ALUMINUM PHOSPHATE SOL, ITS PRODUCTION METHOD AND ITS USE AS A BINDING MATERIAL IN A CATALYST FOR THE CONVERSION OF HYDROCARBON PETROLEUM PRODUCTS

Abstract

The present application relates to a phosphorus-aluminum sol, a preparation method therefor, and a use thereof as a binder in a hydrocarbon oil conversion catalyst. The present application also relates to a hydrocarbon oil conversion catalyst, a preparation method therefor, and a hydrocarbon oil catalytic conversion method using the catalyst. The phosphorus-aluminum sol provided by the present application has an appropriate colloidal particle size, a high degree of polymerization, high stability, and good adhesion, when used in a catalyst containing a molecular sieve, such as an FCC catalyst, the phosphorus-aluminum sol can reduce the blockage of molecular sieve pores, and when synergizing with other matrix materials in the catalyst, the phosphorus-aluminum sol can improve hydrothermal stability, catalytic performance and mechanical strength of the catalyst.

Description

Aluminum phosphate sol, preparation method thereof and use thereof as binder in hydrocarbon oil conversion catalyst

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to patent application number 202311436432.2, filed on October 31, 2023, entitled “A low-carbon olefin additive for promoting heavy oil conversion, its preparation method, catalyst and method for catalytic conversion of hydrocarbon oil”, patent application number 202311435723.X, filed on October 31, 2023, entitled “A low-carbon olefin additive for heavy oil cracking, its preparation method, catalyst and application”, and patent application number 202311435192.4, filed on November 1, 2023, entitled “A catalytic composition for high-yield low-carbon olefins and light oil, its preparation method and method for catalytic conversion of hydrocarbon oil”. The contents of the above applications are all incorporated herein by reference in their entirety. Technical Field

[0003] The present application relates to a phosphoaluminum sol, a preparation method thereof, and its application as a binder in a hydrocarbon oil conversion catalyst. The present application also relates to a hydrocarbon oil conversion catalyst, a preparation method thereof, and a hydrocarbon oil catalytic conversion method using the catalyst. Background Art

[0004] Aluminophosphate sol is widely used in catalysts, building materials, refractories, inorganic coatings, and other fields. It is not only a commonly used binder in refractories, but also a key component in inorganic coating formulations. It can also be used in siliceous, high-alumina, magnesia, silicon carbide, and oxide concretes. When used as a matrix in the preparation of certain catalytic cracking catalysts, it not only acts as a binder but also improves the catalyst's reactivity.

[0005] In catalytic conversion processes, especially in catalytic conversion processes for converting hydrocarbon oils into low-boiling-point hydrocarbon products, developing catalysts that can maintain high stability while achieving high selectivity and high target product yields is a very challenging goal. Phosphorus-aluminum binders play a role in stabilizing the structure, enhancing mechanical strength, and possibly participating in the catalytic reaction. As a potential solution, the research and development of molecular sieve catalysts containing phosphorus-aluminum matrices are of great significance for improving the efficiency and economy of the entire catalytic conversion process. However, there is very little information in the prior art about molecular sieve catalysts containing phosphorus-aluminum matrices that stably and selectively convert hydrocarbon molecules to produce light low-carbon olefins. Such catalysts still find it difficult to meet the requirements of high hydrothermal stability, high activity and selectivity, and high conversion rate.

[0006] CN1070384A provides a method for preparing a phosphorus-containing aluminum sol: orthophosphoric acid or aluminum dihydrogen phosphate is added to the aluminum sol, followed by high-temperature depolymerization and concentration to obtain the phosphorus-containing aluminum sol. CN1070385A provides a method for preparing a phosphorus-containing aluminum sol: reacting a mixture of metallic aluminum, hydrochloric acid (or aluminum chloride), and orthophosphoric acid (or aluminum dihydrogen phosphate) under certain conditions, followed by high-temperature depolymerization and concentration to obtain the phosphorus-containing aluminum sol.

[0007] CN1417296A provides a chlorine-free phosphorus-containing aluminum sol that can be used as a petroleum hydrocarbon cracking catalyst and its preparation method. The preparation method comprises: beating an acid-peptized aluminum hydroxide or aluminum oxide with decationized water to form a slurry with a solid content of 15-35% by weight, adding concentrated phosphoric acid to the slurry at a weight ratio of P / Al = 1.2-6 while stirring, then heating to 65-95°C and reacting at this temperature for 15-90 minutes until it becomes a transparent colloid. The chlorine-free phosphorus-containing aluminum sol can be mixed with conventional chlorine-containing aluminum sol for use.

[0008] CN102847547B discloses an inorganic binder containing a phosphorus-aluminum compound and a preparation method thereof. Acid-peptized aluminum hydroxide and / or aluminum oxide and clay are slurried and dispersed with decationized water to form a slurry with a solid content of 15-45% by weight. Concentrated phosphoric acid is added to the slurry at a weight ratio of P / Al of 1-6 while stirring, and then reacted at 50-99°C for 15-90 minutes.

[0009] CN115215311A provides an aluminum phosphate sol, a preparation method and application thereof, and a catalytic cracking catalyst and a preparation method thereof. The colloid particles of the aluminum phosphate sol have an outer layer structure and an inner structure within the outer layer. The preparation method comprises: (1) mixing an aluminum source with water to form an aluminum source slurry; (2) bringing the aluminum source slurry obtained in step (1) into first contact with a first phosphoric acid to obtain a second slurry; and (3) bringing the second slurry obtained in step (2) into second contact with a second phosphoric acid to react at elevated temperature.

[0010] Existing methods for preparing phosphate-aluminum sols are costly and complex, and are prone to solidification or precipitation of the reaction product due to fluctuations in reaction conditions during the preparation process. The resulting phosphate-aluminum sols typically have a low degree of polymerization (DOP), for example, less than 1, and a high content of free phosphate, which readily reacts with other alumina colloids in the catalyst, affecting its bonding properties. Consequently, the resulting hydrocarbon-to-oil conversion catalysts are not highly active.

[0011] Therefore, there is a need in the art for a phosphate-aluminum sol having high polymerization degree, high stability, appropriate colloidal particle size, and good adhesion, and a high-performance hydrocarbon oil conversion catalyst based on the phosphate-aluminum sol.

[0012] Summary of the Invention

[0013] An object of the present invention is to provide a phosphate aluminum sol binder and a preparation method thereof. The phosphate aluminum sol has high polymerization degree, high stability, appropriate colloidal particle size, and good bonding properties.

[0014] Another object of the present invention is to provide a hydrocarbon oil conversion catalyst prepared using the phosphorus aluminum sol and a hydrocarbon oil catalytic conversion method using the catalyst, so as to effectively improve the target product yield of the hydrocarbon oil catalytic conversion method, such as the light olefin yield and total liquid yield, increase the olefin content in liquefied petroleum gas (LPG), reduce oil slurry and coke, promote diesel conversion, and / or reduce gasoline loss.

[0015] In order to achieve the above object, in the first aspect, the present invention provides a phosphate aluminum sol, wherein the phosphate aluminum sol contains Al, P and a stabilizer, and the P / Al weight ratio thereof is 1.6-6:1; 31 In the P nuclear magnetic resonance spectrum, the peak area of ​​the resonance signal with a chemical shift of -12±2ppm is QP0 2 The peak area of ​​the resonance signal with a chemical shift of 0±2ppm is QP0 0 , QP0 2 / QP0 0 =1.5-5, and the average particle size of the phosphate aluminum sol is 10-30nm.

[0016] In a second aspect, the present invention provides a method for preparing the aluminum-phosphorus sol according to the first aspect, comprising:

[0017] 1) Under stirring conditions at a temperature of 50°C to 95°C, an aluminum salt source, decationized water, and a stabilizer are mixed and slurried to obtain an aluminum oxide precursor solution.

[0018] 2) adding phosphate to the alumina precursor solution at a P / Al weight ratio of 1.6-6:1 under stirring at a temperature of 25° C.-70° C. to react and obtain a phosphate-aluminum sol.

[0019] In a third aspect, the present invention provides a hydrocarbon oil conversion catalyst, which contains a molecular sieve, a phosphate-aluminum binder, other inorganic binders different from the phosphate-aluminum binder, an optional metal component, an optional medium- and macroporous inorganic oxide material, and an optional clay, wherein the phosphate-aluminum binder is derived from the phosphate-aluminum sol according to the first aspect or the phosphate-aluminum sol prepared by the method according to the second aspect.

[0020] In a fourth aspect, the present invention provides a method for preparing the hydrocarbon oil conversion catalyst according to the third aspect, comprising:

[0021] a) mixing and slurrying the molecular sieve, the other inorganic binder, the metal source of the optional metal component, the optional medium- and macroporous inorganic oxide material, the optional clay, and water, and controlling the pH value of the slurry to be greater than 2.5 to obtain a first slurry;

[0022] b) mixing the first slurry with the phosphate aluminum sol to obtain a second slurry, spray drying and calcining the mixture to obtain the catalyst.

[0023] In a fifth aspect, the present invention provides a catalyst composition comprising a co-catalyst and an optional main catalyst, wherein the co-catalyst is the hydrocarbon oil conversion catalyst according to the third aspect, and the optional main catalyst is preferably a catalytic cracking catalyst.

[0024] In a sixth aspect, the present invention provides a method for catalytic conversion of hydrocarbon oil, comprising contacting hydrocarbon oil with the hydrocarbon oil conversion catalyst according to the third aspect or the catalyst composition according to the fifth aspect to carry out a reaction.

[0025] The phosphate-aluminum sol provided by the present invention has a higher QP than the phosphate-aluminum sol of the prior art at the same phosphorus-aluminum ratio. 2 / QP0 0 The aluminum-phosphorus sol provided by the present invention has a high degree of polymerization and also has an appropriate colloidal particle size and concentrated size distribution, as well as high stability and good bonding properties.

