Highly stable catalytic cracking composition and method for its preparation, catalytic cracking aid and use

Abstract

The present application relates to the field of oil refining catalyst, disclose a kind of high stability catalytic cracking composition and its preparation method, catalytic cracking aid and application.The catalytic cracking composition includes catalytic cracking aid and catalytic cracking catalyst;With dry basis weight as benchmark, the catalytic cracking aid includes: 5-50 weight% clay, 5-40 weight% silicon species with SiO2, 30-80 weight% aluminum species with Al2O3, 0.5-15 weight% magnesium with oxide and 0.5-10 weight% active adjustment element with oxide;With low temperature nitrogen adsorption method determination, the total pore volume of the catalytic cracking aid is not less than 0.5mL / g, and the pore volume of the pore with a pore diameter of 10-100nm accounts for more than 80% of the total pore volume.The catalytic cracking composition is used in heavy oil catalytic cracking, greatly reduces the coke selectivity, and increases the light oil yield.

Description

Technical Field

[0001] This invention relates to the field of refining catalysts, specifically to a highly stable catalytic cracking composition, its preparation method, catalytic cracking aid, and its applications. Background Technology

[0002] The oil refining industry is facing significant challenges, including scarce and degraded petroleum resources and the need for low-carbon emissions. Catalytic cracking, a key process, can convert heavy oil and residual oil into high-value products such as liquefied petroleum gas (LPG), gasoline, and diesel. These heavy feedstocks are characterized by large molecular size, high density, high carbon residue, and high heavy metal content, placing more stringent requirements on the catalysts and additives used in catalytic cracking. Catalytic cracking additives are the most flexible, rapid, and effective means to promote the deep conversion of heavy feedstocks, increase high-value-added products, and reduce coke yield. In particular, the development of heavy oil catalytic cracking additives places greater emphasis on adjusting and optimizing the matrix properties. By altering the acidity and pore structure of the matrix, the diffusion efficiency of reactants and products is enhanced, thereby more effectively promoting the cracking capacity of large heavy oil molecules.

[0003] US5045519A discloses a method for preparing a catalyst support containing aluminosilicates, which involves mixing an aluminum-containing compound and a silica compound, wherein the aluminum-containing compound is obtained by hydrolysis of a C2-C20 alcohol-based aluminum salt, and simultaneously or subsequently adding silica purified by an ion exchanger, followed by drying and calcination to obtain the catalyst. Based on this, WO9712011A1 discloses a bottom oil cracking aid (BCA) without molecular sieves, containing 5-30 wt% of the aluminosilicate compound prepared by US5045519A, 15-30 wt% of acidifiable alumina, 5-25 wt% of non-acidifiable alumina or a phosphorus-containing compound, 30-60 wt% of clay, and may also contain less than 5 wt% of inert silicon species and less than 2 wt% of a metal trapping agent. However, the aluminosilicate compound used in this aid has a high preparation cost.

[0004] CN102974337A discloses a catalytic cracking additive and its preparation method. This additive contains mesoporous silica-alumina material, a metal trapping agent, and clay and / or heat-resistant inorganic oxides. The mesoporous silica-alumina material preferably has a pseudo-boehmite crystal phase structure, with an oxide weight ratio of (0-0.2)Na₂O·(40-90)Al₂O₃·(10-60)SiO₂. When applied to heavy oil catalytic cracking, it exhibits strong heavy oil cracking capability, higher light oil yield, and better coke selectivity. However, there is still room for improvement in the hydrothermal stability and pore structure of this additive.

[0005] CN108786782A discloses a catalytic cracking aid for reducing coke yield and its preparation method. This catalytic cracking aid, based on a catalyst mass composition of 100 parts, comprises 5-25 parts of rare earth-containing macroporous silica-alumina material, 15-42 parts of alumina material, 1-10 parts of heavy metal scavenger, and 30-60 parts of clay. The rare earth-containing macroporous silica-alumina material, based on oxide weight, has the following anhydrous chemical formula: (0-0.3)Na₂O:(2-16)Al₂O₃:(75-92)SiO₂:(2-10)RE₂O₃; its pore volume is 0.8-2 mL / g, and its specific surface area is 150-350 m² / g. 2 With a most probable pore size of 30-100 nm and a B / L acid ratio of 0.6-1.9, this additive exhibits good reactivity in improving the coke selectivity of the catalyst. However, this catalytic cracking additive introduces a significant amount of clay, which can cause blockage of the existing medium and large hollow structures.

[0006] Therefore, there is an urgent need to develop a highly stable catalytic cracking composition. Summary of the Invention

[0007] The purpose of this invention is to overcome the problems of poor stability and low alkali center content in existing catalytic cracking additives, and to provide a highly stable catalytic cracking composition, its preparation method, catalytic cracking additive, and its application. The catalytic cracking composition of this invention includes specific catalytic cracking additives with high alkali center content and high microreactivity retention. When used in heavy oil catalytic cracking, this composition significantly reduces coke selectivity and increases light oil yield.

[0008] To achieve the above objectives, a first aspect of the present invention provides a catalytic cracking composition comprising a catalytic cracking promoter and a catalytic cracking catalyst; the catalytic cracking promoter, based on a dry weight basis, comprises: 5-50 wt% clay, 5-40 wt% silicon species (calculated as SiO2), 30-80 wt% aluminum species (calculated as Al2O3), 0.5-15 wt% magnesium (calculated as oxides), and 0.5-10 wt% an activity regulating element (calculated as oxides); the SiO2 / Al2O3 molar ratio of the silicon species and aluminum species is 0.05-2; the activity regulating element is selected from at least one of P, B, Group IIIB elements, and Group IVB elements.

[0009] The content of base centers in the catalyst was determined to be 0.05-0.5 mmol / g by CO2-TPD method;

[0010] The microreaction activity retention of the catalytic cracking aid before and after treatment at 800℃ and 100% steam for 17 hours is not less than 60%.

