A high-strength, large-pore-volume, high-solid-content catalytic cracking catalyst and a preparation method thereof

Abstract

The application discloses a high-strength, large-pore-volume and high-solid-content catalytic cracking catalyst and a preparation method thereof. The raw material of the catalytic cracking catalyst comprises a zeolite molecular sieve, a matrix and a binder. The matrix is composed of a gamma-alumina precursor with a peptization index of less than or equal to 50% and clay. The binder comprises a phosphorus-containing compound, an aluminum-containing compound and a multi-metal chelate. The catalytic cracking catalyst is prepared in a high-shear emulsifier. Compared with existing catalytic cracking catalysts, the catalytic cracking catalyst provided by the application has higher wear resistance, a large pore volume, a high molecular sieve content, a high solid content and excellent reaction performance.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to a high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst and its preparation method. Background Technology

[0002] Catalytic cracking has become the most important process for heavy oil processing due to its significant advantages, including high heavy oil conversion efficiency, good product quality, non-hydrogenation capability, and low operating pressure. However, with the increasing deterioration and heavier composition of heavy oil, harmful impurities such as vanadium, nickel, alkali metals, alkaline earth metals, and alkaline nitrogen are increasing, and the amount of slag added is also constantly rising. This makes heavy oil difficult to crack, resulting in more coke being generated on the catalyst and faster deactivation. Therefore, there is a need to develop catalytic cracking catalysts with higher activity, stronger heavy oil conversion capacity, stronger resistance to heavy metals, and better coke selectivity.

[0003] To achieve the above objectives, it is necessary to increase the molecular sieve content or pore volume of the catalytic cracking catalyst. Preparing a macroporous catalyst is one solution. Furthermore, the development of new catalytic cracking technologies, such as short or ultra-short contact times and technologies for reducing olefin catalytic cracking, also requires catalysts with high molecular sieve content and / or macroporous structures. The binder in the catalytic cracking catalyst provides a certain heat capacity during the catalytic cracking reaction, and its performance directly affects the catalyst's physicochemical properties such as particle size, attrition index, and pore volume. Therefore, current research on catalysts largely focuses on the modification of the binder.

[0004] However, in existing technologies, when modifying the binder to develop catalytic cracking catalysts with higher activity, stronger heavy oil conversion capacity, stronger resistance to heavy metals, and better coke selectivity, increasing the content of the active component molecular sieve and increasing the pore volume of the catalytic cracking catalyst often leads to a deterioration in the catalyst's anti-wear performance, resulting in problems such as abnormal fluidization, catalyst loss, scale buildup in the flue gas turbine, and increased solid content in the slurry, which affect the long-term operation of the catalytic cracking unit.

[0005] For example, Chinese patent document CN201680055564.2 discloses a method for manufacturing a fluidized bed catalytic cracking catalyst additive composition using a novel binder. The steps involve mixing an alumina source with water to form a slurry; adding a certain amount of P2O5 source to the alumina slurry; then stirring the slurry and reacting it under controlled temperature and time conditions to form an aluminum phosphate binder; adding zeolite, a certain amount of silica binder, and a certain amount of clay to the aluminum phosphate binder; and spray drying the slurry to form catalyst additive particles. The catalyst additive composition comprises about 35 wt% to about 65 wt% zeolite; about 0 wt% to about 10 wt% silica; about 15 wt% to about 50 wt% clay; and an aluminum phosphate binder comprising about 2.5 wt% to 5 wt% amorphous or pseudoboehmite alumina and about 7 wt% to 15 wt% phosphoric acid. However, the aluminum phosphate binder prepared by this method provides limited improvement in catalyst strength, and the catalyst has a low pore volume.

[0006] US Patent document US4407730 discloses a catalyst support that, after being calcined at 500°C for 10 hours, is essentially composed of a magnesium oxide-alumina-aluminum phosphate matrix. The support has an average pore size of 10-300 angstroms and a specific surface area of ​​100-350 μm. 2 The catalyst support has a pore volume of 0.3-1.5 ml / g, with magnesium oxide content of 0.5% to less than 10 mol% or 25-75 mol%, aluminum oxide content of 2-90 mol%, and aluminum phosphate content of 3-95 mol%. The preparation method involves mixing an aqueous solution of aluminum nitrate, magnesium nitrate, and 85% phosphoric acid solution, then adding ammonium hydroxide solution, precipitating at pH=9, filtering, drying, and calcining at 500℃ for about 10 hours. The catalytic cracking catalyst prepared by mixing this catalyst support with zeolite exhibits high gasoline selectivity and can be used as a catalyst for cracking high-metal-content feedstocks. In this literature, magnesium oxide is added during the preparation of the binder to capture high-content metal ions in the feedstock, thereby achieving the effect of processing high-metal-content feedstocks. However, the introduction of metal ions into the binder causes the formation of a fixed crystalline phase with the aluminum phosphate binder. In actual reactions, the capturing effect of magnesium ions reduces the binding performance of the binder. Simultaneously, the use of aluminum phosphate binder reduces the pore volume and specific surface area of ​​the catalyst, and it is prone to cracking at high temperatures, resulting in poor high-temperature wear resistance.

[0007] US Patent document US5286369 discloses a catalytic cracking method for hydrocarbon feedstocks. This method involves reacting a hydrocarbon feedstock under catalytic cracking process conditions in the presence of a catalyst. The catalyst contains one zeolite selected from ultrastable Y zeolite, ZSM-5 zeolite, Beta zeolite, SAPO zeolite, and ALPO zeolite, and a crystalline aluminum phosphate binder. The crystalline aluminum phosphate binder has a specific surface area of ​​less than 20 m² / g and a pore volume of less than 0.1 mL / g. However, the specific surface area and pore volume of the crystalline aluminum phosphate binder in this method are relatively small, and the reactivity of the resulting catalyst needs further improvement.

[0008] Chinese patent document CN201110180891.X discloses an inorganic binder containing a phosphorus-aluminum compound and its preparation method. The binder contains 15-40 wt% Al₂O₃, 45-80 wt% P₂O₅, and 1-40 wt% clay, with a P / Al weight ratio of 1-6, a pH value of 1-3.5, and a solid content of 15-60 wt%. The preparation method includes: dispersing acid-soluble aluminum hydroxide and / or alumina, along with clay and decationized water, into a slurry with a solid content of 15-45 wt%; adding concentrated phosphoric acid to the slurry under stirring at a P / Al weight ratio of 1-6; and then reacting at 50-99°C for 15-90 minutes. However, the binder prepared by this method has a small pore volume and is prone to cracking at high temperatures, resulting in poor thermal abrasion performance of the catalyst prepared using this binder.