[0026] The phosphate-aluminum sol provided by the present invention can polymerize at high temperatures to form a high-melting-point, highly adhesive material, which can improve the strength, high-temperature resistance, and / or wear resistance of the material. The phosphate-aluminum sol can be used as a binder for preparing catalysts, a binder for refractory materials, or an additive for coatings. For example, the phosphate-aluminum sol provided by the present invention, due to its appropriate colloidal size and high degree of polymerization, can reduce the blockage of the molecular sieve pores when used to prepare a catalyst containing a molecular sieve, such as an FCC catalyst, thereby improving the hydrothermal stability, catalytic performance, and mechanical strength of the catalyst, such as improving the wear resistance (wear strength) of the FCC catalyst, and increasing the cracking activity, reactant conversion rate, and / or target product selectivity. For example, in some cases, it can improve the selectivity of gasoline, propylene, and / or butene.

[0027] The phosphate aluminum sol provided by the present invention, its preparation method and its use as a binder in a hydrocarbon oil conversion catalyst have at least one of the following advantages, preferably multiple or all of the advantages:

[0028] 1. The raw materials for the preparation of phosphate aluminum sol adopt low-cost aluminum salt and phosphate, thereby reducing the production cost.

[0029] 2. The synthesis time is shortened by adopting a specific preparation method.

[0030] 3. By adopting specific preparation raw materials and screening preparation procedures and reaction conditions, the stability of the phosphate aluminum sol is improved, and precipitation, solidification or stratification is avoided, thereby extending the storage time and service life of the phosphate aluminum sol.

[0031] 4. The obtained aluminum-phosphorus sol has a higher QP0 at the same aluminum-phosphorus ratio. 2 / QP0 0 , there are relatively few free phosphates and relatively more polymerized phosphates, which can reduce the reaction between the phosphate-aluminum sol and other binders, and at the same time reduce the destructive effect on the non-framework Al and framework Al in the molecular sieve, which is beneficial to improving the activity and hydrothermal stability of the molecular sieve.

[0032] 5. The obtained phosphoaluminum sol has an appropriate and uniform particle size, abundant surface hydroxyl groups, high aggregation and high matrix activity, which is more conducive to matching with molecular sieves, reducing the blockage of molecular sieve pores and improving the selectivity of light olefins in FCC catalysts.

[0033] 6. The obtained aluminum-phosphorus sol has good adhesiveness and can be used in catalyst preparation to improve the mechanical strength of the catalyst.

[0034] 7. The obtained aluminum-phosphorus sol has a synergistic effect with the molecular sieve and other matrix materials in the catalyst, which can effectively increase the yield of light olefins, increase the olefin content in LPG, promote heavy oil conversion, reduce coke and oil slurry, and / or increase the yield of gasoline and LPG.

[0035] Other features and advantages of the present application will be described in detail in the subsequent detailed description. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The accompanying drawings are used to provide a further understanding of the present application and constitute a part of the specification. Together with the following detailed description, they are used to explain the present application but do not constitute a limitation of the present application. In the accompanying drawings:

[0037] Figure 1 is a graph showing the aluminum phosphate sol obtained in Example 1 and Comparative Example 1. 31 P NMR spectrum.

[0038] FIG2 is a transmission electron microscope image of the phosphate aluminum sol obtained in Example 1. DETAILED DESCRIPTION

[0039] The following describes the specific embodiments of the present application in detail with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present application and are not intended to limit the present application.

[0040] Any specific numerical value disclosed herein (including the endpoints of a numerical range) is not limited to the exact value of the numerical value, but should be understood to also include values ​​close to the exact value, such as all possible values ​​within ±5% of the exact value. Moreover, for a disclosed numerical range, any combination of the endpoints of the range, between the endpoints and the specific points in the range, and between the specific points can be used to generate one or more new numerical ranges, and these new numerical ranges should also be considered to be specifically disclosed herein.

[0041] Unless otherwise specified, the terms used herein have the same meaning as commonly understood by those skilled in the art. If a term is defined herein and its definition is different from the commonly understood meaning in the art, the definition herein shall prevail.

[0042] In the present application, the term "weakly acidic organic acid" refers to an organic compound that can only partially ionize hydrogen ions in aqueous solution, thereby exhibiting relatively weak acidity, such as an organic acid having one or more, preferably 1-3, carboxyl (-COOH) functional groups.

[0043] In this application, except for the contents explicitly stated, any matters or issues not mentioned are directly applicable to those known in the art without any changes. Moreover, any embodiment described herein can be freely combined with one or more other embodiments described herein, and the technical solutions or technical ideas formed thereby are deemed to be part of the original disclosure or original record of this application, and should not be regarded as new content not disclosed or anticipated herein, unless a person skilled in the art considers that the combination is obviously unreasonable.

[0044] All patent and non-patent literature, including but not limited to textbooks and journal articles, mentioned herein are incorporated by reference in their entirety.

[0045] Aluminum phosphate sol

[0046] As described above, in the first aspect, the present invention provides a phosphate aluminum sol, wherein the phosphate aluminum sol contains Al, P and a stabilizer, wherein the P / Al weight ratio is 1.6-6:1, QP0 2 / QP0 0 =1.5-5, and the average particle size of the phosphate aluminum sol is 10-30nm.

[0047] The P / Al weight ratio (calculated as element) of the phosphate aluminum sol according to the present invention is 1.6-6: 1, such as 1.6-5.8: 1, such as 1.7-5.6: 1. In some embodiments, the P / Al weight ratio (calculated as element) of the phosphate aluminum sol can be 1.6: 1, 1.7: 1, 1.8: 1, 1.9: 1, 2: 1, 2.1: 1, 2.2: 1, 2.3: 1, 2.4: 1, 2.5: 1, 2.6: 1, 2.7: 1, 2.8: 1, 2.9: 1, 3: 1, 3.1: 1, 3.2: 1, 3.3: 1, 3.4: 1, 3.5: 1, 3.6: 1, 3.7: 1, 3.8: 1, 3.9: 1, 4. .7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.7:1, 5.8:1, 5.9:1, 6:1, or in a range consisting of any two of the above values.

[0048] QP0 of the aluminum phosphate sol according to the present invention 2 / QP0 0 =1.5-5, such as 1.5-4, such as 1.5-3.3. In some embodiments, the QP of the aluminum phosphate sol is 2 / QP0 0 The aluminum phosphate sol may be 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, or within a range consisting of any two of the above values. 31 In the P nuclear magnetic resonance spectrum, the peak area of ​​the resonance signal with a chemical shift of -12±2ppm is defined as QP0 2 The peak area of ​​the resonance signal with a chemical shift of 0±2ppm is defined as QP0 0 At the same phosphorus to aluminum ratio, QP0 2 / QP0 0 A higher degree of polymerization indicates a higher degree of polymerization. A higher degree of polymerization means relatively fewer free phosphates and more highly polymerized phosphates, which can reduce the reaction between free phosphates in the phosphate-aluminum sol and other binders. It can also reduce the destructive effects on non-framework Al and framework Al in the molecular sieve, which is beneficial to improving the activity and hydrothermal stability of the molecular sieve.

[0049] Preferably, the aluminophosphate sol according to the present invention may contain 3-15 wt %, for example 3-12 wt %, of Al, calculated as Al2O3. In some embodiments, the aluminophosphate sol may contain 3 wt %, 4 wt %, 5 wt %, 6 wt %, 7 wt %, 8 wt %, 9 wt %, 10 wt %, 11 wt %, 12 wt %, 13 wt %, 14 wt %, 15 wt %, or a range consisting of any two of the above values, of Al, calculated as Al2O3.

[0050] Preferably, the aluminum phosphate sol according to the present invention may contain 15-40 wt%, for example 15-35 wt%, of P, calculated as PO. In some embodiments, the aluminum phosphate sol may contain 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, 20 wt%, 21 wt%, 22 wt%, 23 wt%, 24 wt%, 25 wt%, 26 wt%, 27 wt%, 28 wt%, 29 wt%, 30 wt%, 31 wt%, 32 wt%, 33 wt%, 34 wt%, 35 wt%, 36 wt%, 37 wt%, 38 wt%, 39 wt%, 40 wt%, or a range consisting of any two of the above values, calculated as PO.

[0051] Preferably, the phosphate aluminum sol according to the present invention may contain 0.1-10 wt %, such as 0.5-5 wt %, 2-4 wt % of a stabilizer. In some embodiments, the phosphate aluminum sol may contain 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt %, 0.5 wt %, 0.6 wt %, 0.7 wt %, 0.8 wt %, 0.9 wt %, 1.0 wt %, 1.5 wt %, 2 wt %, 2.5 wt %, 3 wt %, 3.5 wt %, 4 wt %, 4.5 wt %, 5 wt %, 5.5 wt %, 6 wt %, 6.5 wt %, 7 wt %, 7.5 wt %, 8 wt %, 8.5 wt %, 9 wt %, 9.5 wt %, 10 wt %, or a range consisting of any two of the above values ​​of stabilizer.

[0052] Preferably, the stabilizer can be a weakly acidic organic acid. For example, the stabilizer can be selected from at least one of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid. The stabilizer is preferably oxalic acid, acetic acid, citric acid, or a combination thereof.

[0053] Preferably, the pH value of the phosphate aluminum sol according to the present invention can be 0.5-2.5, for example 0.8-1.9. In some embodiments, the pH value of the phosphate aluminum sol can be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, or a range consisting of any two of the above values.

[0054] %, 47 wt %, 48 wt %, 49 wt %, 50 wt %, or a range consisting of any two of the above values.

