparative catalytic cracking catalyst DCAT-2, the reaction conversion rate of the catalyst CAT-1 prepared in Example 1 is increased by 0.71 percentage points, the total liquid yield (liquefied gas + gasoline + diesel) is increased by 1.46 percentage points, the coke yield is reduced by 1.09 percentage points, the coke factor is reduced, the low-carbon olefin (ethylene + propylene + butene) yield is increased by 3.02 percentage points, which shows the characteristics of excellent heavy oil conversion, reduced coking and prolific low-carbon olefin.

[0275] The above results show that, compared with the comparative catalytic cracking catalysts DCAT-1, DCAT-2 and DCAT-5 of Comparative Examples 1, 2 and 5, the reaction conversion rate of the catalytic cracking catalysts CAT-1, CAT-2, CAT-3 and CAT-4 of the present application is increased, the heavy oil yield is reduced, the coke factor is reduced, and the low-carbon olefin (ethylene + propylene + butene) yield is increased. It is shown that, when the catalytic cracking catalyst prepared by using the waste liquid containing titanium tetrachloride provided by the present application is used, the efficient conversion of heavy oil is promoted, the coking tendency is reduced, and the low-carbon olefin is prolific, and the selectivity of the catalytic cracking reaction is improved.

[0276] The results of Table 4 also show that, compared with the catalysts DCAT-1, DCAT-2 and DCAT-5 prepared by using Comparative Examples, the catalysts prepared by using pure titanium tetrachloride and the combination of titanium tetrachloride and n-hexane in Example 6 and Example 7 also show the characteristics of reduced heavy oil, reduced coke factor and high low-carbon olefin yield, which shows that the catalysts prepared by using pure titanium tetrachloride and the combination of titanium tetrachloride and n-hexane can improve the selectivity of the catalytic reaction of the catalyst.

[0277] Test Example 3

[0278] This test example is used to evaluate the performance of the catalytic cracking catalyst of Example 5.

[0279] The catalytic cracking catalyst CAT-5 prepared in Example 5 and the comparative catalytic cracking catalysts DCAT-3 and DCAT-4 prepared in Comparative Examples 3 and 4 are respectively subjected to aging treatment at 800℃ and 100% steam for 17h, and then the catalytic cracking reaction performance evaluation is carried out on a heavy oil micro-reaction evaluation device (ACE) by using waxy oil of Lanzhou Petrochemical Company as raw oil.

[0280] The results of the evaluation of the reaction selectivity of the catalytic cracking catalysts of Example 5, Comparative Examples 3-4 are shown in Table 5. In Table 5, total liquid yield = LPG yield + gasoline yield + diesel yield; coke factor = (100 - conversion rate) x coke yield / conversion rate.

[0281] Table 5

[0282]

[0283] Referring to Table 5, compared with the comparative catalyst DCAT-4, the reaction conversion rate of the catalytic cracking CAT-5 prepared in Example 5 is increased by 1.12 percent points, the coke yield is reduced by 1.01 percent points, the coke factor is reduced, the low-carbon olefin (ethylene + propylene + butene) yield is increased by 7.35 percent points, which shows the characteristics of excellent heavy oil conversion, reduced coking and prolific low-carbon olefin.

[0284] The results of Table 5 show that, compared with the catalysts DCAT-3, DCAT-4 of Comparative Examples 3, 4, the reaction conversion rate of the catalytic cracking CAT-5 of the present application is increased, the heavy oil yield is reduced, the coke factor is reduced, and the low-carbon olefin (ethylene + propylene + butene) yield is increased. It is shown that, compared with the prior art titanium-containing catalyst, the use of the catalyst provided by the present application can promote the efficient conversion of heavy oil, reduce the heavy oil yield, reduce the coking tendency, and produce more low-carbon olefins, and improve the selectivity of the catalytic cracking reaction.

[0285] The above test results show that, when the catalyst system formed by mixing the catalyst A component and the catalyst B component is used in the catalytic cracking process, the heavy oil conversion in the catalytic cracking process is promoted, the heavy oil yield is reduced, the coking tendency is reduced while producing more low-carbon olefins such as ethylene and propylene, and the catalyst has excellent reaction selectivity and use performance.