[0009] Chinese patent document CN99126287.5 discloses a phosphorus- and zeolite-containing catalytic cracking catalyst, comprising zeolite, clay, and a binder. The catalyst further contains a phosphorus- and aluminum-containing additive uniformly dispersed within the catalyst. Based on the total weight of the catalyst, the zeolite content is 25-70 wt%; the clay content is 5-55 wt%; the binder content is 5-50 wt%; and the phosphorus- and aluminum-containing additive content, based on the additive solids content, is 0.5-20 wt%. The phosphorus- and aluminum-containing additive is a reaction product obtained by reacting a phosphoric acid solution with aluminum oxides and / or hydroxides, having a specific gravity of 1.2-1.7 g / mL and an atomic ratio of phosphorus to aluminum greater than 1 to 12. However, this scheme still uses conventional binders to prepare catalytic cracking catalysts and adds a small amount of aluminum phosphate binder. Due to the small amount added, it cannot significantly improve the catalyst attrition index. At the same time, the phosphorus in the introduced aluminum phosphate additive exists in a free state and migrates into the molecular sieve of the active center during calcination, destroying the molecular sieve structure and affecting the reaction performance. On the other hand, the colloidal particles of conventional binders such as aluminum sol and acidified pseudoboehmite are small in size and fill the pores between the matrix and active components, resulting in a small catalyst pore volume.

[0010] As mentioned above, the aluminum phosphate sol (or aluminum phosphate solution) used in the prior art is prepared by reacting phosphorus compounds with aluminum sol or silica sol under controlled pH > 3 conditions; or by precipitating a phosphoric acid solution containing aluminum nitrate and magnesium nitrate with ammonium hydroxide solution at pH = 9 conditions; or by precipitating a solution containing phosphoric acid and rare earth ions with an alkaline solution; or by precipitating a solution containing aluminum ions, phosphate, and hydrogen phosphate with an alkaline solution; or by directly adding an ammonium salt of phosphoric acid, ammonium salt of orthophosphate, and ammonium salt of diphosphite, and a phosphoric acid compound to a slurry containing silica, clay, and zeolite; or by directly adding an aluminum phosphate solution with a pH of 0–1 to a slurry containing zeolite. While these methods can increase the wear resistance of catalysts to some extent, their wear resistance remains insufficient when the molecular sieve content in the catalyst is high or the catalyst pore volume is large. It was also found that when the molecular sieve content in the catalyst was high or the catalyst pore volume was large, the catalyst particles experienced varying degrees of breakage when using existing aluminum phosphate sol to prepare the catalyst, especially after high-temperature steam aging. This is because when preparing the phosphoric acid binder using the above method, the binder is mixed with the matrix material and molecular sieve for a long time. The matrix material and molecular sieve contain a large amount of chloride, ammonium, nitrate and various metal ions, resulting in impurities in the formed aluminum phosphate crystals. At high temperatures, especially in the presence of steam, the crystal structure is prone to collapse. Chloride, ammonium and nitrate, which are stably bonded with the binder components, become unstable and generate gases such as hydrogen chloride, ammonia, nitrogen and oxygen, respectively. The generation of these gases causes a large number of "bubbles" to form inside the catalyst particles. When the temperature rises, these bubbles will burst out from inside the catalyst, causing damage to the shape of the catalyst particles. In severe cases, this leads to the breakage of the catalyst particles, thereby reducing the bonding effect of various binders and greatly reducing the anti-wear performance of the catalyst. Summary of the Invention

[0011] To overcome the above-mentioned shortcomings, the present invention provides a high-strength, large-pore-volume, high-solid-content catalytic cracking catalyst and its preparation method. Compared with existing catalytic cracking catalysts, the phosphorus- and zeolite-containing catalytic cracking catalyst provided by the present invention has higher wear resistance, larger pore volume, higher molecular sieve content, higher solid content, and better reaction performance.

[0012] To achieve the above objectives, the present invention provides the following technical solution:

[0013] A high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst, wherein the raw materials of the catalytic cracking catalyst include zeolite molecular sieves, a matrix and a binder, wherein the matrix is ​​composed of γ-alumina precursors with a colloidal index ≤50% and clay, and the binder includes phosphorus-containing compounds, aluminum-containing compounds and polymetallic chelates.

[0014] The catalytic cracking catalyst is prepared in a high-shear emulsifier.

[0015] Optionally, in the catalytic cracking catalyst provided by the present invention, the multi-metal chelate is selected from at least one of phosphonic acid metal chelates, aminocarboxylic acid metal chelates, hydroxyaminocarboxylic acid metal chelates, carboxylic acid metal chelates, and carbonyl metal chelates.

[0016] Optionally, in the catalytic cracking catalyst provided by the present invention, the multi-metal chelate is a mixture of at least two metal chelates or a chelate containing at least two metals, wherein the metal in the multi-metal chelate is at least one of rare earth metal ions, transition metal ions, alkali metal ions, and alkaline earth metal ions; preferably, the metal in the multi-metal chelate is a transition metal ion and a rare earth metal ion; the ratio of various metal ions in the multi-metal chelate is not specifically limited and can be adjusted according to the actual situation. The present invention recommends a molar ratio of transition metal ions to rare earth metal ions of 5 to 15:1 in the multi-metal chelate.

[0017] Preferably, the rare earth metal ions are selected from rare earth metal ions, such as lanthanum ions, cerium ions, neodymium ions, samarium ions, etc.; the transition metal ions are selected from copper, silver, nickel, zinc, cobalt, cadmium, etc.

[0018] Optionally, in the catalytic cracking catalyst provided by the present invention, the multimetallic chelate is selected from at least two of the following: copper and lanthanum bimetallic hydroxyethyl ethylenediamine triacetic acid chelate, or aminotrimethylphosphonic acid copper chelate, n-acyl ethylenediamine triacetic acid silver chelate, hydroxyethyl ethylenediamine triacetic acid chelated lanthanum, hydroxyethyl ethylenediamine triacetic acid chelated cerium, ethylenediaminetetraacetic acid chelated copper, ethylenediaminetetraacetic acid chelated silver, diethylenetriamine chelated yttrium, aminotrimethylphosphonic acid chelated zinc, DOTA chelated lanthanum, β-diketone rare earth cerium, and copper and lanthanum bimetallic hydroxyethyl ethylenediamine triacetic acid chelate.

[0019] Optionally, in the catalytic cracking catalyst provided by the present invention, the ratio of the total molar amount of metal ions in the metal chelate to the molar amount of phosphorus in the phosphorus-containing compound is 5 to 20:1.