[0055] Preferably, the kinetic viscosity of the aluminum-phosphorus sol according to the present invention may be 10-50 cP. In some embodiments, the dynamic viscosity of the aluminum phosphate sol can be 10cP, 11cP, 12cP, 13cP, 14cP, 15cP, 16cP, 17cP, 18cP, 19cP, 20cP, 21cP, 22cP, 23cP, 24cP, 25cP, 26cP, 27cP, 28cP, 29cP, 30cP, 31cP, 32cP, 33cP, 34cP, 35cP, 36cP, 37cP, 38cP, 39cP, 40cP, 41cP, 42cP, 43cP, 44cP, 45cP, 46cP, 47cP, 48cP, 49cP, 50cP, or in a range consisting of any two of the above values.

[0056] The average particle size (also referred to as particle size) of the phosphate-aluminum sol according to the present invention is 10-30 nm, for example, 15-28 nm. Preferably, the particle size of the phosphate-aluminum sol according to the present invention is primarily concentrated between 10-30 nm, and the particle size aggregation is greater than 85%, for example, 85-95%. The particle size of the phosphate-aluminum sol is primarily concentrated between 10-30 nm, meaning that the aggregation of particles with a size between 10-30 nm in the phosphate-aluminum sol is greater than 85%. The aggregation refers to the ratio of particles with a size between 10-30 nm to the total number of particles. The particle size (also referred to as particle size) is measured by transmission electron microscopy and is the maximum projected dimension of the particles. The average particle size is the arithmetic mean of the particle sizes. The phosphate-aluminum sol according to the present invention has an appropriate and uniform particle size, which is more conducive to matching with the molecular sieve, reducing blockage of the molecular sieve pores, and improving the selectivity of the catalyst.

[0057] The aluminum phosphate sol according to the present invention contains a balance of water, preferably a water content of 10-30% by weight.

[0058] The aluminum phosphate sol according to the present invention contains cations derived from phosphate, such as ammonium ions, in an amount of, for example, 5-15% by weight.

[0059] The aluminum phosphate sol according to the present invention contains inorganic acid radicals derived from an aluminum salt source, such as one or more of sulfate, chloride, and nitrate, and the content of the inorganic acid radicals is, for example, 10-50% by weight.

[0060] Preferably, the molar ratio of the organic acid radical of the stabilizer to Al in the phosphate-aluminosol according to the present invention is 0.05-0.5: 1. In some embodiments, the molar ratio of the organic acid radical of the stabilizer to Al in the phosphate-aluminosol may be 0.05: 1, 0.06: 1, 0.07: 1, 0.08: 1, 0.09: 1, 0.1: 1, 0.15: 1, 0.2: 1, 0.25: 1, 0.3: 1, 0.35: 1, 0.4: 1, 0.45: 1, 0.5: 1, or within a range consisting of any two of the foregoing values.

[0061] The phosphate-aluminum sol according to the present invention has a higher degree of polymerization than the phosphate-aluminum sols of the prior art at the same phosphorus-to-aluminum ratio. In addition, the phosphate-aluminum sol according to the present invention also has an appropriate colloidal particle size and a concentrated size distribution, as well as high stability and good adhesion. The phosphate-aluminum sol according to the present invention can undergo polymerization at high temperatures to form a high-melting-point, highly adhesive material, which can improve the strength, high-temperature resistance and / or wear resistance of the material. The phosphate-aluminum sol can be used as a binder for preparing catalysts, a binder for refractory materials, or an additive for coatings. For example, the phosphate-aluminum sol according to the present invention, due to its appropriate colloidal particle size and high degree of polymerization, can reduce blockage of the molecular sieve pores when used to prepare catalysts containing molecular sieves, such as FCC catalysts, and improve the hydrothermal stability, catalytic performance and mechanical strength of the catalyst, such as improving the wear resistance (wear strength) of the FCC catalyst, and increasing cracking activity, reactant conversion and / or target product selectivity. For example, in some cases, it can improve gasoline, propylene and / or butene selectivity.

[0062] Preparation method of aluminum phosphate sol

[0063] In a second aspect, the present invention further provides a method for preparing the aluminum-phosphorus sol according to the first aspect, comprising:

[0064] 1) Under stirring conditions at a temperature of 50°C to 95°C, an aluminum salt source, decationized water, and a stabilizer are mixed and slurried to obtain an aluminum oxide precursor solution.

[0065] 2) adding phosphate to the alumina precursor solution at a P / Al weight ratio of 1.6-6:1 under stirring at a temperature of 25° C.-70° C. to react and obtain a phosphate-aluminum sol.

[0066] Preferably, the temperature of step 1) is 60-90°C; the temperature of step 2) is 30-55°C.

[0067] Preferably, the aluminum salt source may be one or more of aluminum nitrate, aluminum sulfate, and aluminum chloride.

[0068] Preferably, the phosphate may be diammonium hydrogen phosphate and / or ammonium dihydrogen phosphate. The phosphate may be added by adding a phosphate solution or by adding a phosphate solid.

[0069] Preferably, the stabilizer can be a weakly acidic organic acid. For example, the stabilizer can be selected from at least one of glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid, and citric acid. The stabilizer is preferably oxalic acid, acetic acid, citric acid, or a combination thereof.

[0070] In step 1), the decationized water is also known as decationized water or acidic water, which is well known to those skilled in the art. The pH value of the decationized water is preferably 2.8-3.2, and the sodium oxide content is preferably <5 ppm.

[0071] Preferably, in step 1), the weight ratio of the aluminum salt source, decationized water and stabilizer is 100:(50-800):(5-40), preferably 100:(100-750):(6-35), and the aluminum salt is calculated as aluminum oxide;

[0072] In step 2), the weight ratio of the aluminum oxide precursor solution to the phosphate is 100:(50-200), preferably 100:(60-150), and the phosphate is calculated as phosphorus oxide.

[0073] Preferably, the pH value of the aluminum oxide precursor solution can be 0.5-3.0, such as 0.6-2, such as 0.7-1.5. In some embodiments, the pH value of the aluminum oxide precursor solution can be 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, or a range consisting of any two of the above values.

[0074] %, 37 wt %, 38 wt %, 39 wt %, 40 wt %, or a range consisting of any two of the above values.

[0075] Preferably, in step 1), the beating time is more than 5 minutes, for example, 10-50 minutes; in step 2), the reaction time is 10-60 minutes.

[0076] Preferably, the temperature in step 2) can be 10-50°C lower than the temperature in step 1), for example, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, or any range consisting of any two of these values. In some embodiments, step 2) can be performed under heat preservation or temperature control conditions. In other embodiments, step 2) can be performed under non-heating conditions with a slow temperature reduction.

[0077] Preferably, the method for preparing the aluminum-phosphorus sol may include:

[0078] 1) mixing and slurrying an aluminum salt source, decationized water, and a stabilizer at a temperature of 50° C. to 95° C., for example, 60° C. to 80° C., to obtain an aluminum oxide precursor solution having a solid content of 5-40% by weight. The slurrying time is 10-50 minutes to hydrolyze the aluminum salt source, and then the heating is stopped.

[0079] 2) Adding phosphate to the alumina precursor solution at a P / Al weight ratio of 1.6-6:1 at a temperature of 25-70° C., for example, 35-55° C., under stirring, and slowly reacting for 10-60 minutes until a transparent colloid is formed.

[0080] By adopting the specific preparation method according to the present invention, the synthesis time of the phosphate-aluminum sol is shortened, the preparation cost of the phosphate-aluminum sol is reduced, the stability of the phosphate-aluminum sol is improved, and precipitation, solidification or stratification is avoided, thereby extending the storage time and service life of the phosphate-aluminum sol, so that a phosphate-aluminum sol with appropriate particle size, high polymerization degree, high stability, and good adhesion can be obtained.

[0081] Hydrocarbon oil conversion catalyst

[0082] In a third aspect, the present invention also provides a hydrocarbon oil conversion catalyst, which contains a molecular sieve, a phosphate-aluminum binder, other inorganic binders different from the phosphate-aluminum binder, an optional metal component, an optional medium- and macroporous inorganic oxide material, and an optional clay, wherein the phosphate-aluminum binder is the phosphate-aluminum sol according to the first aspect or the phosphate-aluminum sol prepared by the method according to the second aspect, or comes from the phosphate-aluminum sol according to the first aspect or the phosphate-aluminum sol prepared by the method according to the second aspect.

[0083] Preferably, the molecular sieve may be selected from MFI molecular sieve, BEA molecular sieve, or a combination thereof.

[0084] According to the present invention, the other inorganic binder can be any conventionally used by those skilled in the art in preparing the catalyst. Preferably, the other inorganic binder can be selected from one or more of pseudo-boehmite, diaspore, aluminum sol, silica-alumina sol and silica sol.

[0085] According to the present invention, the clay may be any clay commonly used by those skilled in the art in preparing catalysts. Preferably, the clay may be selected from one or more of kaolin, sepiolite, attapulgite, rectorite, montmorillonite, and diatomaceous earth.

[0086] First embodiment of the third aspect

[0087] In a first embodiment of the third aspect, the catalyst comprises a molecular sieve, a phosphorus-aluminum binder, other inorganic binders, a metal component, and optionally a clay.

[0088] Preferably, based on the dry weight of the catalyst, the content of the molecular sieve is 25-75% by weight, the content of the metal component is 0.5-8% by weight as metal oxide, the content of the phosphoaluminum binder is 3-40% by weight as oxide, the content of the other inorganic binder is 1-25% by weight as oxide, and the content of the clay is 0-30% by weight.

[0089] More preferably, based on the dry weight of the catalyst, the content of the molecular sieve is 30-65 wt%, the content of the metal component is 0.8-6 wt% as metal oxide, the content of the phosphoaluminum binder is 8-32 wt% as oxide, the content of the other inorganic binder is 2-20 wt% as oxide, and the content of the clay is 1-25 wt%.