Claims

1. A catalytic cracking catalyst comprising a mixture of catalyst component A and catalyst component B in a weight ratio of 98:2 to 20:80; Based on 100% by weight of the raw materials for catalyst component A, the raw materials for catalyst component A include: 15%-55% modified ZSM-5 molecular sieve, 10%-55% clay, 3%-20% aluminum source, 5%-20% phosphorus from the second modifier, wherein the weight of the modified ZSM-5 molecular sieve, clay, and aluminum source is on a dry basis, and the weight of the phosphorus is on an oxide basis. The modified ZSM-5 molecular sieve is obtained by modifying the raw ZSM-5 molecular sieve with a first modifier; The first modifier includes a titanium source and a phosphorus source; The preparation method of the modified ZSM-5 molecular sieve includes: mixing raw material ZSM-5 with titanium source of first modifier to form a mixture, and performing a first calcination; mixing the product of the first calcination with phosphorus source of first modifier, and performing a second calcination to obtain the modified ZSM-5 molecular sieve. The raw materials of catalyst component B, based on 100% by weight, include: 15%-50% Y-type molecular sieve, 10%-55% clay, 5%-30% aluminum source, and 3%-20% binder; wherein the weights of the Y-type molecular sieve, clay, and aluminum source are on a dry basis, and the weight of the binder is based on oxides.

2. The catalytic cracking catalyst according to claim 1, wherein, The weight ratio of catalyst component A to catalyst component B is 97:3-30:

70.

3. The catalytic cracking catalyst according to claim 1, wherein, Based on the total weight of the modified ZSM-5 molecular sieve as 100%, the modified ZSM-5 molecular sieve includes 0.2%-25% titanium from the first modifier and 0.2%-6% phosphorus from the first modifier; wherein the weight of the titanium and phosphorus is calculated as oxides.

4. The catalytic cracking catalyst according to claim 1, wherein, The modified ZSM-5 molecular sieve further includes modified metal elements, and the first modifier further includes a modified metal source; the modified metal elements include one or more combinations of iron, zinc, magnesium, calcium, zirconium, lanthanum, cerium, and yttrium.

5. The catalytic cracking catalyst according to claim 4, wherein, The weight of the modified metal element from the first modifier, calculated as oxide, is 0-5% of the weight of the modified ZSM-5 molecular sieve and is not zero.

6. The catalytic cracking catalyst according to claim 1, wherein, The method for preparing the modified ZSM-5 molecular sieve includes: fully impregnating the raw material ZSM-5 molecular sieve with an impregnation solution containing a titanium source, drying it, and performing a first calcination; mixing the product of the first calcination with a phosphorus source of a first modifier, and performing a second calcination to obtain the modified ZSM-5 molecular sieve.

7. The catalytic cracking catalyst according to claim 1 or 6, wherein, The first roasting temperature is 450-650℃, and the first roasting time is 1-4h.

8. The catalytic cracking catalyst according to claim 1 or 6, wherein, The second roasting temperature is 450-650℃, and the second roasting time is 1-4h.

9. The catalytic cracking catalyst according to claim 1, wherein, The pH value of the mixture is 0.5-8.

10. The catalytic cracking catalyst according to claim 9, wherein, The pH value of the mixture is 0.5-3.

11. The catalytic cracking catalyst according to claim 6, wherein, The pH value of the impregnation solution is 0.5-8.

12. The catalytic cracking catalyst according to claim 11, wherein, The pH value of the impregnation solution is 0.5-3.

13. The catalytic cracking catalyst according to claim 1, wherein, The second modifier includes a phosphorus source.

14. The catalytic cracking catalyst according to claim 13, wherein, The second modifier also includes a titanium source, which, based on 100% by weight of catalyst component A, contains 0-10% (not zero) titanium oxide from the second modifier.

15. The catalytic cracking catalyst according to claim 13, wherein, The second modifier further includes a modified metal source, which, based on 100% of the weight of catalyst component A, contains 0-5% (not zero) of modified metal elements, calculated as oxides, from the second modifier. The modified metal elements include one or more of iron, zinc, magnesium, calcium, zirconium, lanthanum, cerium, and yttrium.

16. The catalytic cracking catalyst according to claim 1, wherein, The raw materials for catalyst component A also include a binder.

17. The catalytic cracking catalyst according to claim 16, wherein, The binder, calculated as an oxidant, is 0-10% of the weight of catalyst component A, but not 0%.

18. The catalytic cracking catalyst according to claim 1, wherein, Based on the weight of the raw materials of catalyst component A as 100%, the raw materials of catalyst component A include 20%-50% modified ZSM-5 molecular sieve on a dry basis. And / or, based on 100% by weight of the raw materials of catalyst component A, the raw materials of catalyst component A include 10%-50% clay on a dry basis; And / or, based on 100% by weight of the raw material of catalyst component A, the raw material of catalyst component A includes 3%-15% aluminum source on a dry basis; And / or, based on 100% by weight of the raw material of catalyst component A, the raw material of catalyst component A includes 6%-19% phosphorus in oxide form from the second modifier.