[0020] Optionally, in the catalytic cracking catalyst provided by the present invention, the molar ratio of phosphorus in the phosphorus-containing compound to aluminum in the aluminum-containing compound is 4-10:1, preferably 5-8:1. The aluminum-containing compound and the phosphorus-containing compound are not specifically limited and can be conventional in the industry. The aluminum-containing compound includes, but is not limited to, aluminum oxides, aluminum hydroxides, and aluminum-containing organic compounds, such as aluminum oxide, aluminum hydroxide, boehmite, sodium aluminate, aluminum chloride, and aluminum isopropoxide; the phosphorus-containing compound includes, but is not limited to, phosphorus oxides, phosphorus oxyacids, and phosphates, such as phosphoric acid, diammonium hydrogen phosphate, phosphorus pentoxide, organophosphonic acids, sodium phosphate, and calcium phosphate.

[0021] Optionally, in the catalytic cracking catalyst provided by the present invention, the colloid index of the γ-alumina precursor is 20% to 30%; preferably, the XRD pattern of the γ-alumina precursor shows characteristic peaks at 2θ of 14±1°, 28±1°, 38±1°, and 49±1°, such as boehmite, boehmite, etc.

[0022] Optionally, in the catalytic cracking catalyst provided by the present invention, the mass ratio of the γ-alumina precursor to the clay is 1:0.5 to 15, preferably 1:2 to 9.

[0023] Optionally, in the catalytic cracking catalyst provided by the present invention, the clay in the matrix can be any clay commonly used in the art, all of which can meet the requirements of the present invention, such as one or more of the components commonly used as catalytic cracking catalysts, including kaolin, hydrous kaolin, montmorillonite, diatomaceous earth, bentonite, and silicide. Preferably, the clay is selected from kaolin, silicide, hydrous kaolin, or mixtures thereof.

[0024] Optionally, the zeolite molecular sieves commonly used in the art in the catalytic cracking catalyst provided by the present invention can all meet the requirements of the present invention. For example, it can be one or more of various macroporous and mesoporous zeolite molecular sieves that are currently used as active components in catalytic cracking catalysts. Specifically, the zeolite molecular sieve can be selected from one or more of octahedral zeolite molecular sieves, ZSM series zeolite molecular sieves, Beta zeolite molecular sieves, and mordenite molecular sieves.

[0025] Optionally, in the catalytic cracking catalyst provided by the present invention, based on the total dry weight of the catalytic cracking catalyst as 100%, the content of the zeolite molecular sieve is 20wt% to 60wt%, the content of the matrix is ​​20wt% to 75wt%, the content of the binder is 5wt% to 30wt% (preferably the content of the binder is 10wt% to 20wt%), and the solid content of the catalytic cracking catalyst is 35wt% to 60wt% (preferably the solid content of the catalytic cracking catalyst is 40wt% to 50wt%).

[0026] The method for preparing the high-strength, large-pore-volume, and high-solid-content catalytic cracking catalyst recommended in this invention includes the following steps:

[0027] The slurry of zeolite molecular sieve and matrix is ​​mixed with a binder in a high-shear emulsifier for 5 minutes, then spray-dried, calcined, and ion-exchanged to obtain the high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst.

[0028] By controlling the mixing time of the zeolite molecular sieve and matrix slurry with the prepared binder in the high-shear emulsifier to no more than 5 minutes, instantaneous and thorough mixing is achieved. The mixture is then immediately output and spray-dried, realizing continuous "mixing, conveying, and drying" processes. This avoids prolonged contact between the slurry and binder, which could lead to phosphorus migration, damaging the crystal structure and surface acid distribution of the molecular sieve, and deteriorating the binding effect of the binder. Preferably, the mixing time of the zeolite molecular sieve and matrix slurry with the binder in the high-shear emulsifier is no more than 3 minutes.

[0029] Optionally, in the preparation method of the high-strength, large-pore-volume, and high-solid-content catalytic cracking catalyst provided by the present invention, the mixing slurry of the zeolite molecular sieve and the matrix is ​​a well-known operation in the art. Specifically, the zeolite molecular sieve, the matrix, and deionized water can be mixed and slurried, without any special requirements.

[0030] Optionally, in the preparation method of the high-strength, large-pore-volume, and high-solid-content catalytic cracking catalyst provided by the present invention, the spray molding drying refers to the granulation and drying of the material, which is a technology known to those skilled in the art. Existing parameters can be used. For example, the process conditions for spray molding drying in the preparation of catalytic cracking catalysts are generally as follows: the temperature of the spray tower furnace is controlled at 450-600℃, and the temperature of the spray tail gas is controlled at 150-300℃.

[0031] Optionally, in the preparation method of the high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst provided by the present invention, the ion exchange step is used to remove various impurity ions introduced in each step of the preparation process, including Na+. +SO 4- Cl - Wait, typically, washing with large amounts of water or ammonium salt solution is performed under acidic conditions. The ion exchange process conditions recommended by this invention are: acid exchange or ammonium exchange, pH 3.0–3.5, and exchange time of 0.3–2 hours.

[0032] Optionally, the preparation method of the high-strength, large-pore-volume, high-solid-content catalytic cracking catalyst provided by the present invention further includes a binder preparation step, comprising the following steps:

[0033] An aqueous solution of a phosphorus-containing compound with a pH value ≤ 5 is heated to 60–100°C, and an aluminum-containing compound is added and mixed. The mixed solution is then added to a high-shear emulsifier and reacted at 80–120°C to obtain a phosphorus-aluminum binder.

[0034] Then, a multi-metal chelate is added to the phosphorus-aluminum binder to continue the reaction. After the reaction is completed, the binder is obtained.

[0035] Optionally, in the preparation steps of the binder provided by the present invention, the aqueous solution of the phosphorus-containing compound with a pH value ≤ 5 is obtained by fully dissolving the phosphorus-containing compound in deionized water and then adjusting the pH with acid. The acid is not specifically limited; commonly used inorganic and organic acids in this field can meet the requirements. Preferably, the pH of the aqueous solution of the phosphorus-containing compound is ≤ 3. However, when the phosphorus-containing compound is a phosphorus-containing organic or inorganic acid, a small amount of acid may be added or omitted depending on the actual condition of the slurry to ensure the pH value is within this range.

[0036] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0037] Beneficial Effect 1: The catalytic cracking catalyst provided by this invention uses an aluminum phosphate binder containing polymetallic chelates to replace existing binders such as aluminum sol, silica sol, and acidified boehmite in the catalyst. By modifying the aluminum phosphate binder with polymetallic chelates, it can not only prevent the high content of binder during the catalyst preparation process from clogging the pores in the catalyst, but also reduce the amount of acid added during the catalyst preparation process, increase the pH value of the slurry, thereby reducing the corrosion of the zeolite molecular sieve structure by acid and improving the catalyst activity.

