A binder for a catalytic cracking catalyst and its preparation method

Abstract

This invention provides a binder for a catalytic cracking catalyst and its preparation method. The binder comprises a binder, a curing agent, and a modifier. The curing agent is prepared by a hydrothermal reaction of a γ-alumina precursor, an acid, and an alkylammonium salt. The modifier is prepared by reacting a multi-metal chelate ligand, a metal central ligand, ethanol, and an organic acid. The binder comprises a phosphorus-containing compound and an aluminum-containing compound. In the binder for the catalytic cracking catalyst provided by this invention, a multi-metal chelate modifier composed of a multi-metal chelate ligand and multiple metals is introduced. Under the promotion of organic acid and ethanol, a multi-metal chelate modifier can be prepared in situ during the binder preparation process. Compared with directly using commercially available metal chelates, the in-situ prepared multi-metal chelate modifier has better water solubility and can promote the binding of the modifier with the phosphorus-aluminum sol, resulting in a better modification effect.

Description

Technical Field

[0001] This invention belongs to the field of catalyst additive technology, specifically relating to a binder for a catalytic cracking catalyst and its preparation method. Background Technology

[0002] Catalytic cracking catalysts are mainly composed of a matrix, active components, and binders. The binder not only binds the matrix and active components but also provides heat capacity during the catalytic cracking reaction. Furthermore, the binder's performance directly affects the physicochemical properties of the catalyst, such as particle size, wear index, and pore volume. The catalyst's pores are the sites of catalytic reactions and channels for diffusion and mass transfer; their pore structure directly influences the catalyst's activity and selectivity. The catalyst's wear index significantly affects the strength of the catalyst support, easily causing support breakage and leading to a decrease in the quality of the prepared catalyst. Therefore, the binder directly impacts the performance of catalytic cracking catalysts. When developing catalytic cracking catalysts with higher activity, stronger heavy oil conversion capabilities, stronger resistance to heavy metals, and better coke selectivity, increasing the content of the active component molecular sieve and improving the micropore volume of the catalytic cracking catalyst often leads to a deterioration in the catalyst's wear resistance, resulting in problems such as abnormal fluidization, catalyst loss, scale buildup in the flue gas turbine, and increased solids content in the slurry, affecting the long-term operation of the catalytic cracking unit. This also leads to a decrease in the pore size and corresponding specific surface area between binders, reducing the diffusion of reactant macromolecules, resulting in an increase in coke yield and a decrease in the selectivity of the cracking reaction.

[0003] Phosphates are commonly used binders for catalytic cracking catalysts.

[0004] Patent 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 a 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.

[0005] US Patent 4407730 discloses a catalyst support that, after being calcined at 500°C for 10 hours, is essentially composed of a magnesium oxide-alumina-alumina 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 a magnesium oxide content of 0.5% to less than 10 mol% or 25-75 mol%, an aluminum oxide content of 2-90 mol%, and an 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 approximately 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 feedstocks with high metal content.

[0006] US Patent 5286369 discloses a catalytic cracking method for hydrocarbon feedstocks. This method includes 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. An aluminum salt solution of this catalyst is preferably a solution of aluminum nitrate containing 29-61% Al(NO₃)₃·9H₂O, mixed with a phosphoric acid solution, particularly a phosphoric acid solution containing 20-86 wt% phosphoric acid, with a pH of 0.5-0.9 and an aluminum to phosphorus molar ratio of 0.4-1.4, to obtain an aluminum phosphate solution. The obtained aluminum phosphate solution is mixed with a slurry of zeolite (such as Beta zeolite) and clay (preferably kaolin) to obtain a spray-dryable slurry with a solid content of 20-45 wt%. On a dry basis, the slurry contains 8-25 wt% aluminum phosphate, 10-40 wt% zeolite, and 35-82 wt% clay. The slurry is spray-dried at 200-400°C. During the drying process, the aluminum phosphate solution transforms into a binder.

[0007] Patent CN102049284B discloses a catalytic cracking propylene additive, which, based on 100% of the total additive weight, contains 30-80% by weight of molecular sieves, of which ZSM-5 zeolite content is 28-78% by weight, and clay content is 10-65% by weight. The additive contains phosphorus, specifically 5.0-20.0% by weight of P2O5, preferably 7.0-15.0% by weight, and La2O3 content is 0-1.0% by weight. Aluminum phosphate sol is used as a binder, which improves the additive's wear resistance and increases the solid content of the spray slurry, while avoiding chlorine content in the spray slurry and the additive. The prepared catalytic cracking propylene additive exhibits significantly improved activity. When blended with the main catalyst, it causes minimal reduction in the main catalyst's activity, improves product distribution, and demonstrates good selectivity for dry gas and coke, while simultaneously increasing propylene yield and gasoline octane number.

[0008] Patent CN102847547B 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. The preparation method provided by this invention avoids binder solidification caused by localized, intense, and exothermic reactions due to uneven material distribution. The resulting binder can improve the wear resistance, activity, and selectivity of FCC catalysts.

[0009] Patent CN1957070A discloses a catalyst composition comprising a metal phosphate binder and zeolite, which can be used to improve olefin yields in cracking processes. The composition typically also contains aluminum phosphate, and the metal in the metal phosphate is a metal other than aluminum. Depending on the metal chosen, propylene and isobutylene yields can be improved in fluidized catalytic cracking processes compared to catalysts without this metal phosphate binder. The catalyst may also contain non-zeolite molecular sieves, making the catalyst composition suitable for applications beyond catalytic cracking, such as purification and adsorption.

[0010] Patent CN1291915A provides a method for improving the catalytic activity of small-pore and mesoporous acidic zeolite catalysts. This method includes the steps of: treating zeolite with a phosphorus compound to form phosphorus-treated zeolite, and combining the phosphorus-treated zeolite with AlPO4. Optionally, the phosphorus-treated zeolite may be calcined. Optionally, after the step of combining the zeolite with AlPO4, the combined catalyst is steam-dried. Examples of phosphorus-containing compounds that can be used to treat zeolite include phosphoric acid, aluminum hydrogen phosphate or aluminum dihydrogen phosphate, organophosphorus esters, and organophosphorus compounds. Preferred phosphorus-containing compounds are aluminum acid phosphates. Another embodiment provides a method for improving the hydrothermal stability of zeolite catalysts, comprising the steps of: first treating zeolite with a phosphorus-containing compound, and then mixing it with AlPO4.