[0011] The total pore volume of the catalytic cracking aid, as determined by the low-temperature nitrogen adsorption method, is not less than 0.5 mL / g, wherein the pore volume of pores with a diameter of 10-100 nm accounts for more than 80% of the total pore volume.

[0012] A second aspect of the present invention provides a method for preparing a catalytic cracking composition, the method comprising the following steps:

[0013] (1) In the presence of a solvent, clay, silicon source, aluminum source and magnesium source are mixed to obtain silicon-aluminum-magnesium mixed gel;

[0014] (2) Adjust the pH of the silicon-aluminum-magnesium mixed gel to 9-12, and after aging treatment, spray dry to form microspheres of the additive;

[0015] (3) The additive microspheres are subjected to ammonium exchange and then loaded with activity regulating elements to obtain a catalytic cracking additive;

[0016] (4) The catalytic cracking aid and the catalytic cracking catalyst are brought into contact to obtain a catalytic cracking composition;

[0017] The amount of clay, silicon source, aluminum source, magnesium source, and activity regulating element source added is such that, based on dry weight, the catalytic cracking promoter comprises: 5-50 wt% clay, 5-40 wt% silicon species (SiO2), 30-80 wt% aluminum species (Al2O3), 0.5-15 wt% magnesium (oxide), and 0.5-10 wt% activity regulating element (oxide); the SiO2 / Al2O3 molar ratio of the silicon and aluminum species is 0.05-2; and the activity regulating element is selected from at least one of P, B, Group IIIB, and Group IVB elements.

[0018] A third aspect of the present invention provides a catalytic cracking promoter, which, based on a dry weight basis, comprises 5-50 wt% clay, 5-40 wt% silicon species (calculated as SiO2), 30-80 wt% aluminum species (calculated as Al2O3), 0.5-15 wt% magnesium (calculated as oxides), and 0.5-10 wt% activity-regulating elements (calculated as oxides); the SiO2 / Al2O3 molar ratio of the silicon and aluminum species is 0.05-2; and the activity-regulating element is selected from at least one of P, B, Group IIIB, and Group IVB elements.

[0019] The content of base centers in the catalyst was determined to be 0.05-0.5 mmol / g by CO2-TPD method;

[0020] The microreaction activity retention of the catalytic cracking aid before and after treatment at 800℃ and 100% steam for 17 hours is not less than 60%.

[0021] The total pore volume of the catalytic cracking aid, as determined by the low-temperature nitrogen adsorption method, is not less than 0.5 mL / g, wherein the pore volume of pores with a diameter of 10-100 nm accounts for more than 80% of the total pore volume.

[0022] The fourth aspect of the present invention provides a catalytic cracking composition as described in the first aspect above or a catalytic cracking composition prepared by the method described in the second aspect above, or the application of the catalytic cracking aid as described in the third aspect above in heavy oil catalytic cracking.

[0023] Through the above technical solution, the present invention has the following beneficial effects:

[0024] The catalytic cracking composition provided by this invention contains a specific amount of magnesium and specific amounts and types of activity-regulating elements in the additive. After treatment at 800°C and 100% steam for 17 hours, it exhibits high micro-reaction activity retention, abundant macroporous structure and suitable pore distribution, low SiO2 / Al2O3 molar ratio, and high alkali center content. The catalytic cracking composition has excellent hydrothermal stability and high activity stability. It is particularly suitable for the efficient conversion of inferior oils in heavy oil catalytic cracking processes, thereby increasing the yield of light oil while reducing slurry oil yield and coke selectivity. Detailed Implementation

[0025] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0026] The first aspect of this invention provides a catalytic cracking composition comprising a catalytic cracking promoter and a catalytic cracking catalyst; the catalytic cracking promoter, based on a dry weight basis, comprises: 5-50 wt% clay, 5-40 wt% silicon species (calculated as SiO2), 30-80 wt% aluminum species (calculated as Al2O3), 0.5-15 wt% magnesium (calculated as oxides), and 0.5-10 wt% an activity regulating element (calculated as oxides); the SiO2 / Al2O3 molar ratio of the silicon species and aluminum species is 0.05-2; the activity regulating element is selected from at least one of P, B, Group IIIB elements, and Group IVB elements.

[0027] The content of base centers in the catalyst was determined to be 0.05-0.5 mmol / g by CO2-TPD method;

[0028] The microreaction activity retention of the catalytic cracking aid before and after treatment at 800℃ and 100% steam for 17 hours is not less than 60%.

[0029] The total pore volume of the catalytic cracking aid, as determined by the low-temperature nitrogen adsorption method, is not less than 0.5 mL / g, wherein the pore volume of pores with a diameter of 10-100 nm accounts for more than 80% of the total pore volume.

[0030] In this invention, the catalytic cracking composition contains a specific amount of magnesium and specific amounts and types of activity-regulating elements. After treatment at 800°C and 100% steam for 17 hours, it exhibits high micro-reaction activity retention, abundant macroporous structure and suitable pore distribution, low SiO2 / Al2O3 molar ratio, and specific alkali center content. The catalytic cracking composition has excellent hydrothermal stability and high activity stability. When used in heavy oil catalytic cracking, it can increase the yield of light oil while reducing the oil slurry yield and coke selectivity.

[0031] In some embodiments of the present invention, preferably, the alkali center content of the catalyst, as determined by the CO2-TPD method, is 0.1-0.4 mmol / g. For example, it can be 0.1 mmol / g, 0.15 mmol / g, 0.2 mmol / g, 0.25 mmol / g, 0.3 mmol / g, 0.35 mmol / g, 0.4 mmol / g, or any value within the range of any two of the above values. In the present invention, using a catalytic cracking aid with the above-mentioned preferred alkali center content in combination with a catalytic cracking catalyst is more beneficial for improving the selectivity of light oil and reducing coke yield.