[0038] The catalytic cracking catalyst provided by this invention uses a low-colloidal-index γ-alumina precursor in the matrix. Firstly, this reduces the colloidal solubility of the γ-alumina precursor by the acidic medium during catalyst preparation, thereby reducing the blockage of catalyst and zeolite molecular sieve pores by the colloidal alumina. Simultaneously, it precisely controls the presence of free metallic aluminum in the catalyst system, avoiding excessive reaction with the effective components of the binder, which would affect the binder's bonding performance. A small portion of the colloidal γ-alumina precursor can react with phosphorus-containing compounds in the binder under specific conditions to form a binder. Secondly, the low-colloidal-index γ-alumina precursor can form a large number of mesopores during catalyst solidification, increasing the catalyst's pore volume. Thirdly, the use of the low-colloidal-index γ-alumina precursor overcomes the limitation of not being able to increase the catalyst's solid content. By controlling the colloidal solubility, the viscosity of the catalyst slurry can be adjusted, significantly increasing the solid content of the catalyst slurry, which is of great significance for improving the catalyst's sphericity.

[0039] The catalytic cracking catalyst provided by this invention, through the synergistic interaction between its components and the use of a high-shear emulsifier to disperse the components during the preparation process, ultimately produces a catalyst that maintains excellent wear resistance despite having a high molecular sieve content, large pore volume, and high solid content.

[0040] Beneficial Effect 2: The preparation method of the catalytic cracking catalyst provided by the present invention introduces metal chelates during the preparation of the binder. On the one hand, it can effectively avoid the introduction of matrix materials and zeolite molecular sieves or other heteroatoms into the binder. That is, it avoids the impurities introduced during the formation of aluminum phosphate crystals from affecting the crystallinity of aluminum phosphate crystals and causing collapse under high temperature hydrothermal conditions (that is, causing chloride, ammonium, nitrate ions to fail to form a strong bond with the binder, reducing the bubbles formed during the curing and calcination process, and thus forming defect sites in the catalyst, leading to collapse). On the other hand, and more importantly, the introduction of multi-metal chelates during the preparation of the binder allows the metal ions (transition metal ions, alkali metal ions, and / or light rare earth metal ions, etc.) in the chelates to modify the aluminum phosphate binder, strengthening the interaction between aluminum phosphate and the matrix material and zeolite molecular sieve, and improving the bonding strength between the binder and other components. Experiments show that the multi-metal chelates in the binder provided in this invention significantly reduce thermal collapse under high-temperature hydrothermal conditions, thereby greatly improving the thermal wear performance of the catalyst. Simultaneously, the introduction of multi-metal chelates into the binder avoids premature hardening of the colloid during the catalyst forming and drying process, preventing blockage of catalyst pores and resulting in reduced reaction performance, thus increasing the pore volume of the catalyst. Numerous experimental results demonstrate that adding metal chelates to the aluminum phosphate binder allows the formation of micropores and mesopores within the binder during preparation, thereby increasing the pore volume of the catalyst without affecting the binder's bonding performance.

[0041] Beneficial Effect 3: The preparation method of the catalytic cracking catalyst provided by this invention employs a high-shear emulsifier during catalyst preparation. On one hand, this method can disperse low-colloidal-index γ-alumina precursors into a uniform, viscous emulsion slurry and efficiently mix it with zeolite molecular sieves, overcoming the technical challenge of poor solubility of low-colloidal-index γ-alumina precursors and their inability to form a uniform slurry. Simultaneously, the γ-alumina precursors exist in a non-free state, avoiding excessive reactions with phosphorus-containing compounds in the binder. On the other hand, the application of the high-shear emulsifier solves the problem of insufficient mixing between metal chelates and aluminum phosphate binders, promoting the mutual reaction between the aluminum phosphate binder and metal chelates, effectively controlling the microenvironment such as supersaturation distribution within the reactor, and enhancing the role of the multi-metal chelate component in the binder modification process. More importantly, the application of the high-shear emulsifier enables efficient and short-time mixing of the binder, molecular sieve, and matrix slurry, achieving rapid emulsification of the low-solubility γ-alumina precursor and thorough homogenization of the binder and slurry. After uniform mixing, immediate spray drying and molding are performed, avoiding phosphorus migration caused by prolonged contact between the binder and molecular sieve, thus achieving the encapsulation and positioning of phosphorus in the aluminum phosphate binder. This plays an irreplaceable role in improving the catalyst's reactivity. Detailed Implementation

[0042] The present invention will now be described in detail through embodiments. It should be noted that the following embodiments are only for further illustration of the present invention and should not be construed as limiting the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments to the present invention based on the above description.

[0043] For any experimental steps or conditions not specified in the examples and comparative examples, the procedures or conditions described in the literature in this field can be followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0044] The raw materials and equipment involved in this invention are all commercially available and can all meet the requirements for implementing the technical solution of this invention. However, for ease of comparison, the raw materials from the following sources are used in the following embodiments:

[0045] ReY molecular sieves and ZSM-5 molecular sieves were sourced from Lanzhou Petrochemical Company.

[0046] Aluminum hydroxide, phosphoric acid, diammonium hydrogen phosphate, aluminum oxide, sodium phosphate, organophosphonic acid, phosphorus pentoxide, sodium aluminate, aluminum isopropoxide, copper nitrate, lanthanum chloride, copper chelate with ethylenediaminetetraacetic acid, silver chelate with ethylenediaminetetraacetic acid, cerium chelate with ethylenediaminetetraacetic acid, zinc chelate with aminotrimethylphosphonic acid, lanthanum chelate with DOTA, β-diketone rare earth cerium, copper and lanthanum bimetallic hydroxyethylethylenediaminetriacetic acid chelate; all were analytical grade and produced by Sinopharm Group.

[0047] Boehmite, produced by Chalco Shandong Aluminum.