[0090] Further preferably, based on the dry weight of the catalyst, the content of the molecular sieve is 40-60 wt%, the content of the metal component is 1-5.5 wt% as metal oxide, the content of the phosphoaluminum binder is 20-30 wt% as oxide, the content of the other inorganic binder is 10-18 wt% as oxide, and the content of the clay is 5-10 wt%.

[0091] The catalyst having the above composition has better catalytic performance, can further improve the yield of light olefins, promote the conversion of heavy oil, and / or reduce coke and oil slurry.

[0092] Preferably, the pore volume of the catalyst measured by the BJH method is greater than 0.12 mL / g, such as 0.12-0.14 mL / g, more preferably greater than 0.122 mL / g.

[0093] Preferably, the metal in the metal component is selected from at least one of Group VIII metals, preferably one or more of Fe, Co and Ni.

[0094] Preferably, the molecular sieve contains MFI molecular sieve and BEA molecular sieve, the molecular sieve contains a first phosphorus component, the phosphorus-aluminum binder contains a second phosphorus component, and the total content of the first phosphorus component and the second phosphorus component in the catalyst is 10-35% by weight, for example, 15-25% by weight, calculated as P2O5.

[0095] Preferably, the MFI molecular sieve and the BEA molecular sieve are each independently selected from one or more of a hydrogen-type molecular sieve, a phosphorus-containing molecular sieve, and a molecular sieve containing both phosphorus and a transition metal. In a preferred embodiment, at least one of the MFI and BEA molecular sieves contains phosphorus. Preferably, the MFI and BEA molecular sieves are each independently a molecular sieve containing both phosphorus and a transition metal, i.e., the MFI molecular sieve may contain both phosphorus and a transition metal, and the BEA molecular sieve may contain both phosphorus and a transition metal. The MFI and / or BEA molecular sieves may contain a modifying metal, wherein the modified metal is not counted as part of the metal component but is considered part of the molecular sieve component. Preferably, the total content of the modifying metal and the metal component in the molecular sieve is 0.5-8 wt%.

[0096] Preferably, the MFI molecular sieve is a multi-level pore ZSM-5 molecular sieve, the silicon-aluminum ratio of the multi-level pore ZSM-5 molecular sieve is 20-70, the pore volume measured by the BJH method is greater than 0.25 mL / g, the pore volume of pores with a pore diameter of 2-50 nm accounts for 40-70% of the total pore volume; the pore volume of pores with a pore diameter of 2-20 nm accounts for more than 85% of the total mesopore volume, and the micropore volume is greater than 0.1 cc / g.

[0097] Preferably, the BEA molecular sieve is a β molecular sieve having a micropore specific surface area of ​​450-500 m 2 / g, the proportion of the mesopore volume of the β molecular sieve to the total pore volume is 35-60 volume%; the proportion of the strong acid content of the molecular sieve to the total acid content is 25-55%, and the ratio of the B acid content to the L acid content is 35-75.

[0098] According to the present invention, the pore volume, total pore volume and micropore volume determined by the BJH method are measured according to the RIPP 151-90 method (see Petrochemical Analytical Methods, Determination of Pore Volume and Pore Size Distribution of Catalysts by Nitrogen Adsorption Capacitance, Petrochemical Analytical Methods (RIPP Experimental Method), edited by Yang Cuiding et al., Science Press, 1990).

[0099] Preferably, the weight ratio of the BEA molecular sieve to the MFI molecular sieve is (0.01-100):1, preferably (0.1-30):1, and more preferably (0.25-6):1. When the molecular sieves use the above ratio of BEA molecular sieve to MFI molecular sieve, the catalyst can further improve the content of propylene and butene in liquefied gas, increase the olefin content in LPG, promote diesel cracking, and / or reduce gasoline losses, thereby reducing the yields of diesel and slurry oil and improving the yields of gasoline and LPG.

[0100] Second implementation plan of the third aspect

[0101] In a second embodiment of the third aspect, the catalyst contains molecular sieves, phosphorus aluminum binders, other inorganic binders, medium- and macroporous inorganic oxide materials, and optional clay, wherein the medium- and macroporous inorganic oxide materials are preferably macroporous alumina materials, and the molecular sieves are preferably MFI molecular sieves.

[0102] Preferably, based on the dry weight of the catalyst, the content of the MFI molecular sieve is 10-75% by weight, the content of the macroporous alumina material is 1-30% by weight, the content of the phosphorus-aluminum binder is 3-35% by weight as oxide, the content of the other inorganic binder is 1-20% by weight as oxide, and the content of the clay is 0-60% by weight.

[0103] More preferably, based on the dry weight of the catalyst, the content of the MFI molecular sieve is 15-65 weight %, the content of the macroporous alumina material is 2-25 weight %, the content of the phosphorus aluminum binder is 8-32 weight % as oxide, the content of the other inorganic binder is 2-20 weight % as oxide, and the content of the clay is 1-25 weight %.

[0104] Further preferably, based on the dry weight of the catalyst, the content of the MFI molecular sieve is 20-60% by weight, the content of the macroporous alumina material is 2-20% by weight, the content of the phosphorus aluminum binder is 20-30% by weight as oxide, the content of the other inorganic binder is 10-18% by weight as oxide, and the content of the clay is 5-10% by weight.

[0105] The catalyst with the above composition has better catalytic performance, can further improve the yield of light olefins, promote the conversion of heavy oil, and reduce coke and oil slurry.

[0106] Preferably, the MFI molecular sieve is one or more selected from hydrogen-type MFI molecular sieve, phosphorus-containing MFI molecular sieve and transition metal-containing MFI molecular sieve.

[0107] Preferably, the macroporous alumina material has a bimodal pore distribution structure, wherein the pore volume of pores with a pore diameter of 2-10 nm accounts for 20-40% of the total pore volume, and the pore volume of pores with a pore diameter of 10-100 nm accounts for 60-80% of the total pore volume. The bimodal structure of the macroporous alumina material means that the pore distribution spectrum of the macroporous alumina material measured by nitrogen adsorption capacity method has two distinct peaks.

[0108] The macroporous alumina material has a bimodal pore distribution, which facilitates the diffusion of heavy oil macromolecules and reactant molecules, promoting heavy oil precracking and reducing coke formation. The phosphoaluminum binder works synergistically with the macroporous alumina material and MFI molecular sieve, effectively increasing the yield of light olefins (such as propylene) and the content of light olefins (such as propylene) in liquefied gas, promoting heavy oil conversion, and / or reducing coke and oil slurry.

[0109] A third implementation plan of the third aspect

[0110] In a third embodiment of the third aspect, the catalyst contains molecular sieves, phosphorus aluminum binders, other inorganic binders, medium- and macroporous inorganic oxide materials, and optional clay, wherein the medium- and macroporous inorganic oxide materials are preferably porous silicon-aluminum composite materials, and the molecular sieves are preferably MFI molecular sieves.

[0111] Preferably, based on the dry weight of the catalyst, the content of the MFI molecular sieve is 10-75% by weight, the content of the porous silicon-aluminum composite material is 1-30% by weight, the content of the phosphorus-aluminum binder is 3-35% by weight as oxide, the content of the other inorganic binder is 1-20% by weight as oxide, and the content of the clay is 0-60% by weight.

[0112] More preferably, based on the dry weight of the catalyst, the content of the MFI molecular sieve is 15-65 weight %, the content of the porous silicon-aluminum composite material is 2-25 weight %, the content of the phosphorus-aluminum binder is 8-32 weight % as oxide, the content of the other inorganic binder is 2-20 weight % as oxide, and the content of the clay is 1-25 weight %.

[0113] Further preferably, based on the dry weight of the catalyst, the content of the MFI molecular sieve is 20-60 weight%, the content of the porous silicon-aluminum composite material is 2-20 weight%, the content of the phosphorus-aluminum binder is 10-30 weight% as oxide, the content of the other inorganic binder is 10-18 weight% as oxide, and the content of the clay is 5-10 weight%.

[0114] Preferably, the MFI molecular sieve is one or more selected from hydrogen-type MFI molecular sieve, phosphorus-containing MFI molecular sieve and transition metal-containing MFI molecular sieve.

[0115] Preferably, the porous silicon-aluminum composite material has a mass composition of (0.01-1) Na2O:Al2O3:(2-5)SiO2 and a specific surface area of ​​300-600m 2 / g, the total pore volume is 0.15-0.4mL / g, and the volume of medium and large pores with a pore diameter of 2-50nm accounts for 20-40% of the total pore volume.

[0116] Preferably, the porous silicon-aluminum composite material is obtained by hydrothermal crystallization of kaolin. In a specific embodiment, the porous silicon-aluminum composite material is prepared by a method comprising the following steps:

[0117] a) treating metakaolin obtained by calcining kaolin with an inorganic acid at 80-95° C. to obtain a first mixture;

[0118] b) mixing the first mixture, sodium silicate, a directing agent, and an alkaline solution to obtain a second mixture; wherein the second mixture has a composition of (0.1-5) Na2O:Al2O3:(2-10)SiO2:(5-100)H2O in a weight ratio;

[0119] c) After subjecting the second mixture to hydrothermal crystallization, the solid product is taken out, filtered and washed to obtain the porous silicon-aluminum composite material.

[0120] Preferably, in step a), the weight ratio of the inorganic acid to the metakaolin is (0.01-0.1):1, wherein the inorganic acid is H + The metakaolin is measured on a dry basis;

[0121] The weight ratio of the directing agent to the metakaolin is (0.01-1.0):1, and the directing agent is calculated on a dry basis of oxides.

[0122] Preferably, in step b), the alkaline solution may be one or more of sodium hydroxide solution, ammonia water, potassium hydroxide, magnesium hydroxide and sodium carbonate.