[0032] In some embodiments of the present invention, preferably, the microreaction activity retention of the catalytic cracking aid after treatment at 800°C and 100% steam for 17 hours is 65%-85%, for example, it can be 65%, 68%, 70%, 73%, 75%, 78%, 80%, 83%, 85%, or any value within the range of any two of the above values. In the present invention, the catalytic cracking aid exhibits high microreaction activity after treatment under the above extreme conditions for 17 hours, and the preferred aid has superior activity stability and better catalytic effect.

[0033] In this invention, the retention rate of micro-reaction activity of the additive before and after treatment at 800℃ and 100% steam for 17 hours is equal to the micro-reaction activity of the additive after treatment at 800℃ and 100% steam for 17 hours / the micro-reaction activity of the fresh additive * 100%. In this invention, the fresh catalyst is first tested for micro-reaction activity, then aged at 800℃ and 100% steam for 17 hours in a fixed-bed aging device, followed by another micro-reaction activity test. The micro-reaction activity test method includes: evaluating the light oil micro-reaction activity of the sample using the standard method of RIPP92-90 (see "Analytical Methods in Petrochemical Industry" (RIPP Test Methods), edited by Yang Cuiding et al., Science Press, 1990). The catalyst loading is 5.0 g, the reaction temperature is 460℃, the feed oil is straight-run light diesel oil with a distillation range of 235-337℃, and the product composition is analyzed by gas chromatography. The light oil micro-reaction activity is calculated based on the product composition.

[0034] In some embodiments of the present invention, preferably, the total pore volume of the catalytic cracking aid is 0.6-1.5 mL / g, as determined by low-temperature nitrogen adsorption, wherein the pore volume with a diameter of 10-100 nm accounts for 85%-99% of the total pore volume. In the present invention, the total pore volume of the aid can be 0.6 mL / g, 0.8 mL / g, 1 mL / g, 1.2 mL / g, 1.4 mL / g, 1.5 mL / g, or any value within any range of any two of the above values. In the present invention, the pore volume with a diameter of 10-100 nm can account for 85%, 87%, 89%, 91%, 93%, 95%, 97%, 99% of the total pore volume, or any value within any range of any two of the above values. In the present invention, the catalytic cracking aid has a large pore volume and suitable pore distribution, thereby enabling the catalytic cracking composition to have a high light oil yield and effectively reduce slurry oil yield and coke selectivity.

[0035] In some embodiments of the present invention, preferably, based on the dry weight of the catalytic cracking promoter, the catalytic cracking promoter comprises: 10-45 wt% clay, 8-35 wt% silicon species (calculated as SiO2), 35-75 wt% aluminum species (calculated as Al2O3), 1-10 wt% magnesium (calculated as oxides), and 1-8 wt% activity-regulating elements (calculated as oxides). Using the above-preferred amounts of each component is beneficial for fully leveraging the synergistic effect of each component and improving the catalytic performance of the catalytic cracking composition.

[0036] In some embodiments of the present invention, preferably, the SiO2 / Al2O3 molar ratio of the silicon and aluminum species is 0.2-1.5, for example, it can be 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.5, or any value within the range of any two of the above values. Using the above-mentioned preferred SiO2 / Al2O3 molar ratio is more conducive to forming a larger pore volume and suitable pore distribution in the catalytic cracking aid, which is beneficial to further improving the activity and stability of the catalytic cracking composition, achieving efficient heavy oil conversion and low coking.

[0037] In this invention, the total amount of silicon and aluminum species has a wide selection range, as long as the respective amounts of silicon and aluminum species in the catalytic cracking promoter meet the aforementioned range. Preferably, the total amount of silicon and aluminum species, calculated as oxides, is 45-90% by weight, for example, it can be 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, or any value within any range of two of the above values, preferably 50-80% by weight. Using the above-mentioned preferred amounts is beneficial for further endowing the catalytic cracking promoter with a rich macroporous structure and excellent activity stability.

[0038] In some embodiments of the present invention, preferably, the aluminum species exist in the form of aluminum silicate. More preferably, the aluminum species exist primarily in the form of aluminum silicate. This is beneficial for further improving the activity stability and hydrothermal stability of the catalytic cracking additive, and for further optimizing the distribution of active centers, thereby improving the selectivity of light oil products and reducing slurry oil yield and coke selectivity. In the present invention, the presence of aluminum silicate can be confirmed by XRD characterization (an aluminum silicate diffraction peak appears at 22.3 degrees).

[0039] In this invention, the types of activity regulating elements are selected from a wide range. Preferably, the activity regulating element is selected from at least one of P, B, La, Ce, Y, Zr, and Ti, and more preferably from at least one of P, B, La, and Ce. Using the above-mentioned preferred activity regulating elements is more conducive to their synergistic effect with magnesium, thereby improving the efficiency of catalytic cracking reaction, increasing the selectivity of light oil products, and reducing slurry oil yield and coke selectivity.

[0040] In this invention, the type of clay is not particularly limited, and various commonly used clays can be used. Preferably, the clay is selected from at least one of kaolin, bentonite, montmorillonite, sepiolite, diatomaceous earth, tartaric acid, attapulgite, and halloysite, with kaolin being the most preferred. Using the above-mentioned preferred clay is beneficial for further optimizing the pore structure and pore distribution of the catalytic cracking additive and improving its wear resistance.

[0041] In this invention, the specific surface area of ​​the catalytic cracking promoter has a wide selection range. Preferably, the specific surface area of ​​the catalytic cracking promoter is 150-350 m². 2 / g, for example, can be 150m 2 / g、200m 2 / g、250m 2 / g、300m 2 / g, 350m 2 / g, and any value within the range of any two of the above values, preferably 180-300m 2 / g.

[0042] In this invention, the most probable pore size of the catalytic cracking promoter has a wide selection range. Preferably, the most probable pore size of the catalytic cracking promoter is 10-40 nm, and more preferably 15-35 nm.