[0011] Patent CN101376830A discloses a hydrotreating catalyst support and its preparation method. The support contains alumina fibers and a phosphorus auxiliary agent, wherein the phosphorus auxiliary agent is partially or entirely introduced in the form of aluminum dihydrogen phosphate. The addition of alumina fibers and aluminum dihydrogen phosphate during the preparation process improves the mechanical strength and wear resistance of the support, thereby enhancing the mechanical strength and wear resistance of the catalyst, improving catalyst stability, extending catalyst lifespan, and reducing production costs. This support, used as a support for fluidized bed hydrotreating catalysts, can maximize the removal of nitrogen, sulfur, and other heteroatoms from oil products when treating heavy fractions, reducing their olefin and aromatic hydrocarbon content.

[0012] Patent CN1957070A 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. The preparation method provided by this invention avoids binder solidification caused by localized, intense, and exothermic reactions due to uneven material distribution. The resulting binder can improve the wear resistance, activity, and selectivity of FCC catalysts.

[0013] Patent CN1132897C 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, with a specific gravity of 1.2-1.7 g / mL and an atomic ratio of phosphorus to aluminum greater than 1 to 12. This catalyst exhibits higher abrasion resistance.

[0014] As mentioned earlier, 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 is high or the catalyst pore volume is large, especially after high-temperature steam aging. Summary of the Invention

[0015] The purpose of this invention is to provide a binder for catalytic cracking catalysts to solve the problems of decreased strength, small pore volume, and poor affinity of reactant molecules in existing catalytic cracking catalysts and additives as the molecular sieve content and pore volume increase.

[0016] Another objective of this invention is to provide a method for preparing a binder for a catalytic cracking catalyst.

[0017] To achieve the above objectives, the present invention provides a binder for a catalytic cracking catalyst, comprising a binder, a curing agent, and a modifier. The curing agent is prepared by hydrothermal reaction of a γ-alumina precursor, an acid, and an alkylammonium salt. The modifier is prepared by reaction of a multi-chelate ligand, a metal central ligand, ethanol, and an organic acid. The binder comprises a phosphorus-containing compound and an aluminum-containing compound.

[0018] The binder for the catalytic cracking catalyst of the present invention has a colloidal index of ≤50% for the γ-alumina precursor. In this invention, the XRD patterns of the γ-alumina precursor with a colloidal index ≤50% exhibit characteristic peaks at 2θ of 14±1°, 28±1°, 38±1°, and 49±1°, such as boehmite, boehmite, etc.

[0019] The binder of the catalytic cracking catalyst of the present invention, wherein the multi-gnawing chelate ligand is a 2-gnawing chelate ligand having at least 2 coordinating atoms, and the coordinating atoms are P, O or N, O, preferably P, O.

[0020] The binder of the catalytic cracking catalyst of the present invention comprises one or more of the following: aminotrimethylphosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylidene phosphonic acid, diethylenetriaminepentamethylidene phosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-hydroxyphosphonoacetic acid, bis(1,6-hexylenetriaminepentamethylidene phosphonic acid), hexamethylenediaminetetramethylidene phosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and 1,2-ethylenediamine.

[0021] The binder of the catalytic cracking catalyst of the present invention comprises rare earth metals and transition metals.

[0022] The binder for the catalytic cracking catalyst of this invention comprises one or more rare earth metals selected from lanthanum, cerium, neodymium, and samarium; and one or more transition metals selected from copper, silver, nickel, zinc, cobalt, and cadmium. In this invention, the ratio of various metal ions in the metal central ligand is not specifically limited and can be adjusted according to actual conditions. The recommended molar ratio of transition metal to rare earth metal is 5–10:1.

[0023] The binder of the catalytic cracking catalyst of the present invention is a rare earth metal and a transition metal chloride or nitrate.

[0024] The binder for the catalytic cracking catalyst of the present invention, wherein the organic acid in the modifier is one or more of benzoic acid, lactic acid, propionic acid, formic acid, acetic acid, sorbic acid and malic acid.

[0025] The binder for the catalytic cracking catalyst of the present invention has a curing agent in which the molar ratio of acid to γ-alumina precursor is 0.1–1:1, preferably 0.2–0.5:1; and the mass ratio of γ-alumina precursor to alkylammonium salt is 9–20:1, wherein the γ-alumina precursor is calculated as alumina. There are no restrictions on the type of acid in the curing agent; commonly used inorganic or organic acids are acceptable, such as HCl, HNO3, H2SO4, HCOOH, and CH3COOH.

[0026] The binder for the catalytic cracking catalyst of the present invention is not specifically limited to the alkylammonium salt; any conventional alkylammonium salt in the industry is acceptable. The present invention recommends that the alkylammonium salt be one or more of hexadecyltrimethylammonium bromide (CTAB), hexadecylpyridine chloride (CPC), and dimethyloctadecylammonium chloride.

[0027] The binder for the catalytic cracking catalyst of the present invention has a molar ratio of phosphorus in the phosphorus-containing compound to aluminum in the aluminum-containing compound of 1 to 10:1, preferably 2 to 6:1.

[0028] The aluminum-containing compounds and phosphorus-containing compounds described in this invention are not specifically limited, and any conventional compounds used in the industry may be adopted. The aluminum-containing compounds include, but are not limited to, aluminum oxides, aluminum hydroxides, and aluminum-containing organic compounds, such as aluminum oxide, aluminum hydroxide, sodium aluminate monohydrate, aluminum chloride, and aluminum isopropoxide; preferably, aluminum oxides and aluminum hydroxides. The phosphorus-containing compounds include, but are not limited to, phosphorus oxides, phosphorus oxyacids, phosphoric acid, phosphates, or phosphorus-containing organic compounds, such as phosphoric acid, diammonium hydrogen phosphate, phosphorus pentoxide, organophosphonic acid, sodium phosphate, and calcium phosphate. Preferably, phosphorus oxyacids, phosphoric acid, and phosphorus-containing ammonium salts are preferred.

[0029] The binder of the catalytic cracking catalyst of the present invention, based on the dry weight of the binder as 100%, has a binder content of 70-94 wt%, preferably 76-88 wt%; a curing agent content of 4-20 wt%, preferably 8-16 wt%; and a modifier content of 2-10 wt%, preferably 4-8 wt%.

[0030] The binder of the catalytic cracking catalyst of the present invention has a molar ratio of 2 to 5:1 between the multi-chelate ligand and the metal ion in the metal central ligand.