19. The catalytic cracking catalyst according to claim 1, wherein, The raw material of catalyst component B is 100% by weight, and the raw material of catalyst component B also includes 0-10% (not 0) of ZSM-5 molecular sieve on a dry basis; the ZSM-5 molecular sieve includes the raw material ZSM-5 molecular sieve and / or modified ZSM-5 molecular sieve.

20. The catalytic cracking catalyst according to claim 1, wherein, The raw materials of catalyst component B also include a third modifier, which further includes a modified metal source, and the raw materials of catalyst component B also contain 0-5% (not zero) of modified metal elements, calculated as oxides, from the third modifier.

21. The catalytic cracking catalyst according to claim 20, wherein, The modified metal element in the third modifier includes one or more of the following: iron, zinc, magnesium, calcium, zirconium, lanthanum, cerium, and yttrium.

22. The catalytic cracking catalyst according to any one of claims 1, 6, or 14, wherein, The titanium source in the first modifier and the second modifier includes titanium tetrachloride.

23. The catalytic cracking catalyst according to claim 22, wherein, The titanium source in the first and second modifiers includes titanium tetrachloride and hexane in a weight ratio of (4-34):

1.

24. The catalytic cracking catalyst according to claim 22, wherein, The titanium source in the first modifier and the second modifier includes waste liquid containing titanium tetrachloride; based on the total weight of the waste liquid containing titanium tetrachloride as 100%, the waste liquid containing titanium tetrachloride includes: 80%-95% titanium tetrachloride, 2%-5% alkoxy titanium complex, and the balance is hydrocarbons, including hexane.

25. The catalytic cracking catalyst according to any one of claims 1, 6, or 13, wherein, The phosphorus source in the first modifier and the second modifier includes one or more combinations of phosphoric acid, phosphate, phosphorous acid, phosphite, pyrophosphate, pyrophosphate, polyphosphate, polyphosphate, metaphosphate, and metaphosphate.

26. The catalytic cracking catalyst according to claim 25, wherein, The phosphorus source in the first modifier and the second modifier includes one or more of the following: phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, diammonium hydrogen phosphate, magnesium phosphate, aluminum phosphate, phosphorous acid, ammonium phosphite, sodium pyrophosphate, sodium tripolyphosphate, and sodium hexametaphosphate.

27. The catalytic cracking catalyst according to claim 1, wherein, In catalyst component A and catalyst component B, the aluminum source includes one or more of the following: boehmite, amorphous alumina, boehmite, aluminum nitrate, and aluminum chloride.

28. The catalytic cracking catalyst according to claim 1, wherein, The catalyst component B also includes an inorganic oxide support, which includes one or more of the following: silica, alumina containing Brønsted acid centers, and aluminosilicate containing Brønsted acid centers.

29. The catalytic cracking catalyst according to claim 28, wherein, The inorganic oxide support, by weight based on oxides, is 0-30% of the weight of catalyst component B, but not 0.

30. The catalytic cracking catalyst according to claim 1, wherein the raw material of catalyst component B comprises 20%-45% Y-type molecular sieve on a dry basis, based on 100% by weight of the raw material.

31. A method for preparing the catalytic cracking catalyst according to any one of claims 1-30, comprising: Preparation of catalyst component A: Modified ZSM-5 molecular sieve, clay, aluminum source and second modifier are mixed and then pulped to form the first slurry; The first slurry is spray-dried and calcined to obtain catalyst component A; wherein the second modifier includes a phosphorus source; Preparation of catalyst component B: Y-type molecular sieve, clay, aluminum source, binder and third modifier are mixed and slurryed to form a second slurry; the second slurry is spray-dried and calcined to obtain catalyst component B; the third modifier includes a modified metal source; The catalyst component A and catalyst component B are mixed to obtain the catalytic cracking catalyst.

32. The method for preparing the catalytic cracking catalyst according to claim 31, wherein, The raw material for the catalytic cracking catalyst includes a pore structure modifier, which is added to the first slurry and the second slurry. The mass of the pore structure modifier is 0.1%-10% of the total mass of the catalytic cracking catalyst.

33. The method for preparing the catalytic cracking catalyst according to claim 32, wherein, The pore structure improver includes one or more of 1,3,5-trimethylbenzene, 1,3,5-triisopropylbenzene, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, and polyethylene glycol.

34. The application of the catalytic cracking catalyst according to any one of claims 1-30 in a catalytic cracking process.

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