[0043] In this invention, the method for determining pore volume using the low-temperature nitrogen adsorption method includes: using a Micromeritics ASAP 2405N V1.01 automated adsorption instrument, low-temperature static nitrogen adsorption capacity method, with the sample at 1.33 × 10⁻⁶ pore volume. -2 The sample was degassed under vacuum at 300℃ for 4 hours using N2 as the adsorption medium, and the adsorption-desorption isotherm was measured at 77.4K. The specific surface area of ​​the sample was calculated using the BET formula, and the volume of N2 adsorbed by the sample at a relative pressure p / p0 = 0.98 was measured and converted to liquid nitrogen volume, i.e., the total pore volume. Pore distribution was determined according to SH / 0572 (ASTM D 4641) standard, and the pore volume of the 10-100 nm pore portion of the sample was calculated using the BJH desorption branch.

[0044] In some embodiments of the present invention, preferably, the wear index of the catalytic cracking aid is not higher than 2.6 m% / h, and more preferably 0.5-2.5 m% / h. In the present invention, the catalytic cracking aid has excellent wear resistance, which is beneficial for maintaining good catalytic activity, thereby further improving the catalytic effect of the catalytic cracking composition.

[0045] In this invention, the mass ratio of the catalytic cracking catalyst to the catalytic cracking promoter has a wide selection range. Preferably, the mass ratio of the catalytic cracking catalyst to the catalytic cracking promoter is 1:0.05-0.8, more preferably 1:0.15-0.6, for example, it can be 1:0.15, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, or any value within the range of any two of the above values. Using the above-preferred mass ratio is more conducive to improving the activity and stability of the catalytic cracking composition, thereby further promoting heavy oil conversion, improving light oil selectivity, and reducing coke yield.

[0046] In this invention, the type of catalytic cracking catalyst has a wide selection range and can be various catalysts conventionally used in the art for heavy oil catalytic cracking. Preferably, based on the dry weight of the catalytic cracking catalyst, the catalytic cracking catalyst comprises: 0.1-10 wt% rare earth metal elements as oxides, 40-60 wt% aluminum species as Al2O3, and 20-50 wt% silicon species as SiO2. More preferably, based on the dry weight of the catalytic cracking catalyst, the catalytic cracking catalyst comprises: 0.5-6 wt% rare earth metal elements as oxides, 45-58 wt% aluminum species as Al2O3, 25-45 wt% silicon species as SiO2, and 0.05-0.3 wt% sodium as oxides. Using the above-preferred catalytic cracking catalyst is more advantageous for combination with catalytic cracking additives, significantly promoting heavy oil conversion, improving light oil selectivity, and reducing coke yield.

[0047] In this invention, the type of active component is not particularly limited and can be any of the active components commonly used in the art, for example, it can be selected from at least one of Y-type molecular sieves, β-molecular sieves, and ZSM-5 molecular sieves. In this invention, the catalytic cracking aid may also include other commonly used matrices; for example, the commonly used matrices may be selected from at least one of silica and its precursors, alumina and its precursors, and magnesium oxide and its precursors.

[0048] A second aspect of the present invention provides a method for preparing a catalytic cracking composition, the method comprising the following steps:

[0049] (1) In the presence of a solvent, clay, silicon source, aluminum source and magnesium source are mixed to obtain silicon-aluminum-magnesium mixed gel;

[0050] (2) Adjust the pH of the silicon-aluminum-magnesium mixed gel to 9-12, and after aging treatment, spray dry to form microspheres of the additive;

[0051] (3) The additive microspheres are subjected to ammonium exchange and then loaded with activity regulating elements to obtain a catalytic cracking additive;

[0052] (4) The catalytic cracking aid and the catalytic cracking catalyst are brought into contact to obtain a catalytic cracking composition;

[0053] The amount of clay, silicon source, aluminum source, magnesium source, and activity regulating element source added is such that, based on dry weight, the catalytic cracking promoter comprises: 5-50 wt% clay, 5-40 wt% silicon species (SiO2), 30-80 wt% aluminum species (Al2O3), 0.5-15 wt% magnesium (oxide), and 0.5-10 wt% activity regulating element (oxide); the SiO2 / Al2O3 molar ratio of the silicon and aluminum species is 0.05-2; and the activity regulating element is selected from at least one of P, B, Group IIIB, and Group IVB elements.

[0054] In this invention, the preparation method of the catalytic cracking composition involves preparing a silica-alumina-magnesium mixed gel, adjusting the silica-alumina-magnesium mixed gel to a specific pH, and aging it. This process helps to regulate the distribution of active centers, generate a macroporous structure, increase the pore wall thickness, and improve the hydrothermal stability of the macroporous structure. By loading active regulating elements onto the additive microspheres, the distribution of active sites on the additive surface is controlled, further enhancing the stability of the additive. As a result, the additive exhibits good heavy oil cracking capacity and low coke selectivity in the heavy oil catalytic cracking process. The catalytic cracking additive obtained by the above-mentioned specific preparation method, when used in conjunction with the catalytic cracking catalyst in the heavy oil catalytic cracking process, achieves increased light oil yield while reducing slurry oil yield and coke selectivity.

[0055] In some embodiments of the present invention, preferably, the amount of clay, silicon source, aluminum source, magnesium source and activity regulating element source added is such that the resulting catalytic cracking promoter, on a dry basis, comprises: 10-45 wt% clay, 8-35 wt% silicon species calculated as SiO2, 35-75 wt% aluminum species calculated as Al2O3, 1-10 wt% magnesium calculated as oxides and 1-8 wt% activity regulating element calculated as oxides.

[0056] In some embodiments of the present invention, preferably, the SiO2 / Al2O3 molar ratio of the silicon species and aluminum species is 0.2-1.5, for example, it can be 0.2, 0.4, 0.6, 0.8, 1, 1.2, 1.4, 1.5, or any value within the range of any two of the above values.