[0031] To achieve the above objectives, the present invention also provides a method for preparing a binder for a catalytic cracking catalyst, comprising the following steps:

[0032] S1: Mix the γ-alumina precursor with an acid, then add an alkylammonium salt solution to react. After the reaction is complete, perform hydrothermal treatment to obtain a curing agent.

[0033] S2: Mix the multi-gnawing chelate ligand with an organic acid solution to prepare an organic acid solution of the multi-gnawing chelate ligand, add an ethanol solution, mix evenly, and then obtain a multi-gnawing chelate ligand solution.

[0034] S3: Add the metal-centered ligand to the organic acid solution, and after it is completely dissolved, add the ethanol solution and mix well to obtain the metal-centered ligand precursor solution.

[0035] S4: Add equal volumes of the multi-chelate ligand solution and the metal central ligand precursor solution to a high-shear dispersing emulsifier, maintain the temperature at 30-50℃, and adjust the pH of the system to 5-8; after the reaction is complete, a multi-metal composite chelate modifier solution is prepared.

[0036] S5: Add aluminum-containing compounds and phosphorus-containing compounds to a high-shear dispersing emulsifier and mix them with a multi-metal composite chelating modifier solution. Add water to ensure the flowability of the material in the high-shear dispersing emulsifier, and control the pH of the system to 5-7 and the system temperature to 60-80℃ to allow it to react fully.

[0037] S6: Add the curing agent obtained in step S1 to the high shear dispersion emulsifier and react. After the reaction is completed, the binder of the catalytic cracking catalyst is obtained.

[0038] In this invention, when the phosphorus-containing compound added in step S5 is not acidic, an acid can be added to adjust the pH of the system to ≤7. The specific type of acid is not limited, and any conventional inorganic or organic acid in the industry can be used, such as hydrochloric acid, nitric acid, phosphonic acid, etc.

[0039] The method for preparing the binder of the catalytic cracking catalyst of the present invention includes the following steps: In step S1, the mixing conditions of the γ-alumina precursor and the acid are: mixing at 30-100°C for 10-120 min, adding the alkylammonium salt solution, and reacting at 30-100°C for 15-30 min; the hydrothermal treatment temperature is 400-1000°C, the volume content of water vapor is 10-80%, preferably 20-60%, and the time is 1-10 h, preferably 4-6 h.

[0040] In the preparation method of the binder for the catalytic cracking catalyst of the present invention, in step S2, the mass concentration of organic acid in the multi-gnawing chelate solution is 10-30%, the mass concentration of ethanol is 5-20%, and the molar concentration of multi-gnawing chelate is 0.2-1.0 mol / L.

[0041] In the preparation method of the binder for the catalytic cracking catalyst of the present invention, in step S3, the mass concentration of organic acid in the metal central ligand precursor solution is 10-30%, and the mass concentration of ethanol is 5-20%.

[0042] The binder provided by this invention can be applied to catalytic cracking catalysts, catalytic pyrolysis catalysts, or additives.

[0043] It has been found that when the molecular sieve content is high or the pore volume of the additive is large in additives prepared using existing aluminum phosphate sol, the additive particles are prone to varying degrees of breakage. It is speculated that because existing aluminum phosphate sol contains excessive chloride, ammonium, and nitrate ions, these ions may have a stable bond with the binding components, placing these components in an inactive state. During the additive preparation process, this inactive state persists. On the one hand, this stable bond reduces the binding effect of the binding components. On the other hand, during the spray drying process of the additive, especially during steam aging, the chloride, ammonium, and nitrate ions that are stably bonded to the binding components become unstable, generating 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 additive particles. When the temperature rises, these bubbles burst out from the additive, damaging the particle shape and, in severe cases, causing the particles to break. This reduces the binding effect of various binders and significantly decreases the anti-wear performance of the additive.

[0044] The binder for the catalytic cracking catalyst provided by this invention incorporates a multi-meshing chelate ligand and a metal central ligand composed of multiple metals. Under the promotion of organic acids and ethanol, a multi-metal chelate modifier can be prepared in situ during the binder preparation process. Compared to directly using commercially available metal chelates, the in-situ prepared multi-metal chelate modifier exhibits better water solubility, promoting the binding of the modifier with aluminum phosphate sol and resulting in better modification effects. Furthermore, the use of multi-meshing chelate ligands allows for chelation with various metal ions to form multi-metal chelate ligands, reducing dissolution problems between different solvents during binder preparation and minimizing interactions between different chelate ligands. Simultaneously, the proportions of different metals can be flexibly controlled to achieve precise regulation of binder performance. Moreover, the in-situ preparation of the multi-metal chelate modifier overcomes the limitation of a limited variety of commercially available metal chelates, expanding the applicability of binder preparation. Finally, the preferred use of multi-meshing chelate ligands with N, P, and O coordinating atoms reduces the introduction of excessive heteroatoms into the binder, thus minimizing its impact on binder performance and catalyst performance.

[0045] This invention introduces an in-situ prepared multi-metal chelate modifier into the binder of a catalytic cracking catalyst to improve the properties of the phosphate binder. The transition metal ions, alkali metal ions, and light rare earth metal ions in the multi-metal chelate strengthen the interaction between aluminum phosphate and the curing agent, improving strength. Experiments show that the modification with composite metal ions can significantly reduce thermal collapse under high-temperature hydrothermal conditions, significantly improving the catalyst's thermal wear performance. Simultaneously, it can prevent premature hardening of the colloid during catalyst molding and drying, increasing the pore volume of the binder after curing. Numerous experimental results demonstrate that the addition of the multi-metal chelate modifier can form micropores and mesopores within the binder during preparation without affecting its bonding performance.

[0046] The binder for the catalytic cracking catalyst provided by this invention uses a low-solubility-index γ-alumina precursor in the curing agent. This reduces the solubility of the γ-alumina precursor in the acidic medium during preparation, precisely controlling the presence of free metallic aluminum in the catalyst system and preventing excessive reaction with the effective components of the binder, thus affecting the binder's bonding performance. The small portion of the soluble γ-alumina precursor can react with phosphorus-containing compounds in the binder under specific conditions to form the binder. Furthermore, the low-solubility-index γ-alumina precursor can form numerous mesopores during curing, increasing the pore volume of the cured binder.