[0123] The present invention does not impose any specific restrictions on the method of removing the solid in step c), for example, it can be methods such as suction filtration, centrifugal separation, filtration, etc. In a preferred embodiment, the solid product in step c) is taken out and then washed and dried. According to the present invention, hydrothermal crystallization treatment is well known to those skilled in the art. In a preferred embodiment, the conditions of the hydrothermal crystallization treatment include: a temperature of 90-98°C and a time of 4-32h. The hydrothermal crystallization treatment can be carried out under the autogenous pressure of the system or under external pressure, preferably under the autogenous pressure of the system.

[0124] According to the present invention, in step a), kaolin is calcined at 700-900°C for 1-3 hours to obtain the metakaolin. In a specific embodiment, in step a), the weight ratio of the inorganic acid to the metakaolin is (0.01-0.1):1, wherein the inorganic acid is H + The metakaolin is calculated on a dry basis; the weight ratio of the directing agent to the metakaolin is (0.01-1.0):1, and the directing agent is calculated on a dry basis of oxide. According to the present invention, the inorganic acid may include, but is not limited to, hydrochloric acid, sulfuric acid, nitric acid, etc. The directing agent is a NaY molecular sieve synthesis directing agent well known to those skilled in the art. In a specific embodiment, the molar composition of the directing agent is: (10-17)SiO2: (0.7-1.3)Al2O3: (11-18)Na2O: (200-350)H2O. The directing agent can be synthesized according to conventional methods, for example, according to the preparation methods of USP3574538, USP3639099, USP3671191, USP4166099, and EUP0435625.

[0125] The porous silica-alumina composite material's abundant mesopores enhance the diffusion of feedstock molecules and reactants. It also increases the activity of the matrix, facilitating the cracking of heavy oil molecules and increasing the use of gasoline olefins as propylene precursors. The synergistic effect of the phosphorus-alumina binder, the porous silica-alumina composite material, and the MFI molecular sieve enables the catalyst to increase the yield of catalytically cracked liquefied gas and propylene. The combined yield of gasoline and liquefied gas is high, the coke yield is lower, and the total liquid yield and conversion rate are high, significantly improving heavy oil cracking capacity and propylene olefin selectivity.

[0126] Preparation method of hydrocarbon oil conversion catalyst

[0127] In a fourth aspect, the present invention further provides a method for preparing the hydrocarbon oil conversion catalyst according to the third aspect, the method comprising:

[0128] a) mixing and slurrying the molecular sieve, the other inorganic binder, the metal source of the optional metal component, the optional medium- and macroporous inorganic oxide material, the optional clay, and water, and controlling the pH value of the slurry to be greater than 2.5 to obtain a first slurry;

[0129] b) mixing the first slurry with the phosphorus-aluminum binder to obtain a second slurry, spray drying and calcining the mixture to obtain the catalyst.

[0130] Preferably, in step a), the molecular sieve, the optional medium- and macroporous inorganic oxide material, the optional clay and water are first mixed and slurried, and then the other inorganic binder is added to the obtained mixture and mixed and slurried to obtain the first slurry, which is beneficial to further improve the catalytic performance and mechanical strength of the catalyst.

[0131] Preferably, in step a), the pH of the slurry is controlled to be greater than 2.5, preferably greater than 2.5 and less than 5. In some embodiments, the pH of the slurry is controlled to be 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, or in a range consisting of any two of the above values.

[0132] Preferably, the metal source is one or more of iron salts, cobalt salts and nickel salts, preferably FeCl3·6H2O.

[0133] According to the present invention, spray drying is a technical means well known to those skilled in the art, and the specific method is not described here in detail. Preferably, the inlet temperature of the spray drying can be 300-700°C, and the outlet temperature can be 80-200°C.

[0134] Preferably, the calcination temperature is 400-700° C., preferably 450-600° C., and the calcination time is 0.5-100 hours, preferably 0.5-10 hours.

[0135] Catalyst composition and its application

[0136] In a fifth aspect, the present invention provides a catalyst composition comprising a co-catalyst and an optional main catalyst, wherein the co-catalyst is the hydrocarbon oil conversion catalyst according to the third aspect.

[0137] According to the present invention, the main catalyst may be one commonly used by those skilled in the art in hydrocarbon oil catalytic conversion processes. Preferably, the main catalyst is a catalytic cracking catalyst.

[0138] Preferably, the weight ratio of the main catalyst to the co-catalyst is 100: 15-100: 2. In some embodiments, the weight ratio of the main catalyst to the co-catalyst can be 100: 15, 100: 14, 100: 13, 100: 12, 100: 11, 100: 10, 100: 9, 100: 8, 100: 7, 100: 6, 100: 5, 100: 4, 100: 3, 100: 2, or within a range consisting of any two of the above values.

[0139] The present invention also provides use of the hydrocarbon oil conversion catalyst according to the third aspect or the catalyst composition according to the fifth aspect in a hydrocarbon oil catalytic conversion reaction.

[0140] In a sixth aspect, the present invention provides a method for catalytic conversion of hydrocarbon oil, comprising contacting hydrocarbon oil with the hydrocarbon oil conversion catalyst according to the third aspect or the catalyst composition according to the fifth aspect to carry out a reaction.

[0141] Preferably, the reaction conditions include: a temperature of 300-700°C, preferably 400-600°C, more preferably 400-550°C; and / or a weight hourly space velocity of 4-120 hours. -1 , preferably 4-80 hours -1 , more preferably 8-16 hours -1 and / or the agent-oil weight ratio is 1-20, preferably 2-10, more preferably 4-8.

[0142] According to the present invention, the hydrocarbon oil may include but is not limited to wax oil, residual oil and recycled oil.

[0143] The hydrocarbon oil catalytic conversion method according to the present invention can be carried out using various existing catalytic cracking reactors, such as fixed bed reactors, fluidized bed reactors, riser reactors, multi-reaction zone reactors, etc.

[0144] The hydrocarbon oil catalytic conversion method provided by the present invention can improve the reactant conversion rate and target product selectivity by using the catalyst or catalyst composition according to the present invention with improved hydrothermal stability, catalytic performance and mechanical strength. For example, in some cases, it can improve gasoline, propylene and / or butene selectivity, promote heavy oil conversion, and reduce coke and oil slurry.

[0145] In order to facilitate the understanding of the present invention, the present invention lists the following embodiments, but the embodiments are only used to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0146] Example

[0147] The present application is further described below through specific embodiments, but does not constitute a limitation of the present application.

[0148] In the following examples and comparative examples, the raw materials used are as follows:

[0149] Pseudoboehmite: Shandong Aluminum Company, solid content 60 wt%;

[0150] Concentrated phosphoric acid: Beijing Chemical Plant, chemically pure, 85 wt%;

[0151] Decationized water (acidic water): pH 2.8-3.2, sodium oxide content <5 ppm (mass);

[0152] Kaolin: Catalyst-specific kaolin produced by China Kaolin Corporation, quartz sand <3.5 wt%, Al2O3 44.0 wt%, Fe2O3 0.56 wt%, Na2O 1.5 wt%, solid content 80 wt%;

[0153] Anhydrous aluminum sulfate: Sinopharm Group, analytical grade, content 99%;

[0154] Aluminum nitrate nonahydrate: Sinopharm Group, analytical grade, content 99%;

[0155] Ammonium dihydrogen phosphate: Sinopharm Group, analytical grade, content 99%;

[0156] Diamine hydrogen phosphate: Sinopharm Group, analytical grade, content 99%;

[0157] Oxalic acid: Sinopharm Group, analytical grade, content 99%;

[0158] Hydrochloric acid: Sinopharm Group / Beijing Chemical Plant, analytical grade, concentration 36-38 wt%;

[0159] Alumina sol: Sinopec Catalyst Qilu Branch, Al2O3 content is 21.5% by weight;

[0160] Kaolin: Suzhou Kaolin Company, solid content is 78% by weight.

[0161] FeCl3·6H2O: Xilong Scientific Co., Ltd., chemically pure, purity 99%.

[0162] MPZ molecular sieve: Sinopec Catalyst Qilu Branch, P2O5 content is 7.25% by weight, Fe2O3 content is 1.95% by weight, and crystallinity is 72%.

[0163] Phosphorus-containing β molecular sieve: H-β molecular sieve was saturated with 0.2 mol / L ammonium dihydrogen phosphate solution with stirring for two hours, dried at 120°C for 10 hours, and calcined at 500°C for 3 hours to obtain phosphorus-modified β molecular sieve P-β, wherein the P2O5 content was 6.23% by mass and the crystallinity was 78%.

[0164] Macroporous alumina material: Shandong Aluminum Company, solid content is 80% by weight, the pore volume of pores with a pore diameter of 2-10nm accounts for 20-40% of the total pore volume, and the pore volume of pores with a pore diameter of 10-100nm accounts for 60-80% of the total pore volume.

[0165] Sodium silicate solution: 20.65 wt% SiO2, 5.25 wt% Na2O, technical grade.

[0166] Catalytic cracking catalyst SLA-1: Sinopec Catalyst Qilu Branch.

[0167] Catalytic cracking catalyst SLA-2: Sinopec Catalyst Qilu Branch.

[0168] In the following examples, percentages and parts are by weight unless otherwise specified.

[0169] Test method:

[0170] The matrix activity and microreaction activity were measured according to Q / SH 3360 211-2007, and the matrix strength was measured according to Q / SH 3360 208-2006.

[0171] In each embodiment and comparative example, 31 P NMR was measured using a Bruker Avance III 500 MHz NMR instrument at a resonance frequency of 202.474 MHz, with H3PO4 as the calibration compound. The resonance peak spectrum was fitted and the peak area was calculated using the integration method. Each chemical shift corresponds to a chemical environment of phosphorus, and QP was used to calculate the peak area. m n To express, m represents the number of Al-OPs, n represents the number of POPs, as follows:

[0172] 0±2ppm:QP0 0 represents one phosphorus oxygen tetrahedron [PO4] or orthophosphoric acid molecule;

[0173] -7±2ppm:QP0 1 Indicates that P is connected to a phosphorus oxygen hydroxyl group, POP;

[0174] -12±2ppm:QP0 2 Indicates that P is connected to two phosphorus oxygen hydroxyl groups, POPOP;

[0175] -17±2ppm: QP1 1 Indicates 1 Al-OPOP.