[0057] In some embodiments of the present invention, preferably, the activity regulating element is selected from at least one of P, B, La, Ce, Y, Zr, and Ti, and more preferably from at least one of P, B, La, and Ce. Using the above-mentioned preferred activity regulating element is more conducive to its synergistic effect with magnesium, thereby improving the efficiency of catalytic cracking reaction, increasing the selectivity of light oil products, and reducing slurry oil yield and coke selectivity.

[0058] In this invention, in step (1), preferably, magnesium is present in the gel framework by preparing a silica-alumina-magnesium mixed gel. This is beneficial for improving the catalytic activity and stability of the catalytic cracking aid, optimizing the pore structure, and thus enabling the catalytic cracking composition to have a better catalytic effect in the heavy oil catalytic cracking reaction.

[0059] In some embodiments of the present invention, preferably, the solid content of the silicon-aluminum-magnesium mixed gel is 5-40 wt%, for example, it can be 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, or any value within the range of any two of the above values, preferably 5-35 wt%. Using the above-mentioned preferred solid content of the silicon-aluminum-magnesium mixed gel is beneficial to ensuring uniform mixing and sufficient reaction of the components, optimizing the aging treatment effect, improving the catalytic performance of the catalytic cracking composition, and optimizing the catalytic effect.

[0060] In this invention, in step (1), the solvent, clay, silicon source, aluminum source, and magnesium source can be mixed in one step, or they can be mixed stepwise. Preferably, the mixed solution of clay and aluminum source is first mixed with acid, then silicon source is added for a second mixing, and then magnesium source is added for a third mixing. The above-mentioned preferred preparation method is beneficial for forming a silicon-aluminum-magnesium mixed gel with uniform structure and good performance. In this invention, the solvent is preferably water.

[0061] In this invention, the methods and conditions for the first, second, and third mixing are not particularly limited, as long as it ensures that the components are mixed uniformly. Preferably, the mixing time is independently 0.5-5 hours, for example, it can be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or any value within the range of any two of the above values.

[0062] In this invention, the type of magnesium source has a wide range of selection. The magnesium source is a magnesium-containing compound, preferably selected from at least one of magnesium oxide, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium oxalate, and magnesium acetate, and more preferably selected from at least one of magnesium oxide, magnesium sulfate, magnesium nitrate, and magnesium acetate.

[0063] In this invention, the type of aluminum source is not particularly limited, and various aluminum sources conventionally used in the art can be used in this invention. Preferably, the aluminum source is selected from at least one of aluminum sol, aluminum sulfate, aluminum isopropoxide, aluminum chloride, aluminum nitrate, boehmite, alumina, aluminum hydroxide, and sodium aluminate, and is more preferably aluminum sulfate and / or aluminum sol.

[0064] In this invention, the type of silicon source is not particularly limited, and various silicon sources conventionally used in the art can be used in this invention. Preferably, the silicon source is selected from at least one of water glass, alkaline silica sol, acidic silica sol, tetraethyl orthosilicate, and tetramethoxysilane, and is more preferably water glass and / or alkaline silica sol.

[0065] In this invention, the type of clay is not particularly limited, and various commonly used clays can be used. Preferably, the clay is selected from at least one of kaolin, bentonite, montmorillonite, sepiolite, diatomaceous earth, tartaric acid, attapulgite, and halloysite, with kaolin being the most preferred. Using the above-mentioned preferred clay is beneficial for further optimizing the pore structure and pore distribution of the catalytic cracking additive and improving its wear resistance.

[0066] In this invention, the amount of acid used has a wide range of selection. Preferably, the amount of acid used is such that the pH of the mixture obtained after the first mixing is 1-4, for example, it can be 1, 2, 3, 4, or any value within the range of any two of the above values. The above-mentioned preferred pH range is beneficial for forming a stable silica-alumina-magnesium mixed gel.

[0067] In this invention, the type of acid is not particularly limited, and various substances that can provide acidity commonly used in the art can be used in this invention. Preferably, the acid is an inorganic acid and / or an organic acid, and is preferably selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, and citric acid.

[0068] In this invention, the mixing conditions in step (1) are not particularly limited, as long as the components are mixed evenly. Preferably, the mixing time is 0.5-5 hours, for example, it can be 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, or any value within the range of any two of the above values.

[0069] In this invention, the aging treatment conditions have a wide range of selection. Preferably, the aging treatment conditions include: a temperature of 10-100℃, more preferably 20-80℃; and a time of 1-24h, more preferably 4-20h. Using the above-mentioned preferred aging treatment conditions is beneficial for further consolidating the skeletal structure of the silica-alumina-magnesium gel and for ensuring a firm bond between magnesium and the gel skeleton.

[0070] In this invention, preferably, in step (2), the pH is adjusted to 9.5-11.5 by contacting the silica-alumina-magnesium mixed gel with an alkali. For example, it can be 9.5, 10, 10.5, 11, 11.5, or any value within the range of any two of the above values.

[0071] In this invention, the type of alkali is not particularly limited, and various substances that can provide alkalinity commonly used in the art can be used in this invention. Preferably, the alkali is selected from at least one of ammonia, sodium hydroxide, sodium carbonate, and sodium aluminate, with ammonia being the most preferred.

[0072] In this invention, the method and conditions for spray drying are not particularly limited, and can be any spray drying method and conditions conventionally used in the art. Preferably, the exhaust gas temperature during spray drying is 100-300°C, more preferably 120-200°C. These preferred spray drying conditions facilitate the rapid drying of the atomized slurry into tiny droplets into spherical particles, thereby obtaining well-shaped additive microspheres and further improving the catalytic performance and catalytic effect of the prepared catalytic cracking composition.

[0073] In some embodiments of the present invention, preferably, the method in step (2) further includes optionally calcining the spray-dried product. In the present invention, optional calcination means that calcination may or may not be performed.