[0048] Evaluation and analysis methods:

[0049] The surface area of ​​the catalyst was determined by the low-temperature nitrogen adsorption-desorption method (NB / SH / T0959);

[0050] The pore volume of the catalyst was tested using the water droplet method (NB / SH / T0955);

[0051] The catalyst attrition index was determined using the straight tube method (NB / SH / T0964);

[0052] The thermal collapse rate of the catalyst was tested on a small-scale fixed fluidized bed abrasion system (all parts are made of stainless steel) in the laboratory. The specific steps are as follows:

[0053] The catalyst in the fluidized bed undergoes continuous fluidization and abrasion under the action of fluidizing air. The extremely fine particles abraded are filtered out of the fluidized bed by the gas flow, while larger particles are blocked by the filter and remain in the fluidized bed for further abrasion. The gas inlet pipe has five evenly distributed air inlets with a diameter of 1 mm at its front end and around its perimeter, and the filter element has a filtration accuracy of 1 μm. In the experiment, 100 g of the prepared catalyst was first weighed and recorded as w1, then added to the fluidized bed. The preheater was heated to 150℃, and the fluidized bed temperature was raised to 200℃. The air generator was turned on, and the gas flow rate was adjusted to 40 m / s. The apparent gas velocity inside the reactor was 0.8 m / s. After 4 hours of fluidization and abrasion, the remaining catalyst mass in the reactor was weighed and recorded as w2. The preheater temperature was changed to 650℃, and the fluidized bed temperature to 680℃, while other conditions remained unchanged. The remaining catalyst weight was measured again and recorded as w3. The thermal collapse rate L is then calculated as follows:

[0054] L=(w2-w3) / w2×100%

[0055] The catalyst reaction performance was tested on a small fixed fluidized bed microreactor according to the method NB / SH / T0952-2017.

[0056] Example 1

[0057] The catalytic cracking catalyst provided in this embodiment, based on the total dry weight of the catalytic cracking catalyst as 100%, and with a solid content of 35wt% in the catalytic cracking catalyst slurry, contains 20wt% ReY molecular sieve, 5wt% boehmite (colloidal index of 0), 70wt% kaolin, and 5wt% binder.

[0058] The binder has a phosphorus / aluminum molar ratio of 4:1, with phosphoric acid as the phosphorus compound and aluminum hydroxide as the aluminum compound. The polymetallic chelate is a mixture of copper chelated with ethylenediaminetetraacetic acid (EDTA) and lanthanum chelated with hydroxyethyl EDTA. The ratio of the total molar number of copper and lanthanum ions to the molar number of phosphorus ions in this polymetallic chelate is 5:1, and the molar ratio of copper ions to lanthanum ions is also 5:1.

[0059] The preparation method of the above-mentioned catalytic cracking catalyst is as follows:

[0060] Preparation of the binder: Concentrated phosphoric acid (85%) was diluted with deionized water to 40 wt%, at which point the pH value was 1.0. Then, aluminum hydroxide was added in proportion and stirred at 100°C until completely dissolved. The mixture of phosphoric acid and aluminum hydroxide was then added to a high-shear emulsifier and reacted rapidly at 100°C for 10 min. Then, a mixed solution of ethylenediaminetetraacetic acid chelated copper and hydroxyethyl ethylenediaminetriacetic acid chelated lanthanum was added in proportion, and the reaction was continued at 100°C for 5 min to obtain the binder.

[0061] Preparation of catalytic cracking catalyst: At room temperature, ReY molecular sieve, boehmite, kaolin and deionized water were mixed evenly in proportion to obtain a slurry of zeolite molecular sieve and matrix. The slurry of the above binder and the zeolite molecular sieve and matrix was added to a high-shear emulsifier and emulsified at high speed for 2 minutes. The emulsifier was then immediately discharged and spray-dried. The spray-drying conditions were that the furnace temperature of the spray tower was controlled at 580℃ and the tail gas temperature was controlled at 160℃. The resulting material was calcined at 450℃ for 1 hour and then ion-exchanged with an ammonium chloride solution with a pH of 3.0-3.5 for 0.5 hours to obtain the catalytic cracking catalyst.

[0062] The physicochemical properties and catalytic performance of the catalyst are shown in Table 2.

[0063] Example 2

[0064] The catalytic cracking catalyst provided in this embodiment, based on the total dry weight of the catalytic cracking catalyst as 100%, and with a solid content of 50wt% in the catalytic cracking catalyst slurry, contains 60wt% ReY molecular sieve, 13.3wt% boehmite (colloidal index of 50%), 6.7wt% kaolin, and 20wt% binder.

[0065] The molar ratio of phosphorus to aluminum in the binder is 10:1; the polymetallic chelate is a mixed solution of silver chelated by ethylenediaminetetraacetic acid and cerium chelated by hydroxyethylethylenediaminetriacetic acid, wherein the ratio of the total molar number of silver ions and cerium ions to the molar number of phosphorus in diammonium hydrogen phosphate is 20:1, and the molar ratio of silver ions to cerium ions is 15:1.

[0066] The preparation method of the above-mentioned catalytic cracking catalyst is as follows:

[0067] Preparation of the binder: Dissolve diammonium hydrogen phosphate in deionized water and adjust the pH to 5.0 with hydrochloric acid. Then add aluminum oxide in proportion and stir at 60°C until completely dissolved. Then add the mixed solution to a high-shear emulsifier and maintain the reaction temperature at 60°C for 10 min for rapid reaction. Then add a mixed solution of silver chelated with ethylenediaminetetraacetic acid and cerium chelated with hydroxyethyl ethylenediaminetriacetic acid in proportion and continue to react at 60°C for 5 min to obtain the binder.

[0068] Preparation of catalytic cracking catalyst: At room temperature, ReY molecular sieve, boehmite, kaolin and deionized water were mixed evenly in proportion to obtain a slurry of zeolite molecular sieve and matrix. The slurry of the above binder and the zeolite molecular sieve and matrix was added to a high-shear emulsifier and emulsified at high speed for 2 minutes. The emulsifier was then immediately discharged and spray-dried. The spray-drying conditions were that the furnace temperature of the spray tower was controlled at 580℃ and the tail gas temperature was controlled at 160℃. The resulting material was calcined at 150℃ for 1 hour and then ion-exchanged with an ammonium sulfate solution with a pH of 3.0-3.5 for 0.3 hours to obtain the catalytic cracking catalyst.

[0069] The physicochemical properties and catalytic performance of the catalyst are shown in Table 2.

[0070] Example 3

[0071] The catalytic cracking catalyst provided in this embodiment, based on the total dry weight of the catalytic cracking catalyst as 100%, and with a solid content of 40wt% in the catalytic cracking catalyst slurry, contains 40wt% ReY molecular sieve, 10wt% boehmite (colloidal index of 20%), 20wt% kaolin, and 30wt% binder.

[0072] The binder has a phosphorus / aluminum molar ratio of 5:1, with the phosphorus-containing compound being an organophosphonic acid (80% concentration) and the aluminum-containing compound being aluminum hydroxide. The polymetallic chelate is a mixture of aminotrimethylphosphonic acid-chelated zinc and DOTA-chelated lanthanum. The ratio of the total molar number of zinc and lanthanum ions to the molar number of phosphorus ions in this polymetallic chelate is 10:1, and the molar ratio of zinc ions to lanthanum ions is also 10:1.