[0047] The present invention provides a method for preparing a high-strength, large-pore-volume phosphorus-containing binder. This method involves adding a γ-alumina precursor and subjecting the material to hydrothermal treatment. Under harsh conditions, the crystal structure of the γ-alumina precursor partially collapses and recrystallizes, further increasing its pore volume and pore size, and increasing the number of mesopores. Simultaneously, the surface structure of the γ-alumina precursor is modified, providing a favorable environment for the adhesion of metal ions in subsequent modifiers. Furthermore, the γ-alumina precursor is used as a curing agent for the aluminum phosphate binder, increasing both pore volume and bonding strength. Pretreatment with an alkylammonium salt before hydrothermal treatment of the γ-alumina precursor makes pore expansion during the hydrothermal process more efficient, resulting in a pore size distribution more concentrated in the mesopore range, eliminating macropores larger than 20 nm. This improves both the binder's pore volume and its adhesive performance.

[0048] The present invention provides a method for preparing a high-strength, large-pore-volume phosphorus-containing binder. This method employs a high-shear emulsification reactor, which can disperse low-colloidal-index γ-alumina precursors into a uniform, viscous emulsion slurry. This overcomes the technical challenge of poor solubility in low-colloidal-index γ-alumina precursors, preventing the formation of a uniform slurry. Furthermore, the application of the high-shear emulsification reactor solves the problem of insufficient mixing between the multi-metal chelate and the aluminum phosphate binder, promoting the interaction between the binder and the multi-metal chelate, effectively controlling the microenvironment such as supersaturation distribution within the reactor, and enhancing the effect of the binder's modifying components. Detailed Implementation

[0049] 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.

[0050] For any experimental steps or conditions not specified in the examples and comparative examples, the procedures and 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.

[0051] 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:

[0052] Y-type molecular sieves and alumina sol were sourced from Lanzhou Petrochemical Company;

[0053] Boehmite, boehmite, and boehmite are produced by Shandong Aluminum Plant of China Aluminum Corporation.

[0054] Kaolin is produced by China Kaolin Co., Ltd.

[0055] Formic acid, acetic acid, propionic acid, benzoic acid, oxalic acid, lactic acid, citric acid, nitric acid, hydrochloric acid, hexadecyltrimethylammonium bromide (CTAB), hexadecylpyridine chloride, dimethyloctadecylammonium chloride, 1,2-ethylenediamine, ethylenediaminetetraacetic acid, hydroxyethylidene diphosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, lanthanum chloride, cerium nitrate, neodymium sulfate, samarium chloride, copper nitrate, silver nitrate, zinc sulfate, nickel chloride, aluminum oxide, aluminum hydroxide, aluminum isopropoxide, aluminum chloride, aluminum sulfate, phosphorus pentoxide, phosphoric acid, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate are all analytical grade and produced by Sinopharm Group.

[0056] Example 1

[0057] In the adhesive provided in this embodiment, based on a dry basis of 100%, the content of the adhesive is 70 wt%, the content of the curing agent is 20 wt%, and the content of the modifier is 10 wt%. The molar ratio of the multi-chelating ligand to the metal ion in the metal central ligand in the modifier is 2:1. The specific preparation method is as follows:

[0058] S1: Boehmite with a gel solubility index of 50% was mixed with deionized water, and hydrochloric acid was added. The molar ratio of hydrochloric acid to boehmite (calculated as alumina) was 0.1:1. The mixture was reacted at 30°C for 2 hours, and then hexadecyltrimethylammonium bromide (CTAB) solution was added. The mixture was reacted at 30°C for 30 minutes. Then, hydrothermal treatment was carried out at 400°C with a water vapor content of 10% for 10 hours to obtain curing agent particles. The mass ratio of boehmite to CTAB was 9:1.

[0059] S2: Mix the bidentate chelating ligand 1,2-ethylenediamine with formic acid solution to prepare an organic acid solution of the bidentate chelating ligand. After mixing evenly, add ethanol solution to obtain a 1,2-ethylenediamine ligand solution. The molar concentration of 1,2-ethylenediamine is 0.2 mol / L, the mass concentration of organic acid in the solution is 30%, and the mass concentration of ethanol is 20%.

[0060] S3: Lanthanum chloride and copper nitrate were added to a formic acid solution. After complete dissolution, an ethanol solution was added and mixed thoroughly to obtain a mixed metal central ligand precursor solution. The mass concentration of formic acid in the precursor solution was 30%, the mass concentration of ethanol was 20%, the molar concentration of the mixed metal in the precursor solution was 0.1 mol / L, and the molar ratio of lanthanum chloride to copper nitrate was 1:5.

[0061] S4: The 1,2-ethylenediamine ligand solution obtained from S2 and the metal-containing central ligand precursor solution obtained from S3 are added to a high-shear dispersing emulsifier at a volume ratio of 1:1. The temperature is maintained at 50℃, and ammonia is added to adjust the pH of the system to 8. The reaction is carried out for 30 minutes to obtain a multi-metal composite chelating modifier solution.

[0062] S5: Add aluminum oxide and phosphorus pentoxide (P / Al molar ratio of 1:1) to a high shear dispersion emulsifier and mix with a multi-metal composite chelating modifier solution. Add an appropriate amount of water to ensure that the binder has good fluidity, and add hydrochloric acid (concentration of 38%) to adjust the pH of the system to 7. Maintain the system temperature at 60℃ and react for 20 minutes.

[0063] S6: Add the curing agent prepared in S1 to the mixed slurry described in S5, and react at 60°C for 30 minutes. After the reaction is completed, the binder of the catalytic cracking catalyst is obtained.

[0064] Example 2

[0065] In the adhesive provided in this embodiment, based on a dry basis of 100%, the content of the adhesive is 94 wt%, the content of the curing agent is 4 wt%, and the content of the modifier is 2 wt%. The molar ratio of the multi-chelating ligand to the metal ion in the metal central ligand in the modifier is 5:1. The specific preparation method is as follows:

[0066] S1: Boehmite with a gel solubility index of 30% was mixed with deionized water, oxalic acid was added, and the molar ratio of oxalic acid to boehmite (calculated as alumina) was 1:1. The mixture was reacted at 100°C for 10 min, and then hexadecylpyridine chloride (CPC) solution was added. The mixture was reacted at 100°C for 15 min. Then, the mixture was hydrothermally treated at 1000°C with a water vapor content of 80% for 1 h to obtain curing agent particles. The mass ratio of boehmite to CPC was 20:1.

[0067] S2: Mix the hexa-chelating ligand ethylenediaminetetraacetic acid (EDTA) with an acetic acid solution to prepare an acetic acid solution of EDTA multi-chelating ligands. After mixing evenly, add an ethanol solution to obtain an EDTA ligand solution. The molar concentration of EDTA is 1 mol / L, the mass concentration of organic acid in the solution is 10%, and the mass concentration of ethanol is 5%.