[0176] The particle size of the aluminum-phosphorus sol was measured using a FEI Tecnai G2 F20 field emission transmission electron microscope (TEM) manufactured by FEI Corporation of the United States. The test conditions were as follows: the accelerating voltage of the instrument was 200 kV, and the point resolution was 0.24 nm.

[0177] 100 phosphate-aluminum sol particles were randomly selected from the TEM image and their maximum projected size was measured as the particle size. The arithmetic mean was calculated as the average particle size. The ratio of the number of particles with a size between 10-30 nm to the total number of particles was the aggregation degree.

[0178] The component contents of the aluminum-phosphorus sol were analyzed and calculated by inductively coupled plasma emission spectroscopy (ICP). The component contents of the catalyst, such as the oxide content, were determined by X-ray fluorescence (see "Analytical Methods in Petrochemical Engineering," edited by Yang Cuiding et al., Science Press, 1990).

[0179] The dynamic viscosity of the aluminum-phosphorus sol was measured using a SYD-265B petroleum product kinematic viscometer according to GB / T 265 “Determination of kinematic viscosity of petroleum products and calculation method of dynamic viscosity”.

[0180] When the prepared catalyst is used to evaluate the performance of catalytic cracking reactions, an ACE device is used for evaluation.

[0181] The RIPP standard method described in the present invention can be specifically referred to in "Petrochemical Analytical Methods" (RIPP Experimental Method), edited by Yang Cuiding et al., Science Press, 1990.

[0182] Nitrogen adsorption method (GB / T5816-1995) was used to determine the specific surface area and pore volume: Nitrogen adsorption method (RIPP 151-90, "Determination of pore volume and pore size distribution of catalysts by nitrogen adsorption capacity", see "Analytical Methods in Petrochemical Industry" (RIPP Experimental Method), edited by Yang Cuiding et al., Science Press, 1990) defines pores larger than 2 nm as mesopores. The formula for calculating mesopore porosity is (V 总孔 -V 微孔 ) / V 总孔 ×100%.

[0183] Examples 1-4 and Comparative Examples 1-3 are preparation examples of phosphate aluminum sol.

[0184] Phosphate aluminum sol Example 1

[0185] 0.56 kg of anhydrous aluminum sulfate was mixed with 0.25 kg of deionized water and 0.05 kg of oxalic acid, heated to 70°C, and slurried for 30 minutes. Then, 0.56 kg of ammonium dihydrogen phosphate was added to the slurry while stirring at 45°C. The mixture was then stirred at 45°C for 45 minutes to produce aluminum phosphate sol P-1. The material ratios and product properties are shown in Table 1.

[0186] Figure 1 shows the aluminum phosphate sol obtained in this example. 31 P NMR spectrum. As shown in Figure 1, under the same phosphorus-aluminum ratio, the product of Example 1 has a higher QP than the product of Comparative Example 1. 2 / QP0 0 .

[0187] Figure 2 shows a transmission electron microscope image of the phosphate aluminum sol obtained in this example. As can be seen from Figure 2, the colloidal particles of the phosphate aluminum sol according to the present invention are distributed in a monodisperse state.

[0188] Phosphate aluminum sol Examples 2-4

[0189] Examples 2-4 were prepared using different material ratios according to the steps of Example 1. The material ratios and product properties are shown in Table 1.

[0190] Phosphate aluminum sol comparative example 1

[0191] The aluminum phosphate sol was prepared according to Chinese patent ZL201110180891.X.

[0192] At room temperature (25°C), 0.98 kg of pseudo-boehmite (containing 0.6 kg of Al₂O₃), 0.2 kg of kaolin (0.16 kg on a dry basis), and 0.44 kg of deionized water were mixed and slurried for 30 minutes. With stirring, 2.01 kg of concentrated phosphoric acid (85% by mass) was added to the slurry at a rate of 0.03 kg of phosphoric acid / minute / kg of alumina source. The mixture was heated to 70°C and reacted at this temperature for 45 minutes to produce aluminophosphorus sol DP-1. The material ratios and product properties are shown in Table 1.

[0193] Phosphate aluminum sol comparative example 2

[0194] (1) 0.27 kg of pseudo-boehmite (dry basis) was mixed with 0.24 kg of deionized water at 20° C. and stirred for 60 minutes to obtain a pseudo-boehmite slurry;

[0195] (2) adding 0.40 kg of phosphoric acid to the pseudo-boehmite slurry for a first contact, wherein the temperature after the first contact is 23° C., and then stirring for 30 minutes;

[0196] (3) 0.134 kg of phosphoric acid was added dropwise to the mixture after the first contact for a second contact, resulting in a mixture at 32°C. The mixture was then heated to 60°C with stirring and stirred at 60°C for 90 minutes to obtain aluminophosphorus sol DP-2. The material ratios and product properties are shown in Table 1.

[0197] Phosphate aluminum sol comparative example 3

[0198] Comparative Example 3: Aluminophosphate sol was prepared according to the steps of Comparative Example 2 using different material ratios. The material ratios and product properties are shown in Table 1.

[0199] Matrix Example 1

[0200] 55 g (on a dry basis) of the phosphate aluminum sol of Example 1 was mixed with 25 g of acidified pseudo-boehmite (on a dry basis, acid-aluminum ratio (mass of hydrochloric acid / boehmite dry basis = 0.16), and solid content of the acidified pseudo-boehmite slurry was 10 wt %), and 20 g of kaolin (on a dry basis), and the mixture was beaten and stirred for 15 min, spray-dried, and calcined at 500°C for 2 h.

[0201] Matrix Examples 2-4

[0202] Matrix Examples 2-4 were prepared according to the steps of Matrix Example 1 using the aluminum phosphate sols of Examples 2-4, respectively.

[0203] Matrix Comparative Examples 1-3

[0204] Matrix Comparative Examples 1-3 were prepared according to the steps of Matrix Example 1 using the phosphate aluminum sols of Comparative Examples 1-3, respectively.

[0205] The properties of the matrices prepared in matrices examples 1-4 and comparative examples 1-3 are shown in Table 1.

[0206] Table 1.

[0207] As can be seen from Table 1, the QP0 of the aluminum phosphate sol according to the present invention is 2 / QP0 0 The phosphate-aluminum sol according to the present invention has a higher activity and lower strength than the phosphate-aluminum sol according to the comparative example, indicating a high ratio between the amount of polymerized phosphate and the amount of free phosphate, a small and uniformly distributed average particle size, and a high degree of aggregation. Compared with Comparative Examples 1 and 2, Example 1 shows that the matrix prepared from the phosphate-aluminum sol according to the present invention has higher activity and lower strength at the same or higher phosphate-aluminum ratio, indicating that the free phosphate has less impact on the matrix and better adhesion.

[0208] Examples A1-6 are preparation examples of catalysts CAT-A1 to CAT-A6.

[0209] Example A1

[0210] a) weighing P-β molecular sieve and MPZ molecular sieve, adding decationized water, and beating for 20 minutes to obtain a molecular sieve slurry; adding kaolin, aluminum sol, FeCl3·6H2O, and pseudo-boehmite to the decationized water and beating for 20 minutes, adding the molecular sieve slurry with stirring, adding hydrochloric acid to adjust the pH of the slurry to 3.0, and continuing to beat for 45 minutes to obtain a first slurry;

[0211] b) Phosphorus aluminum sol P-1 was added to the first slurry obtained in step a), and stirred for 5 minutes to obtain a second slurry. The second slurry was spray-dried to obtain microspheres, which were then calcined at 500°C for 2 hours to obtain catalyst CAT-A1. The material ratios and catalyst parameters are shown in Table 2.

[0212] Examples A2-A6

[0213] Examples A2-A6 Catalysts CAT-A2 to CAT-A6 were prepared by following the same steps as Example A1 using different material ratios. The material ratios and catalyst parameters are shown in Table 2.

[0214] Comparative Example A1

[0215] MPZ molecular sieve, kaolin, FeCl₃·6H₂O, and pseudo-boehmite were weighed, decationized water and aluminum sol were added, and the mixture was slurried for 120 minutes. Hydrochloric acid was added to adjust the pH of the slurry to 3.0, and then slurrying was continued for 45 minutes. Aluminophosphate sol DP-1 was added and stirred for 5 minutes. The resulting slurry was spray-dried to obtain microspheres, which were then calcined at 500°C for 1 hour to obtain catalyst DCAT-A1. The material ratios and catalyst parameters are shown in Table 2.

[0216] Comparative Example A2

[0217] Comparative Example A2: Catalyst DCAT-A2 was prepared by the same steps as Example A1, except that phosphate-alumina sol DP-1 was used instead of phosphate-alumina sol P-1. The material ratios and catalyst parameters are shown in Table 2.

[0218] Comparative Example A3

[0219] Comparative Example A3: Catalyst DCAT-A3 was prepared using the same procedures as Example A1, except that, as shown in Table 2, an equal amount of MPZ molecular sieve was used in place of P-β molecular sieve in step a). The material ratios and catalyst parameters are shown in Table 2.

[0220] Table 2.

[0221] Examples B1-6 are preparation examples of catalysts CAT-B1 to CAT-B6.