[0074] In this invention, the calcination conditions have a wide range of selection. Preferably, the calcination conditions include: a temperature of 300-600℃, a time of 0.5-5h, and a heating rate of 2-10℃ / min.

[0075] In this invention, the types of the activity-regulating element sources have a wide range of selection. Preferably, the activity-regulating element is a soluble compound containing the activity-regulating element. Preferably, the phosphorus source is selected from one or more of orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate, and pyrophosphoric acid; the boron source is selected from boric acid and / or boron oxide; the La, Ce, Y, Zr, Ti, and Fe sources are each independently a salt containing the corresponding metal element, preferably a nitrate and / or a chloride.

[0076] In some embodiments of the present invention, preferably, the ammonium exchange results in a sodium oxide content on the surface of the additive microspheres of no more than 0.3% by weight, and more preferably 0.05-0.25% by weight. In the present invention, maintaining the sodium oxide content on the surface of the additive microspheres within the above-mentioned preferred range through ammonium exchange is beneficial for optimizing the acidity and active sites on the additive surface, thereby improving the catalytic activity and stability of the catalytic cracking composition. In the present invention, the sodium oxide content on the surface of the additive microspheres is determined using the method Q / SH 361906-2018 (Q / SH 3360-205).

[0077] In this invention, the ammonium exchange method can be a conventional ammonium exchange method used in the art. Preferably, the ammonium exchange method includes: bringing the auxiliary microspheres and the ammonium salt into a first contact in the presence of a solvent.

[0078] In some embodiments of the present invention, preferably, the mass ratio of the additive microspheres to the ammonium salt, on a dry basis, is 1:0.01-0.6. For example, it can be 1:0.01, 1:0.02, 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, or any value within the range of any two of the above values, preferably 1:0.02-0.5. Using the above-mentioned preferred mass ratio helps ensure sufficient exchange of ammonium ions with sodium oxide while avoiding excessive exchange, optimizing the distribution of active sites on the additive surface, thereby improving the catalytic activity of the catalytic cracking composition, increasing the yield of light oil while reducing slurry oil yield and coke selectivity.

[0079] In this invention, the amount of solvent used in the ammonium exchange process has a wide range of options. Preferably, the mass ratio of the auxiliary agent microspheres to the solvent, on a dry basis, is 1:5-20, more preferably 1:8-15. Using the above-mentioned preferred mass ratio is beneficial for improving the efficiency of ammonium exchange. The solvent used in this invention is preferably water.

[0080] In this invention, the type of ammonium salt used in the ammonium exchange is not particularly limited, as long as it enables ion exchange between the auxiliary microspheres and the ammonium salt. Preferably, the ammonium salt used in the ammonium exchange is selected from at least one of ammonium chloride, ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium oxalate, and ammonium phosphate, and more preferably from at least one of ammonium chloride, ammonium sulfate, and ammonium oxalate.

[0081] In this invention, the ammonium exchange conditions have a wide range of selection. Preferably, the ammonium exchange conditions include: a temperature of 20-100℃, more preferably 20-80℃; and a time of 10-120 min. Using the above-mentioned preferred ammonium exchange conditions is beneficial for reducing sodium oxide content and optimizing active sites.

[0082] In this invention, by first exchanging the additive microspheres with ammonium and then loading them with active regulating elements, it is beneficial to reduce the sodium oxide content and increase the loading of active metals, thereby improving the catalytic performance of the catalytic cracking composition, increasing the yield of light oil, and reducing the yield of slurry oil and the selectivity of coke.

[0083] In this invention, the method for loading the activity-regulating element is not particularly limited. Preferably, the loading method includes: in the presence of a solvent, subjecting the activity-regulating element source to a second contact with the product obtained from ammonium exchange, performing impregnation and / or ion exchange.

[0084] In this invention, the impregnation method is not particularly limited, and impregnation methods and conditions conventionally used in the art can be employed. Preferably, the impregnation method is a saturated impregnation method. More preferably, the product obtained from ammonium exchange is contacted with an impregnation solution containing a soluble compound of an active regulating element. This invention does not particularly limit the type of soluble compound containing the active regulating element; substances conventionally used in the art can be employed.

[0085] In some embodiments of the present invention, preferably, the mass ratio of the additive microspheres to the active regulating element source (based on oxides) is 1:0.005-0.1, for example, it can be 1:0.005, 1:0.01, 1:0.02, 1:0.03, 1:0.04, 1:0.05, 1:0.06, 1:0.07, 1:0.08, 1:0.09, 1:0.1, or any value within the range of any two of the above values, preferably 1:0.01-0.08. Using the above-mentioned preferred mass ratio is more conducive to controlling the distribution of active sites on the additive surface, while further enhancing the stability of the additive, improving the catalytic performance of the catalytic cracking additive, and exhibiting excellent catalytic effect. In the present invention, the amount of solvent in the loaded active regulating element has a wide selection range. Preferably, the mass ratio of the additive microspheres to the solvent (based on dry weights) is 1:5-15, more preferably 1:8-10. Using the above-mentioned preferred mass ratio is beneficial for promoting the uniform distribution of the active regulating elements. The solvent used in this invention is preferably water.

[0086] According to the present invention, when the active regulating element is two or more elements, the loading can be carried out in one step or in steps, and the present invention does not have any particular limitation on this.

[0087] In this invention, the conditions for the second contact have a wide range of selection. Preferably, the conditions for the second contact include a temperature of 20-100°C, more preferably 20-80°C. In this invention, when the second contact is performed by ion exchange, the contact time is preferably 15-120 min, more preferably 30-90 min; when the second contact is performed by impregnation, the contact time is preferably 10-30 h, more preferably 12-24 h. Using the above-mentioned preferred conditions for the second contact helps ensure that the active regulating elements are fully loaded onto the surface of the additive microspheres, thereby optimizing the catalytic performance and catalytic effect of the catalytic cracking composition.