[0068] S3: Cerium nitrate and silver nitrate are added to an acetic acid solution. After complete dissolution, an ethanol solution is added and mixed thoroughly to obtain a mixed metal central ligand precursor solution. The mass concentration of acetic acid in the precursor solution is 10%, the mass concentration of ethanol is 5%, the molar concentration of the mixed metal in the precursor solution is 0.2 mol / L, and the molar ratio of cerium nitrate to silver nitrate is 1:10.

[0069] S4: The ethylenediaminetetraacetic acid ligand solution obtained in S2 and the metal central ligand precursor solution obtained in S3 are added to a high shear dispersion emulsifier at a volume ratio of 1:1. The temperature is maintained at 30℃, and ammonia water is added to adjust the pH of the system to 5. The reaction is carried out for 50 minutes to obtain a multi-metal composite chelating modifier solution.

[0070] S5: Add aluminum hydroxide and phosphoric acid (P / Al molar ratio of 10:1) to a high shear dispersion emulsifier and mix with the multi-metal composite chelating modifier solution. Add an appropriate amount of water to ensure that the binder has good fluidity. Adjust the pH of the system to 5 according to the actual pH value of the mixed solution. Maintain the system temperature at 80℃ and react for 10 minutes.

[0071] S6: Add the curing agent prepared in S1 to the mixed slurry described in S5, and react at 80°C for 10 minutes. After the reaction is completed, the binder of the catalytic cracking catalyst is obtained.

[0072] Example 3

[0073] In the adhesive provided in this embodiment, based on an adhesive dry basis of 100%, the content of adhesive is 76 wt%, the content of curing agent is 16 wt%, and the content of modifier is 8 wt%. The molar ratio of the multi-chelate ligand to the metal ion in the metal central ligand in the modifier is 3:1.

[0074] The specific preparation method is as follows:

[0075] S1: Boehmite with a peptizability index of 20% was mixed with deionized water, and nitric acid was added. The molar ratio of nitric acid to boehmite (calculated as alumina) was 0.2:1. The mixture was reacted at 80°C for 30 min, and then dimethyloctadecyl ammonium chloride solution was added. The mixture was reacted at 80°C for 15 min. Then, the mixture was hydrothermally treated at 800°C with a water vapor content of 20% for 6 h to obtain curing agent particles. The mass ratio of boehmite to dimethyloctadecyl ammonium chloride was 14:1.

[0076] S2: Mix the tetraglycated ligand hydroxyethylidene diphosphonic acid with a propionic acid solution to prepare a propionic acid solution of the hydroxyethylidene diphosphonic acid multiglycated ligand. After mixing evenly, add an ethanol solution to obtain a hydroxyethylidene diphosphonic acid ligand solution. The molar concentration of hydroxyethylidene diphosphonic acid is 0.6 mol / L, the mass concentration of organic acid in the solution is 20%, and the mass concentration of ethanol is 10%.

[0077] S3: Neodymium sulfate and nickel sulfate are added to a propionic acid solution. After complete dissolution, an ethanol solution is added and mixed thoroughly to obtain a mixed metal central ligand precursor solution. The mass concentration of propionic acid in the precursor solution is 20%, the mass concentration of ethanol is 10%, the molar concentration of the mixed metal in the precursor solution is 0.2 mol / L, and the molar ratio of neodymium chloride to nickel nitrate is 1:8.

[0078] S4: The hydroxyethylidene diphosphonic acid ligand solution obtained in S2 and the metal central ligand precursor solution obtained in S3 are added to a high shear dispersion emulsifier at a volume ratio of 1:1. The temperature is maintained at 40℃, and ammonia water is added to adjust the pH of the system to 7. The reaction is carried out for 40 minutes to obtain a multi-metal composite chelating modifier solution.

[0079] S5: Add aluminum isopropoxide and ammonium dihydrogen phosphate (P / Al molar ratio of 2:1) to a high shear dispersion emulsifier and mix with the multi-metal composite chelating modifier solution. Add an appropriate amount of water to ensure that the binder has good fluidity. Adjust the pH of the system to 6.0, maintain the temperature at 70℃, and react for 15 min.

[0080] S6: Add the curing agent prepared in S1 to the mixed slurry described in S5, and react at 70°C for 20 minutes. After the reaction is completed, the binder of the catalytic cracking catalyst is obtained.

[0081] Example 4

[0082] In the adhesive provided in this embodiment, based on a dry basis of 100%, the content of adhesive is 88 wt%, the content of curing agent is 8 wt%, and the content of modifier is 4 wt%. The molar ratio of the multi-chelating ligand to the metal ion in the metal central ligand in the modifier is 3:1.

[0083] The specific preparation method is as follows:

[0084] S1: Boehmite with a gel solubility index of 20% was mixed with deionized water, and citric acid was added. The molar ratio of citric acid to boehmite (calculated as alumina) was 0.5:1. The mixture was reacted at 60°C for 1 hour. A mixed solution of dimethyloctadecyl ammonium chloride and hexadecyltrimethylammonium bromide (CTAB) was added, and the mixture was reacted at 80°C for 20 minutes. Then, the mixture was calcined at 600°C with a water vapor content of 60% for 4 hours to obtain curing agent particles. The mass ratio of boehmite to dimethyloctadecyl ammonium chloride to hexadecyltrimethylammonium bromide (CTAB) was 28:1:1.

[0085] S2: Mix the tetra-chelating ligand hexamethylenediaminetetramethylenephosphonic acid with a benzoic acid solution to prepare a benzoic acid solution containing hexamethylenediaminetetramethylenephosphonic acid multi-chelating ligands. After mixing evenly, add an ethanol solution to obtain a hexamethylenediaminetetramethylenephosphonic acid ligand solution. The molar concentration of hexamethylenediaminetetramethylenephosphonic acid is 0.6 mol / L, the mass concentration of organic acid in the solution is 20%, and the mass concentration of ethanol is 10%.

[0086] S3: Add samarium chloride and zinc nitrate to a benzoic acid solution. After complete dissolution, add an ethanol solution and mix thoroughly to obtain a mixed metal central ligand precursor solution. The mass concentration of benzoic acid in the precursor solution is 20%, the mass concentration of ethanol is 10%, the molar concentration of the mixed metal in the precursor solution is 0.2 mol / L, and the molar ratio of samarium chloride to zinc nitrate is 1:6.