[0222] Example B1

[0223] a) weighing MPZ molecular sieve, adding decationized water, and beating for 20 minutes to obtain a molecular sieve slurry; adding kaolin, macroporous alumina material, aluminum sol and pseudo-boehmite to the decationized water and beating for 20 minutes, adding the molecular sieve slurry with stirring, adding hydrochloric acid to adjust the pH of the slurry to 3.0, and then continuing to beating for 45 minutes to obtain a first slurry;

[0224] b) Phosphorus aluminum sol P-1 was added to the first slurry obtained in step a), and stirred for 5 minutes to obtain a second slurry. The second slurry was spray-dried to obtain microspheres, which were then calcined at 500°C for 2 hours to obtain catalyst CAT-B1. The material ratios and catalyst parameters are shown in Table 3.

[0225] Examples B2-B6

[0226] Examples B2-B6 Catalysts CAT-B2 to CAT-B6 were prepared by following the same steps as Example B1 using different material ratios. The material ratios and catalyst parameters are shown in Table 3.

[0227] Comparative Example B1

[0228] MPZ molecular sieve, kaolin, and pseudo-boehmite were weighed, decationized water and aluminum sol were added, and the mixture was slurried for 120 minutes. Hydrochloric acid was added to adjust the pH of the slurry to 3.0, and then slurrying was continued for 45 minutes. Aluminophosphate sol DP-1 was added and stirred for 5 minutes. The resulting slurry was spray-dried to obtain microspheres, which were then calcined at 500°C for 1 hour to obtain catalyst DCAT-B1. The material ratios and catalyst parameters are shown in Table 3.

[0229] Comparative Example B2

[0230] Comparative Example B2: Catalyst DCAT-B2 was prepared by the same steps as Example B1, except that phosphate-alumina sol DP-1 was used instead of phosphate-alumina sol P-1. The material ratios and catalyst parameters are shown in Table 3.

[0231] Comparative Example B3

[0232] Comparative Example B3: Catalyst DCAT-B3 was prepared by the same steps as Example B1, except that no macroporous alumina material was added. The material ratios and catalyst parameters are shown in Table 3.

[0233] Table 3.

[0234] Examples 5-6 are preparation examples of the porous silicon-aluminum composite material of the present invention.

[0235] Example 5

[0236] Preparation of the directing agent: Weigh 245 g of sodium silicate solution (containing 20.65 wt% SiO2 and 5.25 wt% Na2O), slowly add 118 g of sodium metaaluminate solution (containing 3.22 wt% Al2O3 and 20.7 wt% Na2O) under rapid stirring, stir for 1 hour, and age at room temperature for 48 hours to obtain the directing agent.

[0237] (1) 100 g (dry basis) of kaolin was calcined at 800° C. for 2 h to obtain metakaolin, and then treated with 2 L of 3 mol / L hydrochloric acid at 85° C. for 1 h under stirring, and then filtered and washed to obtain a first mixture;

[0238] (2) under stirring, the first mixture obtained in step (1) was mixed with 415 g of a sodium silicate solution (containing 20.65 wt % SiO2 and 5.25 wt % Na2O), 60 g of a directing agent, and 98 g of a 5 wt % sodium hydroxide solution to obtain a second mixture having a composition of a weight ratio of 0.69 Na2O:Al2O3:3.27SiO2:9.78H2O;

[0239] (3) The second mixture was heated to 92°C and stirred at constant temperature for hydrothermal crystallization for 20 hours. After the crystallization was completed, the crystallization tank was quenched, filtered, and washed with water until the pH value of the washing liquid was less than 10. The mixture was then dried at 120°C for 2 hours to obtain a porous silicon-aluminum composite material Y1. The properties of the composite material are shown in Table 4.

[0240] Example 6

[0241] (1) Weighing 100 g (dry basis) of kaolin and calcining it at 900° C. for 2 h to obtain metakaolin, then treating it with 2 L of 3 mol / L hydrochloric acid at 90° C. for 1.5 h with stirring, and then filtering and washing to obtain a first mixture;

[0242] (2) The first mixture obtained in step (1) was mixed with 450 g of a sodium silicate solution (containing 20.65 wt % SiO2 and 5.25 wt % Na2O), 60 g of a directing agent (the same directing agent as used in Example 5), and 120 g of a 5 wt % sodium hydroxide solution under stirring to obtain a second mixture having a composition of a weight ratio of 0.75 Na2O:Al2O3:3.43SiO2:10.81H2O;

[0243] (3) The second mixture was heated to 95°C and stirred at constant temperature for hydrothermal crystallization for 28 hours. After the crystallization was completed, the crystallization tank was quenched, filtered, and washed with water until the pH value of the washing liquid was less than 10. The washing liquid was then dried at 120°C for 2 hours to obtain a porous silicon-aluminum composite material Y2. The properties of the composite material are shown in Table 4.

[0244] Table 4.

[0245] ※ Medium and macroporosity: the ratio of the volume of medium and macropores with a pore diameter of 2-50 nm to the total pore volume.

[0246] Examples C1-6 are preparation examples of catalysts CAT-C1 to CAT-C6.

[0247] Example C1

[0248] a) weighing MPZ molecular sieve, adding decationized water, and beating for 20 minutes to obtain a molecular sieve slurry; adding kaolin, porous silica-alumina composite material, aluminum sol and pseudo-boehmite to the decationized water and beating for 20 minutes, adding the molecular sieve slurry under stirring, adding hydrochloric acid to adjust the pH of the slurry to 3.0, and then continuing to beat for 45 minutes to obtain a first slurry;

[0249] b) Phosphorus aluminum sol P-1 was added to the first slurry obtained in step a), and stirred for 5 minutes to obtain a second slurry. The second slurry was spray-dried to obtain microspheres, which were then calcined at 500°C for 2 hours to obtain catalyst CAT-C1. The material ratios and catalyst parameters are shown in Table 5.

[0250] Examples C2-C6

[0251] Examples C2-C6 Catalysts CAT-C2 to CAT-C6 were prepared by following the same steps as Example C1 using different material ratios. The material ratios and catalyst parameters are shown in Table 5.

[0252] Comparative Example C1

[0253] MPZ molecular sieve, kaolin, and diatomite were weighed, decationized water and aluminum sol were added, and the mixture was slurried for 120 minutes. Hydrochloric acid was added to adjust the pH of the slurry to 3.0, and then slurrying was continued for 45 minutes. Aluminophosphate sol DP-1 was added and stirred for 5 minutes. The resulting slurry was spray-dried to obtain microspheres, which were then calcined at 500°C for 1 hour to obtain DCAT-C1. The material ratios and catalyst parameters are shown in Table 5.

[0254] Comparative Example C2

[0255] Comparative Example C2: Catalyst DCAT-C2 was prepared using the same procedures as Example C1, except that phosphate-alumina sol DP-1 was used instead of phosphate-alumina sol P-1. The material ratios and catalyst parameters are shown in Table 5.

[0256] Comparative Example C3

[0257] Comparative Example C3: Catalyst DCAT-C3 was prepared by the same steps as Example C1, except that the porous silicon-aluminum composite material was not added. The material ratios and catalyst parameters are shown in Table 5.

[0258] Table 5.

[0259] The following test examples take a fixed fluidized bed reactor as an example to illustrate the catalytic cracking reaction effect of the catalyst according to the present invention.

[0260] Test Case A

[0261] Catalytic cracking main catalyst SLA-1, along with 30g of CAT-A1-6 and DCAT-A1-3, was aged at 800°C in a 100% steam atmosphere for 17 hours. Different amounts of the aged catalysts were mixed with SLA-1 (properties shown in Table 6). The catalyst mixture was loaded into the reactor of a small-scale fixed fluidized bed reactor and subjected to catalytic cracking of the feedstock oil shown in Table 7. Table 8 shows the reaction conditions and evaluation results.

[0262] Table 6. Properties of Catalytic Cracking Main Catalyst SLA-1

[0263] Table 7. Properties of the evaluated feedstock oil

[0264] Table 8. Evaluation results of CAT-A1 to 6 and DCAT-A1 to 3

[0265] As can be seen from Table 8, compared with the comparative catalyst, the catalyst according to the present invention can effectively increase the content of propylene and butene in catalytic cracking liquefied gas, improve the olefin content in LPG, reduce the sum of the yields of diesel and slurry oil, and increase the sum of the yields of gasoline and LPG.

[0266] Test Case B

[0267] Catalytic cracking main catalyst SLA-2, along with 30g of CAT-B1-6 and DCAT-B1-3, was aged at 800°C in a 100% steam atmosphere for 17 hours. Different amounts of the aged catalysts were mixed with SLA-2 (properties shown in Table 9). The catalyst mixture was loaded into the reactor of a small-scale fixed fluidized bed reactor and subjected to catalytic cracking of the feedstock oil shown in Table 10. Table 11 shows the reaction conditions and results.

[0268] Table 9. Properties of Catalytic Cracking Main Catalyst SLA-2

[0269] Table 10. Properties of the evaluated feedstock oil

[0270] Table 11. Evaluation results of CAT-B1 to 6 and DCAT-B1 to 3

[0271] As can be seen from Table 11, compared with the comparative example catalyst, the catalyst according to the present invention can effectively increase the catalytic cracking liquefied gas and propylene yields, and the propylene concentration in the liquefied gas is higher, the total liquid yield is high, the yields of slurry oil and coke are low, and the heavy oil cracking capacity is significantly improved.

[0272] Test Case C

[0273] Catalytic cracking main catalyst SLA-2, along with 30g of CAT-C1-6 and DCAT-C1-3, was aged at 800°C in a 100% steam atmosphere for 17 hours. Different amounts of the aged catalysts were mixed with SLA-2 (properties shown in Table 9). The catalyst mixture was loaded into the reactor of a small-scale fixed fluidized bed reactor and subjected to catalytic cracking of the feedstock oil shown in Table 10. Table 12 shows the reaction conditions and results.

[0274] Table 12. Evaluation results of CAT-C1 to 6 and DCAT-C1 to 3

[0275] As can be seen from Table 12, compared with the comparative catalyst, the catalyst composition according to the present invention can increase the yield of propylene, and has a high light oil yield (i.e., the total yield of gasoline and liquefied gas), a high total liquid yield and conversion rate, a lower coke yield, and significantly improves the heavy oil cracking capacity and propylene selectivity.