[0088] In some embodiments of the present invention, preferably, the method in step (3) further includes: calcining the product loaded with the activity regulating element.

[0089] In this invention, the calcination conditions have a wide range of selection. Preferably, the calcination conditions include: a temperature of 400-600℃, more preferably 450-550℃; and a time of 0.5-3h, more preferably 1-2.5h. Using the above-mentioned preferred calcination conditions is beneficial for fixing the activity regulating elements and optimizing the performance of the catalytic cracking composition.

[0090] In this invention, the method in step (3) further includes: optionally performing solid-liquid separation and drying on the mixture loaded with the activity regulating element before calcination. The drying method and conditions described in this invention are not particularly limited and can be any drying method and conditions conventionally used in the art. Preferably, the drying temperature is 80-200℃ and the time is 0.5-24h.

[0091] In this invention, the mass ratio of the catalytic cracking catalyst to the catalytic cracking promoter has a wide selection range. Preferably, the mass ratio of the catalytic cracking catalyst to the catalytic cracking promoter is 1:0.05-0.8, more preferably 1:0.1-0.6. Using the above-mentioned preferred mass ratio is more conducive to improving the catalytic activity of the catalytic cracking composition, thereby further promoting heavy oil conversion, improving light oil selectivity, and reducing coke production.

[0092] The catalytic cracking catalyst is defined in the same way as in the first aspect, and will not be described again here.

[0093] A third aspect of the present invention provides a catalytic cracking promoter, which, based on a dry weight basis, comprises 5-50 wt% clay, 5-40 wt% silicon species (calculated as SiO2), 30-80 wt% aluminum species (calculated as Al2O3), 0.5-15 wt% magnesium (calculated as oxides), and 0.5-10 wt% activity-regulating elements (calculated as oxides); the SiO2 / Al2O3 molar ratio of the silicon and aluminum species is 0.05-2; and the activity-regulating element is selected from at least one of P, B, Group IIIB, and Group IVB elements.

[0094] The content of base centers in the catalyst was determined to be 0.05-0.5 mmol / g by CO2-TPD method;

[0095] The microreaction activity retention of the catalytic cracking aid before and after treatment at 800℃ and 100% steam for 17 hours is not less than 60%.

[0096] The total pore volume of the catalytic cracking aid, as determined by the low-temperature nitrogen adsorption method, is not less than 0.5 mL / g, wherein the pore volume of pores with a diameter of 10-100 nm accounts for more than 80% of the total pore volume.

[0097] In this invention, the catalytic cracking aid is defined in the same scope as in the first aspect and has all the technical features of the catalytic cracking aid described in the first method, which will not be repeated here.

[0098] The fourth aspect of the present invention provides a catalytic cracking composition as described in the first aspect above or a catalytic cracking composition prepared by the method described in the second aspect above, or the application of the catalytic cracking aid as described in the third aspect above in heavy oil catalytic cracking.

[0099] In this invention, the catalytic cracking composition is used in the heavy oil catalytic cracking process, and is particularly suitable for the efficient conversion of inferior oils, avoiding the condensation and coking of heavy oil macromolecules and over-cracking, thereby increasing the yield of light oil while reducing the oil slurry yield and coke selectivity.

[0100] The present invention will be described in detail below through embodiments. In the present invention, unless otherwise specified, room temperature refers to 25±5℃.

[0101] In the following examples, the raw materials used in the preparation of the catalyst are described as follows: the solid content of kaolin is 79% by weight; the alumina content in the alumina sol is 22% by weight; the concentration of aluminum sulfate solution as Al2O3 is 90 g / L; the solid content of boehmite is 65%; the concentration of water glass as SiO2 is 250 g / L; the industrial agent (brand name HSC) was provided by Sinopec Catalyst Company, and its main properties are listed in Table 2.

[0102] Specific surface area and pore volume analysis: A Micromeritics ASAP 2405NV1.01 automated adsorption analyzer was used, employing the low-temperature static nitrogen adsorption capacity method. The sample surface area was 1.33 × 10⁻⁶. -2 The sample was degassed under vacuum at 300℃ for 4 hours using N2 as the adsorption medium, and the adsorption-desorption isotherm was measured at 77.4K. The specific surface area of ​​the sample was calculated according to the BET formula, and the volume of N2 adsorbed by the sample at a relative pressure p / p0 = 0.98 was measured and converted into liquid nitrogen volume, i.e., total pore volume. The pore distribution was calculated using the SH / 0572 (ASTM D 4641) standard, and the pore volume of the 10-100 nm pore portion of the sample was calculated using the BJH desorption branch.

[0103] Catalytic cracking additive strength: A certain amount of sample is placed in a fixed device and milled under a constant airflow for 5 hours. The average percentage of wear in the last four hours (excluding the first hour) is called the wear index of the additive, expressed as % per hour. The method and standard are: NB / SH / T 0964-2017.

[0104] Microreactor activity test of catalytic cracking additive: The microreactor activity of light oil in the sample was evaluated using the standard method of RIPP92-90 (see "Analytical Methods for Petrochemical Industry" (RIPP Test Methods), edited by Yang Cuiding et al., Science Press, 1990). The sample loading was 5.0 g, the reaction temperature was 460 ℃, the feed oil was straight-run light diesel oil with a distillation range of 235-337 ℃, and the product composition was analyzed by gas chromatography. The microreactor activity of light oil was calculated based on the product composition.

[0105] Example 1

[0106] (1) Add 909g of aluminum sol and 190g of kaolin to 300g of deionized water and mix. Then add hydrochloric acid to the resulting slurry to adjust the pH of the slurry to 2.5 and stir for 1h. Then add 550g of water glass solution and stir for 2h. Then add 20g of magnesium oxide and stir for 1h to obtain a silica-alumina-magnesium gel with a solid content of 24.4wt%.