[0087] S4: The hexamethylenediamine tetramethylphosphonic acid ligand solution obtained in S2 and the metal central ligand precursor solution obtained in S3 are added to a high shear dispersion emulsifier at a volume ratio of 1:1. The temperature is maintained at 40℃, and ammonia water is added to adjust the pH of the system to 7. The reaction is carried out for 40 minutes to obtain a multi-metal composite chelating modifier solution.

[0088] S5: Add aluminum isochloride and ammonium dihydrogen phosphate (P / Al molar ratio of 6:1) to a high shear dispersion emulsifier and mix with the multi-metal composite chelating modifier solution. Add an appropriate amount of water to ensure that the binder has good fluidity. Adjust the pH of the system to 6.0, maintain the temperature at 70℃, and react for 15 min.

[0089] S6: Add the curing agent prepared in S1 to the mixed slurry described in S5, and react at 70°C for 20 minutes. After the reaction is completed, the binder of the catalytic cracking catalyst is obtained.

[0090] Example 5

[0091] In the adhesive provided in this embodiment, based on a dry basis of 100%, the adhesive content is 82 wt%, the curing agent content is 10 wt%, and the modifier content is 8 wt%. The molar ratio of the multi-chelating ligand to the metal ion in the metal central ligand in the modifier is 3:1.

[0092] The specific preparation method is as follows:

[0093] S1: Boehmite with a gel solubility index of 20% was mixed with deionized water, and sulfuric acid and hydrochloric acid were added. The molar ratio of boehmite (calculated as alumina) to sulfuric acid was 0.3:1. The mixture was reacted at 70°C for 1 hour. A mixed solution of hexadecylpyridine chloride (CPC) and hexadecyltrimethylammonium bromide (CTAB) was added, with a mass ratio of hexadecylpyridine chloride (CPC) to hexadecyltrimethylammonium bromide (CTAB) of 1:1. The mixture was reacted at 70°C for 30 minutes. Then, the mixture was hydrothermally treated at 700°C with a water vapor content of 50% for 5 hours to obtain curing agent particles. The mass ratio of boehmite, dimethyloctadecylammonium chloride, and CTAB was 20:1:1.

[0094] S2: The octetral chelating ligand diethylenetriaminepentamethylphosphonic acid is mixed with a lactic acid solution to prepare a lactic acid solution of the diethylenetriaminepentamethylphosphonic acid multi-chelating ligand. After mixing evenly, an ethanol solution is added to obtain a diethylenetriaminepentamethylphosphonic acid ligand solution. The molar concentration of diethylenetriaminepentamethylphosphonic acid is 0.6 mol / L, the mass concentration of organic acid in the solution is 20%, and the mass concentration of ethanol is 10%.

[0095] S3: Lanthanum chloride and cadmium nitrate were added to a lactic acid solution. After complete dissolution, an ethanol solution was added and mixed thoroughly to obtain a mixed metal central ligand precursor solution. The mass concentration of lactic acid in the precursor solution was 20%, the mass concentration of ethanol was 10%, the molar concentration of the mixed metal in the precursor solution was 0.2 mol / L, and the molar ratio of lanthanum chloride to cadmium nitrate was 1:8.

[0096] S4: The diethylenetriamine pentamethylphosphonic acid ligand solution obtained in S2 and the metal central ligand precursor solution obtained in S3 are added to a high shear dispersion emulsifier at a volume ratio of 1:1. The temperature is maintained at 40℃, and ammonia water is added to adjust the pH of the system to 7. The reaction is carried out for 40 minutes to obtain a multi-metal composite chelating modifier solution.

[0097] S5: Add aluminum hydroxide and diammonium hydrogen phosphate (P / Al molar ratio of 5:1) to a high shear dispersion emulsifier and mix with a multi-metal composite chelating modifier solution. Add an appropriate amount of water to ensure that the binder has good fluidity. Adjust the pH of the system to 6.0, maintain the temperature at 70℃, and react for 15 min.

[0098] S6: Add the curing agent prepared in S1 to the mixed slurry described in S5, and react at 70°C for 20 minutes. After the reaction is completed, the binder of the catalytic cracking catalyst is obtained.

[0099] Example 6

[0100] The raw materials, contents, and preparation methods of Examples 6 and 5 are the same, except that:

[0101] 1) The multidentate chelating ligand is aminotrimethylphosphonic acid;

[0102] 2) The transition metal in the colloidal modifier is a mixture of cobalt and copper, and the rare earth metal is a mixture of lanthanum and cerium, wherein the molar ratio of cobalt:copper:lanthanum:cerium is 8:8:1:1.

[0103] Comparative Example 1

[0104] Aluminum sol and boehmite were used as binders. The mass ratio of aluminum sol to boehmite (based on alumina) was 1:2, and the gel solubility index of boehmite was 99%. Boehmite was mixed with 25 wt% hydrochloric acid and gelled at 60°C for 30 min, then mixed with the aluminum sol to obtain the binder. The mass ratio of boehmite (based on alumina) to hydrochloric acid was 1:0.2.

[0105] Comparative Example 2

[0106] This comparative example is similar to Example 5, except that it does not include a curing agent and a modifier.

[0107] Aluminum hydroxide and diammonium hydrogen phosphate (P / Al molar ratio of 5:1) and an appropriate amount of water were added to a high-shear dispersing emulsifier to ensure that the binder had good fluidity. The pH of the system was adjusted to 6.0, the temperature was maintained at 70℃, and the reaction was carried out for 15 minutes.

[0108] Comparative Example 3

[0109] This comparative example is similar to Example 5, except that it does not include a curing agent and is replaced with an equal amount of boehmite.

[0110] The binder provided in this comparative example, based on a 100% dry basis, contains 82 wt% adhesive, 12 wt% boehmite, and 6 wt% modifier. The molar ratio of the multi-chelate ligand to the metal ion in the metal central ligand in the modifier is 3:1.

[0111] The specific preparation method is as follows:

[0112] S1: The octetral chelating ligand diethylenetriaminepentamethylphosphonic acid is mixed with a lactic acid solution to prepare a lactic acid solution of the diethylenetriaminepentamethylphosphonic acid multi-chelating ligand. After mixing evenly, an ethanol solution is added to obtain a diethylenetriaminepentamethylphosphonic acid ligand solution. The molar concentration of diethylenetriaminepentamethylphosphonic acid is 0.6 mol / L, the mass concentration of organic acid in the solution is 20%, and the mass concentration of ethanol is 10%.