[0276] The preferred embodiments of the present disclosure are described in detail above in conjunction with the accompanying drawings. However, the present disclosure is not limited to the specific details of the above embodiments. Within the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure, and these simple modifications all fall within the scope of protection of the present disclosure.

[0277] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, the present disclosure will not further describe various possible combinations.

[0278] In addition, the various embodiments of the present disclosure may be arbitrarily combined, and as long as they do not violate the concept of the present disclosure, they should also be regarded as the contents disclosed by the present disclosure.

Claims

1. An aluminophosphate sol, wherein this aluminophosphate sol contains aluminum, phosphorus and a stabilizer and has a P / Al mass ratio of 1.6-6:1; wherein the aluminophosphate sol exhibits an NMR spectrum 31 P, where the peak area of ​​the resonance signal at a chemical shift of -12±2 ppm is designated as QP0 2 , and the peak area of ​​the resonance signal at a chemical shift of 0±2 ppm is designated as QP0 0 , the ratio QP0 2 / QP0 0 is 1.5-5, and the aluminophosphate sol has an average colloidal particle size of 10-30 nm.

2. An aluminophosphate sol according to claim 1, wherein, relative to the total mass of the aluminophosphate sol, the aluminophosphate sol contains aluminum in an amount equal to -15 wt.%, calculated as Al2O33, phosphorus in an amount equal to 15-40 wt.%, calculated as P2O5, and a stabilizer in an amount equal to 0.1-10 wt.%; preferably, the aluminophosphate sol contains aluminum in an amount equal to -12 wt.%, calculated as Al2O33, phosphorus in an amount equal to 15-35 wt.%, calculated as P2O5, and a stabilizer in an amount equal to 0.5-5 wt.%; and / or the pH value of the aluminophosphate sol is in the range of 0.5-2.5; and / or the solid content of the aluminophosphate sol is in the range of 15-50 wt.%; and / or the dynamic viscosity of the aluminophosphate sol is in the range of 10-50 cP.

3. An aluminophosphate sol according to claim 1 or 2, wherein the stabilizer is a weakly acidic organic acid, which is preferably selected as at least one of the following acids: glycolic acid, oxalic acid, acetic acid, malonic acid, malic acid, tartaric acid, succinic acid, adipic acid, maleic acid, itaconic acid and citric acid, preferably oxalic acid, acetic acid, citric acid or a combination thereof; and / or the molar ratio of organic acid anions in the stabilizer and aluminum is in the range of 0.05-0.5:

1.

4. A method for producing an aluminophosphate sol according to any one of paragraphs 1-3, including 1) in the process of stirring at a temperature of 50°C-95°C, stirring the initial aluminum salt, decationized water and stabilizer to obtain a suspension, so that a solution of aluminum oxide precursor is obtained; 2) during the stirring process at a temperature of 25-70°C, adding phosphate to the solution of the aluminum oxide precursor at a P / Al weight ratio of 1.6-6:1 to carry out the reaction so that an aluminophosphate sol is obtained.

5. The method according to paragraph 4, wherein one or more salts representing aluminum nitrate, aluminum sulfate and aluminum chloride are selected as the initial aluminum salt; and / or the pH value of the aluminum oxide precursor solution is in the range of 0.5-3.0; and / or the solid content of the aluminum oxide precursor solution is in the range of 5-40 wt.%; and / or the phosphate is ammonium hydrogen phosphate and / or ammonium dihydrogen phosphate; and / or in step (1) the duration of stirring of the suspension is in the range of 10-50 min; in step (2) the duration of the reaction is in the range of 10-60 min.

6. A catalyst for converting hydrocarbon petroleum products, wherein the catalyst comprises a molecular sieve, an aluminophosphate binder material, one or more additional inorganic binders that are not an aluminophosphate binder material, an optional metal component, an optional meso-macroporous inorganic oxide material, and an optional clay, wherein the source of the aluminophosphate binder material is an aluminophosphate sol according to any one of claims 1-3 or an aluminophosphate sol made by the method according to any one of claims 4-5.

7. The catalyst of claim 6, wherein, based on the dry weight of the catalyst, the catalyst comprises a molecular sieve in an amount of 25-75 wt.% and preferably 30-65 wt.%, a metal component in an amount of 0.5-8 wt.% and preferably 0.8-6 wt.%, calculated as the metal oxide, an aluminophosphate binder in an amount of 3-40 wt.% and preferably 8-32 wt.%, calculated as the oxide, one or more additional inorganic binders in an amount of 1-25 wt.% and preferably 2-20 wt.%, calculated as the oxide, and clay in an amount of 0-30 wt.% and preferably 1-25 wt.%; and / or wherein the molecular sieve comprises a molecular sieve of the MFI type and a molecular sieve of the BEA type, the molecular sieve comprises a first phosphate component, the aluminophosphate binder material comprises a second phosphate component, and the total content of the first phosphate component and the second phosphate component in the catalyst, in terms of P2O5, is in the range of 10-35 wt.%; and / or the catalyst has a pore volume, determined by the Barrett-Joyner-Halenda (BJH) method, of more than 0.12 ml / g; and / or wherein at least one of the metals of group VIII is selected as the metal for the metal component, preferably one or more metals representing Fe, Co and Ni.

8. The catalyst of claim 6, wherein the meso-macroporous inorganic oxide material is a macroporous alumina material, and the molecular sieve is an MFI type molecular sieve; Based on the dry weight of the catalyst, the catalyst comprises a molecular sieve of the MFI type in an amount of 10-75 wt.% and preferably 15-65 wt.%, a macroporous alumina material in an amount of 1-30 wt.% and preferably 2-25 wt.%, an aluminophosphate binder in an amount of 3-35 wt.% and preferably 8-32 wt.%, based on the oxide, one or more additional inorganic binders in an amount of 1-20 wt.% and preferably 2-20 wt.%, based on the oxide, and clay in an amount of 0-60 wt.% and preferably 1-25 wt.%; and / or the macroporous alumina material has a structure with a bimodal pore size distribution, wherein the pore volume occupied by pores having a pore size of 2-10 nm is 20-40% of the total pore volume, and the pore volume occupied by pores having a pore size of 10-100 nm is 60-80% of the total pore volume; and / or one or more of the following molecular sieves are selected as the MFI type molecular sieve: an MFI type molecular sieve in hydrogen form, a phosphorus-containing MFI type molecular sieve, and a transition metal-containing MFI type molecular sieve.

9. The catalyst of claim 6, wherein the meso-macroporous inorganic oxide material is a porous aluminosilicate composite material, and the molecular sieve is an MFI type molecular sieve; based on the dry weight of the catalyst, the catalyst comprises a molecular sieve of the MFI type in an amount of 10-75 wt.% and preferably 15-65 wt.%, a porous aluminosilicate composite material in an amount of 1-30 wt.% and preferably 2-25 wt.%, an aluminophosphate binder in an amount of 3-35 wt.% and preferably 8-32 wt.%, based on the oxide, one or more additional inorganic binders in an amount of 1-20 wt.% and preferably 2-20 wt.%, based on the oxide, and clay in an amount of 0-60 wt.% and preferably 1-25 wt.%; and / or porous aluminosilicate composite material has a mass composition of (0.01-1)Na2O:Al2O3:(2-5)SiO2, a specific surface area of ​​300-600 m 2 / g, total pore volume of 0.15-0.4 ml / g, and the pore volume of meso-macropores with a pore size of 2-50 nm, which is 20-40% of the total pore volume; and / or one or more of the following molecular sieves are selected as the MFI type molecular sieve: a hydrogen form MFI type molecular sieve, a phosphorus-containing MFI type molecular sieve, and a transition metal-containing MFI type molecular sieve.

10. The catalyst according to any one of paragraphs 6-9, in which one or more of the following materials are selected as one or more additional inorganic binder materials: pseudoboehmite, acidified pseudoboehmite, alumina sol, aluminosilicate sol and silicic oxide sol; and / or one or more of the following materials are selected as clay: kaolin, sepiolite, attapulgite, rectorite, montmorillonite and diatomite.

11. A method for producing a catalyst according to any one of paragraphs 6-10, wherein the method includes a) mixing a molecular sieve, one or more additional inorganic binders, a metal source for an optional metal component, an optional meso-macroporous inorganic oxide material, an optional clay, and water to form a slurry, adjusting the pH of the slurry to a level greater than 2.5 such that a first slurry is formed; b) mixing the first suspension with an aluminophosphate sol to form a second suspension, and then spray drying and calcining to form a catalyst.

12. The method according to claim 11, wherein the metal source is a soluble metal salt, which is selected as at least one of the salts of the metals of group VIII, preferably one or more salts of iron salts, cobalt salts and nickel salts, preferably FeCl3·6H2O; and / or spray drying is carried out at an inlet temperature of 300-700°C and an outlet temperature of 80-200°C; and / or calcination is carried out at a temperature of 400-700°C for a period of time of 0.5-100 hours.

13. A catalytic composition, wherein the catalytic composition comprises an auxiliary catalyst and an optional pre-catalyst, wherein the auxiliary catalyst is a catalyst according to any one of claims 6 to 10, and the optional pre-catalyst is preferably a catalytic cracking catalyst.

14. A method for the catalytic conversion of hydrocarbon petroleum products, comprising bringing the hydrocarbon petroleum product into contact with a catalyst according to any one of paragraphs 6-10 or with a catalytic composition according to paragraph 13 to carry out a reaction.

15. The method according to claim 14, wherein the reaction is carried out under the following conditions: the temperature is 300-700°C, the mass hourly space velocity is 4-120 h -1 , and the mass ratio of catalyst to petroleum product is 1-20.