[0073] The preparation method of the above-mentioned catalytic cracking catalyst is as follows:

[0074] Preparation of the binder: Organophosphonic acid (80 wt%) was diluted to 60 wt% with deionized water. Aluminum hydroxide was then added in proportion, followed by a small amount of citric acid to adjust the pH to 2.0. The mixture was stirred at 80°C until completely dissolved. This mixture was then added to a high-shear emulsifier and reacted rapidly at 80°C for 10 minutes. A mixed solution of aminotrimethylphosphonic acid chelated zinc and DOTA chelated lanthanum was then added in proportion, and the reaction was continued at 80°C for another 5 minutes to obtain the binder.

[0075] Preparation of catalytic cracking catalyst: At room temperature, ReY type molecular sieve, pseudoboehmite, kaolin and deionized water were mixed evenly in proportion to obtain a slurry of zeolite molecular sieve and matrix. The slurry of the above binder and the zeolite molecular sieve and matrix was added to a high-shear emulsifier and emulsified at high speed for 1 min. It was then immediately discharged and spray-dried. The spray-drying conditions were that the furnace temperature of the spray tower was controlled at 580℃ and the temperature of the spray exhaust gas was controlled at 160℃. The resulting material was calcined at 150℃ for 1 h and then ion-exchanged with an ammonium nitrate solution with a pH of 3.0 to 3.5 for 0.3 h to obtain the catalytic cracking catalyst.

[0076] The physicochemical properties and catalytic performance of the catalyst are shown in Table 2.

[0077] Example 4

[0078] The catalytic cracking catalyst provided in this embodiment, based on the total dry weight of the catalytic cracking catalyst (100%), and with a solid content of 60 wt% in the catalytic cracking catalyst slurry, contains 40 wt% ReY molecular sieve, 5% ZSM-5 molecular sieve, 4.5% boehmite (colloidal index 30%) as the γ-alumina precursor, 40.5 wt% halloysite, and 10 wt% binder.

[0079] The binder has a phosphorus / aluminum molar ratio of 8:1, with phosphorus pentoxide as the phosphorus compound and sodium aluminate as the aluminum compound. The polymetallic chelate is a mixture of ethylenediaminetetraacetic acid-chelated copper and β-diketone rare earth cerium (iv) chelate. In this polymetallic chelate, the ratio of the total molar number of copper and cerium ions to the molar number of phosphorus is 15:1, and the molar ratio of copper ions to cerium ions is 10:1.

[0080] The preparation method of the above-mentioned catalytic cracking catalyst is as follows:

[0081] Preparation of the binder: Phosphorus pentoxide was added to a certain amount of deionized water, and then nitric acid was added to adjust the pH to 1.5. Sodium aluminate was then added in proportion and stirred at 80°C until completely dissolved. The mixture was then added to a high-shear emulsifier and reacted rapidly at 80°C for 10 min. A mixed solution of ethylenediaminetetraacetic acid chelated copper and β-diketone rare earth cerium (iv) chelate was then added in proportion and reacted at 80°C for another 5 min to obtain the binder.

[0082] Preparation of catalytic cracking catalyst: At room temperature, ReY type molecular sieve, ZSM-5 molecular sieve, boehmite, halloysite and deionized water were mixed evenly in proportion to obtain a slurry of zeolite molecular sieve and matrix. The slurry of the above binder and the zeolite molecular sieve and matrix was added to a high-shear emulsifier and emulsified at high speed for 4 min. It was then immediately discharged and spray-dried. The spray-drying conditions were that the furnace temperature of the spray tower was controlled at 580℃ and the tail gas temperature was controlled at 160℃. The resulting material was calcined at 150℃ for 1 h and then ion-exchanged with an ammonium carbonate solution with a pH of 3.0-3.5 for 0.3 h to obtain the catalytic cracking catalyst.

[0083] The physicochemical properties and catalytic performance of the catalyst are shown in Table 2.

[0084] Example 5

[0085] The catalytic cracking catalyst provided in this embodiment, based on the total dry weight of the catalytic cracking catalyst (100%), and with a solid content of 45 wt% in the catalytic cracking catalyst slurry, contains 50 wt% ReY molecular sieve, 5.3% boehmite as the γ-alumina precursor (with a peptization index of 25%), 26.7% montmorillonite, and 18 wt% binder.

[0086] The binder has a phosphorus / aluminum molar ratio of 6:1, with the phosphorus-containing compound being sodium phosphate and phosphoric acid, and the aluminum-containing compound being aluminum isopropoxide. The polymetallic chelate is a copper-lanthanum bimetallic hydroxyethylethylenediamine triacetic acid chelate, wherein the ratio of the total molar number of copper ions and lanthanum ions to the molar number of phosphorus ions in this polymetallic chelate is 15:1, and the molar ratio of copper ions to lanthanum ions is 10:1.

[0087] The preparation method of the above-mentioned catalytic cracking catalyst is as follows:

[0088] Preparation of the binder: Sodium phosphate was mixed with a certain amount of deionized water, and a certain amount of phosphoric acid (concentration 85%) was added until the pH value was 3. Then aluminum isopropoxide was added in proportion and stirred at 80°C until completely dissolved. The mixed solution was then added to a high-shear emulsifier and reacted rapidly at 80°C for 10 min. Then, a mixed solution of copper chelated with ethylenediaminetetraacetic acid and lanthanum chelated with hydroxyethyl ethylenediaminetriacetic acid was added in proportion, and the reaction was continued at 80°C for 5 min to obtain the binder.

[0089] Preparation of catalytic cracking catalyst: At room temperature, ReY molecular sieve, boehmite, kaolin and deionized water were mixed evenly in proportion to obtain a slurry of zeolite molecular sieve and matrix. The slurry of the above binder and the zeolite molecular sieve and matrix was added to a high-shear emulsifier and emulsified at high speed for 2 minutes. The emulsifier was then immediately discharged and spray-dried. The spray-drying conditions were that the furnace temperature of the spray tower was controlled at 580℃ and the tail gas temperature was controlled at 160℃. The resulting material was calcined at 150℃ for 1 hour and then ion-exchanged with an ammonium bicarbonate solution with a pH of 3.0-3.5 for 0.3 hours to obtain the catalytic cracking catalyst.

[0090] The physicochemical properties and catalytic performance of the catalyst are shown in Table 2.