[0113] S2: Lanthanum chloride and cadmium nitrate were added to a lactic acid solution. After complete dissolution, an ethanol solution was added and mixed thoroughly to obtain a mixed metal central ligand precursor solution. The mass concentration of lactic acid in the precursor solution was 20%, the mass concentration of ethanol was 10%, the molar concentration of the mixed metal in the precursor solution was 0.2 mol / L, and the molar ratio of lanthanum chloride to cadmium nitrate was 1:8.

[0114] S3: The diethylenetriamine pentamethylphosphonic acid ligand solution obtained from S1 and the metal central ligand precursor solution obtained from S2 are added to a high shear dispersion emulsifier at a volume ratio of 1:1. The temperature is maintained at 40℃, and ammonia water is added to adjust the pH of the system to 7. The reaction is carried out for 40 minutes to obtain a multi-metal composite chelating modifier solution.

[0115] S4: Add aluminum hydroxide and diammonium hydrogen phosphate (P / Al molar ratio of 5:1) to a high-shear dispersing emulsifier and mix with a multi-metal composite chelating modifier solution. Add an appropriate amount of water to ensure good fluidity of the binder. Adjust the pH of the system to 6.0, maintain the temperature at 70℃, and react for 15 minutes. The binder for the catalytic cracking catalyst is then obtained.

[0116] Comparative Example 4

[0117] This comparative example is similar to Example 5, except that the modifiers in Example 5 are replaced with lanthanum chloride and cadmium nitrate. The content of lanthanum chloride nitrate and cadmium nitrate in this comparative example is the same as in Example 5.

[0118] The adhesive provided in this comparative example contains 82 wt% adhesive, 12 wt% curing agent, and 6 wt% lanthanum chloride and cadmium nitrate (calculated as metal oxides) modifiers, based on 100% dry binder.

[0119] The specific preparation method is as follows:

[0120] S1: Boehmite with a gel solubility index of 20% was mixed with deionized water, and hydrochloric acid was added. The molar ratio of hydrochloric acid to boehmite (calculated as alumina) was 0.3:1. The mixture was reacted at 70°C for 1 hour. A mixed solution of dimethyloctadecyl ammonium chloride and hexadecyltrimethylammonium bromide (CTAB) was added, and the mixture was reacted at 70°C for 30 minutes. Then, the mixture was hydrothermally treated at 700°C with a water vapor content of 50% for 5 hours to obtain curing agent particles. The mass ratio of boehmite, dimethyloctadecyl ammonium chloride, and CTAB was 20:1:1.

[0121] S2: Add aluminum hydroxide and diammonium hydrogen phosphate (P / Al molar ratio of 5:1) to a high shear dispersion emulsifier and add an appropriate amount of water to ensure that the binder has good fluidity. Adjust the pH of the system to 6.0, maintain the temperature at 70℃, and react for 15 min.

[0122] S3: Add lanthanum chloride and cadmium nitrate to a high-shear dispersing emulsifier and mix with the adhesive. The molar ratio of lanthanum chloride to copper nitrate is 1:8.

[0123] S4: Add the curing agent prepared in S1 to the mixed slurry described in S3, and react at 70°C for 20 minutes. After the reaction is completed, the binder of the catalytic cracking catalyst is obtained.

[0124] Experimental Example

[0125] The binders prepared in Examples 1-5 and Comparative Examples 1-4 were used to replace conventional binder materials such as alumina sol, silica sol, and pseudo-boehmite in the production process of catalytic cracking catalysts, respectively. Catalytic cracking catalysts were prepared with 35% (mass percentage) ultrastable Y-type molecular sieve, 23% (mass percentage) binder, and 42% (mass percentage) kaolin, resulting in a solid content of 35% (mass percentage). The specific methods are as follows:

[0126] First, kaolin and deionized water are mixed and slurried. Then, a binder and a Y-type molecular sieve slurry are added, and the mixture is stirred evenly to obtain a catalyst slurry. This slurry is then spray-dried. The spray-drying conditions are as follows: the furnace temperature of the spray tower is controlled at 580℃, and the exhaust gas temperature is controlled at 160℃. After calcining the obtained catalyst at 500℃ for 1 hour, it is ion-exchanged with an ammonium chloride solution to obtain the catalyst described in the example.

[0127] The binders prepared using the above embodiments and comparative examples were used to prepare catalysts according to the above methods, and their physicochemical properties were tested according to the following evaluation and analysis methods. The specific results are shown in Table 1.

[0128] Evaluation and analysis methods:

[0129] The surface area of ​​the catalyst was determined by the low-temperature nitrogen adsorption-desorption method (NB / SH / T 0959);

[0130] The pore volume of the catalyst was tested using the water droplet method (NB / SH / T 0955);

[0131] The catalyst attrition index was determined using the straight tube method (NB / SH / T 0964);

[0132] The thermal breakdown rate of the catalyst was tested on a small-scale fixed fluidized bed (all parts are made of stainless steel) abrasion system in the laboratory. During the experiment, the catalyst in the fluidized bed was continuously fluidized and abraded under the action of fluidized air or water vapor. The extremely fine powder particles abraded were discharged from the fluidized bed with the gas through the filter element, while larger particles were blocked by the filter element and remained in the fluidized bed for further abrasion. The gas guide tube has five air inlets with a diameter of 1 mm evenly distributed at the front end and around its perimeter, and the filter element has a filtration accuracy of 1 μm. The specific steps are as follows: First, weigh 100g of the prepared catalyst, denoted as w1, and add it to the fluidized bed. Heat the preheater to 150℃ and the fluidized bed temperature to 200℃. Turn on the air generator and adjust the gas flow rate to 40m / s. The apparent gas velocity inside the reactor is 0.8m / s. After 4 hours of fluidized bed wear, weigh the remaining catalyst in the reactor and denoted as w2. Change the preheater temperature to 650℃ and the fluidized bed temperature to 680℃, keeping other conditions unchanged, and repeat the measurement of the remaining catalyst weight, denoted as w3. The thermal collapse rate L is then:

[0133] L=(w2-w3) / w2×100%

[0134] The catalyst reaction performance was tested on a small fixed fluidized bed microreactor according to the method NB / SH / T0952-2017.