[0091] Comparative Example 1

[0092] The catalytic cracking catalyst provided in this comparative example, based on a dry basis total weight of 100% of the catalytic cracking catalyst, and with a solid content of 35wt% in the catalytic cracking catalyst slurry, contains 20wt% ReY molecular sieve, 5wt% boehmite (colloidal index of 0), 70wt% kaolin, 4wt% binder (aluminum sol is used in this comparative example), and 1wt% phosphorus-aluminum additive, wherein the molar ratio of phosphorus to aluminum in the phosphorus-aluminum additive is 4:1, and the molar ratio of magnesium ions to phosphorus is 5:1.

[0093] Preparation of aluminum phosphate additive: Concentrated phosphoric acid (85% concentration) was diluted with deionized water to 40 wt% (pH 1.0), and then aluminum hydroxide was added in proportion and stirred at 100°C until completely dissolved. Magnesium nitrate was added, and the contact time was maintained at 100°C for 2 hours to obtain aluminum phosphate additive.

[0094] Preparation of catalytic cracking catalyst: At room temperature, ReY molecular sieve, boehmite, kaolin and deionized water were mixed evenly in proportion to obtain a slurry of zeolite molecular sieve and matrix. The above binder, phosphorus aluminum additive and the slurry of zeolite molecular sieve and matrix were added to a high-shear emulsifier and emulsified at high speed for 2 minutes. The emulsified mixture was then immediately discharged and spray-dried. The spray-drying conditions were that the furnace temperature of the spray tower was controlled at 580℃ and the tail gas temperature was controlled at 160℃. The resulting material was calcined at 450℃ for 1 hour and then ion-exchanged with an ammonium chloride solution with a pH of 3.0 to 3.5 for 0.5 hours to obtain the catalytic cracking catalyst.

[0095] The physicochemical properties and catalytic performance of the catalyst are shown in Table 2.

[0096] Comparative Example 2

[0097] The content of each raw material and the preparation method of the catalyst in the catalytic cracking catalyst provided in this comparative example are the same as those in Example 5. The only difference from Example 5 is that in this comparative example, boehmite with a colloidal index of 99% is used instead of boehmite with a colloidal solubility of 0 in Example 1, and the binder does not contain polymetallic chelates.

[0098] The specific preparation method of the binder in the comparative example is as follows: Sodium phosphate is mixed with a certain amount of deionized water, a certain amount of phosphoric acid (concentration 85%) is added until the pH value is 3, then aluminum isopropoxide is added in proportion, and stirred at 80°C until completely dissolved. Then the mixture of phosphoric acid and aluminum hydroxide is added to a high-shear emulsifier, and the reaction temperature is maintained at 80°C for a rapid reaction of 10 min to obtain the binder.

[0099] The physicochemical properties and catalytic performance of the catalyst are shown in Table 2.

[0100] Comparative Example 3

[0101] The content and preparation method of each component in the catalytic cracking catalyst provided in this comparative example are the same as those in Example 5. The only difference from Example 5 is that the binder in this comparative example uses a mixed solution of copper nitrate and lanthanum chloride instead of the mixture of ethylenediaminetetraacetic acid chelated copper and hydroxyethyl ethylenediaminetriacetic acid chelated lanthanum in Example 5.

[0102] The physicochemical properties and catalytic performance of the catalyst are shown in Table 2.

[0103] Comparative Example 4

[0104] The content and preparation method of each component in the catalytic cracking catalyst provided in this comparative example are the same as those in Example 5. The only difference from Example 5 is that a high-shear emulsifier is not used in the preparation of the binder and catalyst in this comparative example; instead, it is carried out in a conventional reactor. The specific process is as follows:

[0105] Preparation of the binder: Sodium phosphate was mixed with a certain amount of deionized water, and a certain amount of phosphoric acid (concentration 85%) was added until the pH value was 3. Then aluminum isopropoxide was added in proportion, and the mixture was stirred at 80°C until it was completely dissolved. The mixture was then added to a stirred reactor, and a mixed solution of copper chelated with ethylenediaminetetraacetic acid and lanthanum chelated with hydroxyethyl ethylenediaminetriacetic acid was added in proportion. The mixture was then reacted at 80°C for 10 min to obtain the binder.

[0106] Preparation of catalytic cracking catalyst: At room temperature, ReY molecular sieve, boehmite, kaolin and deionized water were mixed evenly in proportion to obtain a slurry of zeolite molecular sieve and matrix. The slurry of the binder and the zeolite molecular sieve and matrix was added to a stirred reactor and emulsified at high speed for 2 minutes. The emulsion was then immediately discharged and spray-dried. The spray-drying conditions were that the furnace temperature of the spray tower was controlled at 580℃ and the tail gas temperature was controlled at 160℃. The resulting material was calcined at 150℃ for 1 hour and then ion-exchanged with an ammonium bicarbonate solution with a pH of 3.0-3.5 for 0.3 hours to obtain the catalytic cracking catalyst.

[0107] The physicochemical properties and catalytic performance of the catalyst are shown in Table 2.

[0108] Comparative Example 5

[0109] The content and preparation method of each component in the catalytic cracking catalyst provided in this comparative example are the same as those in Example 5. The only difference from Example 5 is that in this comparative example, the multi-metal chelate is added to the molecular sieve slurry. The specific process is as follows:

[0110] Preparation of the binder: Sodium phosphate is mixed with a certain amount of deionized water, and a certain amount of phosphoric acid (concentration 85%) is added until the pH value is 3. Then aluminum isopropoxide is added in proportion and stirred at 80°C until completely dissolved. Then the mixture is added to a high-shear emulsifier and the reaction temperature is maintained at 80°C for 10 minutes to obtain the binder.

[0111] Preparation of catalytic cracking catalyst: At room temperature, ReY molecular sieve, boehmite, kaolin and deionized water were mixed evenly according to the specified ratio. A mixed solution of ethylenediaminetetraacetic acid chelating copper and hydroxyethyl ethylenediaminetriacetic acid chelating lanthanum was added according to the specified ratio to obtain a mixed slurry of zeolite molecular sieve, matrix and multi-metal chelate. The above binder and the mixed slurry were added to a high-shear emulsifier and emulsified at high speed for 2 min. The emulsified mixture was then immediately discharged and spray-dried. The spray-drying conditions were that the furnace temperature of the spray tower was controlled at 580℃ and the tail gas temperature was controlled at 160℃. The resulting material was calcined at 150℃ for 1 h and then subjected to ion exchange with an ammonium bicarbonate solution with a pH of 3.0-3.5 for 0.3 h to obtain the catalytic cracking catalyst.

[0112] The parameters in each of the above embodiments are shown in Table 1-1, and the parameters in each comparative example are shown in Table 1-2.

[0113] Table 1-1 Composition and content of catalysts in each embodiment

[0114]

[0115]

[0116] Note: M / N represents the molar ratio of transition metal ions to rare earth metal ions; P / Al represents the molar ratio of phosphorus in the phosphorus-containing compound to aluminum in the aluminum-containing compound in the binder; metal / P represents the molar ratio of total metal ions to phosphorus in the binder. Except for solids content, all other values ​​in the table are based on the total dry weight of the catalytic cracking catalyst, which is 100%.

[0117] Table 1-2 Composition and content of catalysts prepared in each comparative example

[0118]

[0119]

[0120] Note: M / N represents the molar ratio of transition metal ions to rare earth metal ions; P / Al represents the molar ratio of phosphorus in the phosphorus-containing compound to aluminum in the aluminum-containing compound in the binder; metal / P represents the molar ratio of total metal ions to phosphorus in the binder. Except for solids content, all other values ​​in the table are based on the total dry weight of the catalytic cracking catalyst, which is 100%.

[0121] The physicochemical properties and reaction performance of the catalysts prepared in the above embodiments and comparative examples were characterized and evaluated, and the results are listed in Table 2.

[0122] Table 2 Comparison of physicochemical properties of catalysts

[0123] Wear index, m% Pore ​​volume, ml / g <![CDATA[Specific surface area, m 2 / g]]> Thermal collapse rate, m% Microreactive, m% Comparative Example 1 2.2 0.36 210 14.1％ 64 Comparative Example 2 1.0 0.36 225 5.6％ 71 Comparative Example 3 1.4 0.39 248 13.8％ 72 Comparative Example 4 2.0 0.34 212 12.5％ 59 Comparative Example 5 1.2 0.40 250 11.3％ 75 Example 1 1.0 0.38 220 5.0％ 58 Example 2 1.2 0.39 262 5.5％ 80 Example 3 0.8 0.41 248 6.2％ 72 Example 4 1.0 0.41 252 7.8％ 74 Example 5 0.9 0.42 258 5.6％ 76

[0124] Data Analysis:

[0125] As can be seen from the data in the table above, Comparative Example 1 and Example 1 have the same molecular sieve and matrix composition. The catalyst prepared by the formulation and method of the present invention has a low wear index, a larger pore volume, a smaller thermal collapse rate, and exhibits better wear resistance at high temperatures. At the same time, it has higher micro-reaction activity, indicating that it has better reaction performance.

[0126] As can be seen from Example 5 compared with Comparative Example 2, the catalyst prepared using boehmite with a colloidal index of 25% has a higher pore volume and specific surface area than the catalyst prepared using only aluminum phosphate binder (without multi-metal chelates).

[0127] The comparison between Comparative Example 3 and Example 5 shows that adding the same amount of transition metal and rare earth metal chelates to the aluminum phosphate binder can significantly improve the catalyst's wear index, pore volume, and thermal collapse rate, while using the same amount of inorganic salts of transition metal and rare earth metals does not improve the binder's bonding performance and pore volume.

[0128] The comparison between Comparative Example 4 and Example 5 shows that, under the same formulation, the catalyst prepared using the high-efficiency shear emulsifier described in this invention is beneficial for the emulsification of γ-alumina precursors and the dispersion of metal chelates. The prepared catalyst has better strength, specific surface area, thermal collapse index and microreaction activity.

[0129] The comparison between Comparative Example 5 and Example 5 shows that adding polymetallic chelates to the slurry of molecular sieves and matrix greatly weakens the modification effect on the binder.

[0130] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.

Claims

1. A high-strength, large-pore-volume, high-solid-content catalytic cracking catalyst, characterized in that, The raw materials for the catalytic cracking catalyst include zeolite molecular sieves, a matrix, and a binder. The matrix is ​​composed of γ-alumina precursors with a colloidal index ≤50% and clay. The binder includes phosphorus-containing compounds, aluminum-containing compounds, and polymetallic chelates. The catalytic cracking catalyst was prepared in a high-shear emulsifier; The polymetallic chelate is selected from at least one of phosphonic acid metal chelates, aminocarboxylic acid metal chelates, hydroxyaminocarboxylic acid metal chelates, carboxylic acid metal chelates, and carbonyl metal chelates; The polymetallic chelate is a mixture of at least two metal chelates or a chelate containing at least two metals, wherein the metals in the polymetallic chelate are transition metal ions and rare earth metal ions; The preparation of the adhesive includes the following steps: An aqueous solution of a phosphorus-containing compound with a pH value ≤ 5 is heated to 60–100°C, and an aluminum-containing compound is added and mixed. The mixed solution is then added to a high-shear emulsifier and reacted at 80–120°C to obtain a phosphorus-aluminum binder. Then, a multi-metal chelate is added to the phosphorus aluminum binder to continue the reaction. After the reaction is completed, the binder is obtained. Based on the dry total weight of the catalytic cracking catalyst as 100%, the content of the zeolite molecular sieve is 20wt%~60wt%, the content of the matrix is ​​20wt%~75wt%, the content of the binder is 5wt%~30wt%, and the solid content of the catalytic cracking catalyst is 35wt%~60wt%.

2. The high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst as described in claim 1, characterized in that, The molar ratio of the transition metal ion to the rare earth metal ion in the polymetallic chelate is 5~15:

1.

3. The high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst as described in claim 2, characterized in that, The molar ratio of the total metal ions in the polymetallic chelate to the phosphorus element in the phosphorus-containing compound is 5~20:

1.

4. The high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst as described in claim 1, characterized in that, The molar ratio of phosphorus in the phosphorus-containing compound to aluminum in the aluminum-containing compound is 4~10:

1.

5. The high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst as described in claim 4, characterized in that, The molar ratio of phosphorus in the phosphorus-containing compound to aluminum in the aluminum-containing compound is 5~8:

1.

6. The high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst as described in claim 1, characterized in that, The colloidal index of the γ-alumina precursor is 20%~30%.

7. The high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst as described in claim 1, characterized in that, The mass ratio of the γ-alumina precursor to the clay is 1:0.5~15.

8. The high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst as described in claim 6, characterized in that, The XRD patterns of the γ-alumina precursor show characteristic peaks around 2θ of 14°, 28°, 38°, and 49°.

9. The high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst as described in claim 7, characterized in that, The mass ratio of the γ-alumina precursor to the clay is 1:2~9.

10. A method for preparing a high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst according to any one of claims 1-9, characterized in that, Includes the following steps: The slurry of zeolite molecular sieve and matrix is ​​mixed with binder in a high-shear emulsifier for 5 minutes, then spray-dried, calcined, and ion-exchanged to obtain the high-strength, large-pore-volume, high-solids-content catalytic cracking catalyst.

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