[0135] Table 1

[0136] Wear index, m% Pore ​​volume, ml / g <![CDATA[Specific surface area, m 2 / g]]> Thermal collapse rate, m% Microreactive, m% Example 1 1.4 0.40 292 5.2％ 67 Example 2 0.8 0.35 263 6.9％ 63 Example 3 1.0 0.39 279 5.6％ 66 Example 4 0.8 0.36 268 6.1％ 63 Example 5 0.9 0.38 274 5.8％ 64 Example 6 0.9 0.38 273 5.9％ 64 Comparative Example 1 1.9 0.32 242 8.6％ 60 Comparative Example 2 1.2 0.29 234 11.4％ 58 Comparative Example 3 9.5 0.31 256 5.8％ 62 Comparative Example 4 1.1 0.37 255 9.9％ 62

[0137] As can be seen from the data in the table above, compared with the comparative example, the catalyst prepared by using the binder and preparation method described in this invention instead of the traditional alumina sol and acidified boehmite still has high wear resistance, pore volume and specific surface area on the basis of high molecular sieve content.

[0138] 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 binder for a catalytic cracking catalyst, characterized in that, The product comprises an adhesive, a curing agent, and a modifier. The curing agent is prepared by a hydrothermal reaction of a γ-alumina precursor, an acid, and an alkylammonium salt. The modifier is prepared by a reaction of a multi-chelate ligand, a metal-centered ligand, ethanol, and an organic acid. The adhesive comprises phosphorus-containing compounds and aluminum-containing compounds. The colloidal index of the γ-alumina precursor is ≤50%; the metal central ligand comprises rare earth metals and transition metals. Based on the dry weight of the adhesive as 100%, the content of the adhesive compound is 70~94wt%, the content of the curing agent is 4~20wt%, and the content of the modifier is 2~10wt%; the molar ratio of the multi-chelate ligand to the metal ion in the metal central ligand in the modifier is 2~5:

1.

2. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The multi-gnawing chelate is a 2-gnawing chelate with at least 2 coordinating atoms, and the coordinating atoms are P, O or N, O.

3. The binder for the catalytic cracking catalyst according to claim 2, characterized in that, The coordinating atoms are P and O.

4. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The multi-chelating ligand is one or more selected from aminotrimethylphosphonic acid, hydroxyethylidene diphosphonic acid, ethylenediaminetetramethylidene phosphonic acid, diethylenetriaminepentamethylidene phosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-hydroxyphosphonoacetic acid, bis(1,6-hexylenetriaminepentamethylidene phosphonic acid), hexamethylenediaminetetramethylidene phosphonic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, and 1,2-ethylenediamine.

5. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The rare earth metal is one or more of lanthanum, cerium, neodymium, and samarium; the transition metal is one or more of copper, silver, nickel, zinc, cobalt, and cadmium.

6. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The metal central ligand is a chloride or nitrate of a rare earth metal or a transition metal.

7. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The organic acid in the modifier is one or more of benzoic acid, lactic acid, propionic acid, formic acid, acetic acid, sorbic acid, and malic acid.

8. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The curing agent has a molar ratio of acid to γ-alumina precursor of 0.1 to 1:1; the mass ratio of γ-alumina precursor to alkylammonium salt is 9 to 20:1, wherein the γ-alumina precursor is calculated as alumina.

9. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The molar ratio of acid to γ-alumina precursor in the curing agent is 0.2~0.5:

1.

10. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The alkylammonium salt is one or more of hexadecyltrimethylammonium bromide (CTAB), hexadecylpyridine chloride (CPC), and dimethyloctadecylammonium chloride.

11. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The molar ratio of phosphorus in the phosphorus-containing compound and aluminum in the aluminum-containing compound in the adhesive is 1~10:

1.

12. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, The molar ratio of phosphorus in the phosphorus-containing compound to aluminum in the aluminum-containing compound in the adhesive is 2~6:

1.

13. The binder for the catalytic cracking catalyst according to claim 1, characterized in that, Based on the dry weight of the adhesive as 100%, the content of the adhesive compound is 76~88wt%; the content of the curing agent is 8~16wt%; and the content of the modifier is 4~8wt%.

14. A method for preparing the binder of the catalytic cracking catalyst according to any one of claims 1 to 13, characterized in that, Includes the following steps: S1: Mix the γ-alumina precursor with an acid, then add an alkylammonium salt solution to react. After the reaction is complete, perform hydrothermal treatment to obtain a curing agent. S2: Mix the multi-gnawing chelate ligand with an organic acid solution to prepare an organic acid solution of the multi-gnawing chelate ligand, add an ethanol solution, mix evenly, and then obtain a multi-gnawing chelate ligand solution. S3: Add the metal-centered ligand to the organic acid solution, and after it is completely dissolved, add the ethanol solution and mix well to obtain the metal-centered ligand precursor solution. S4: Add equal volumes of the multi-chelate ligand solution and the metal central ligand precursor solution to a high-shear dispersing emulsifier, maintain the temperature at 30~50℃, and adjust the pH of the system to 5~8; after the reaction is completed, a multi-metal composite chelate modifier solution is prepared. S5: Add aluminum-containing compounds and phosphorus-containing compounds to a high-shear dispersing emulsifier and mix them with a multi-metal composite chelating modifier solution. Add water to ensure the flowability of the material in the high-shear dispersing emulsifier, and control the pH of the system to 5~7 and the system temperature to 60~80℃ to allow it to react fully. S6: Add the curing agent obtained in step S1 to the high shear dispersion emulsifier and react. After the reaction is completed, the binder of the catalytic cracking catalyst is obtained.

15. The method for preparing the binder for the catalytic cracking catalyst according to claim 14, characterized in that, In step S1, the mixing conditions of the γ-alumina precursor and the acid are as follows: mixing at 30–100°C for 10–120 min, adding the alkylammonium salt solution, and reacting at 30–100°C for 15–30 min; the hydrothermal treatment temperature is 400–1000°C, the volume content of water vapor is 10–80%, and the time is 1–10 h.

16. The method for preparing the binder for the catalytic cracking catalyst according to claim 15, characterized in that, The volumetric content of water vapor in the hydrothermal treatment is 20-60%, and the treatment time is 4-6 hours.

17. The method for preparing the binder for the catalytic cracking catalyst according to claim 14, characterized in that, In step S2, the mass concentration of organic acid in the multi-gnawing chelate solution is 10-30%, the mass concentration of ethanol is 5-20%, and the molar concentration of multi-gnawing chelate is 0.2-1.0 mol / L.

18. The method for preparing the binder for the catalytic cracking catalyst according to claim 14, characterized in that, In step S3, the mass concentration of organic acid in the metal central ligand precursor solution is 10-30%, and the mass concentration of ethanol is 5-20%.