[0107] (2) Add ammonia to the obtained silica-alumina-magnesium gel slurry to adjust the pH of the slurry to 11.5, age it at room temperature for 4 hours, and then spray dry the stabilized silica-alumina gel to form it. The tail gas temperature of the spray drying is 170℃, and the gel is calcined at 200℃ for 1 hour to obtain the additive microspheres.

[0108] (3) The auxiliary microspheres (on a dry basis), ammonium sulfate (as oxide) and water were mixed in a mass ratio of 1:0.15:10 for ion exchange. The mixture was stirred at 80°C for 30 minutes, filtered, and repeated twice. The auxiliary microspheres (on a dry basis), P2O5 and water were mixed in a mass ratio of 1:0.04:8 for ion exchange. The mixture was stirred at 60°C for 30 minutes and filtered. The resulting filter cake was dried at 120°C for 12 hours and calcined at 500°C for 1 hour to obtain catalytic cracking auxiliary C1 (composition and properties are shown in Table 1).

[0109] (4) The catalytic cracking additive C1 and the industrial agent (the main properties are listed in Table 2) are mixed at a mass ratio of 3:7 to obtain the catalytic cracking composition.

[0110] Example 2

[0111] (1) 2676 g of aluminum sulfate solution and 177 g of kaolin were mixed, and then hydrochloric acid was added to the resulting slurry to adjust the pH of the slurry to 2.5. After stirring for 1 h, 763 g of water glass solution was added and stirred for 2 h. Then, 40.2 g of magnesium acetate was added and stirred for 0.5 h to obtain a silica-alumina-magnesium gel with a solid content of 13 wt%.

[0112] (2) Add ammonia to the obtained silica-alumina-magnesium gel slurry to adjust the pH of the slurry to 11, age it at 60°C for 4 hours, and then spray dry the stabilized silica-alumina gel to form it. The tail gas temperature of the spray drying is 170°C, and the gel is calcined at 250°C for 1 hour to obtain the additive microspheres.

[0113] (3) The additive microspheres (on a dry basis), ammonium sulfate (as an oxide) and water were mixed in a mass ratio of 1:0.2:10 for ion exchange. The mixture was stirred at room temperature for 30 minutes, filtered, and the process was repeated once. Then, 17.8 g of boric acid was dissolved in 300 g of deionized water to prepare an impregnation solution in a mass ratio of 1:0.02 between the additive microspheres (on a dry basis) and B2O3. The impregnation solution was then contacted with the ion-exchanged additive microspheres and kept at room temperature for 12 h. The mixture was then dried at 100 °C for 12 h and calcined at 450 °C for 2 h to obtain catalytic cracking additive C2 (composition and properties are shown in Table 1).

[0114] (4) The catalytic cracking additive C2 and the industrial agent (the main properties are listed in Table 2) are mixed at a mass ratio of 3:7 to obtain the catalytic cracking composition.

[0115] Example 3

[0116] (1) Add 285 g of kaolin and 269 g of boehmite to 500 g of deionized water and mix them. Then add nitric acid to the slurry to adjust the pH of the slurry to 2 and stir for 3 h. Then add 269 g of alkaline silica sol and stir for 1 h. Then add 30.8 g of magnesium sulfate and stir for 2 h to obtain a silica-alumina-magnesium gel with a solid content of 35 wt%.

[0117] (2) Add ammonia to the obtained silica-alumina-magnesium gel slurry to adjust the pH of the slurry to 9.8, age it at 60°C for 8 hours, and then spray dry the stabilized silica-alumina gel to form it. The tail gas temperature of the spray drying is 190°C, and the gel is calcined at 300°C for 1 hour to obtain the additive microspheres.

[0118] (3) The additive microspheres (on a dry basis), ammonium sulfate (as oxide) and water were mixed in a mass ratio of 1:0.3:15 for ion exchange. The mixture was stirred at 80°C for 30 minutes, filtered, and the process was repeated once. The additive microspheres (on a dry basis), La2O3 and water were mixed in a mass ratio of 1:0.02:10 for ion exchange. The mixture was stirred at room temperature for 60 minutes and filtered. Then, the additive microspheres (on a dry basis), P2O5 and 9.3 g of diammonium hydrogen phosphate were dissolved in 200 g of deionized water to prepare an impregnation solution. The impregnation solution was then contacted with the lanthanum-loaded additive microspheres described above and kept at room temperature for 12 hours. The mixture was then dried at 120°C and calcined at 500°C for 2 hours to obtain catalytic cracking additive C3 (composition and properties are shown in Table 1).

[0119] (4) The catalytic cracking additive C3 and the industrial agent (the main properties are listed in Table 2) are mixed at a mass ratio of 3:7 to obtain the catalytic cracking composition.

[0120] Example 4

[0121] (1) Mix 5070 g of aluminum sulfate solution and 70 g of kaolin for 0.5 h, then add sulfuric acid to the obtained slurry to adjust the pH of the slurry to 3.8, then add 133 g of alkaline silica sol, stir for 2 h, then add 61.5 g of magnesium sulfate, stir for 2 h, and obtain a silica-alumina-magnesium gel with a solid content of 8 wt%.

[0122] (2) Add ammonia to the obtained silica-alumina-magnesium gel slurry to adjust the pH of the slurry to 11.5, age it at 65°C for 8 hours, and then spray dry the stabilized silica-alumina gel to form it. The tail gas temperature of the spray drying is 165°C, and the gel is calcined at 350°C for 1 hour to obtain the additive microspheres.

[0123] (3) The auxiliary microspheres (on a dry basis), ammonium sulfate (as oxide) and water were mixed in a mass ratio of 1:0.2:20 for ion exchange. The mixture was stirred at 80°C for 30 minutes, filtered, and repeated twice. The auxiliary microspheres (on a dry basis), P2O5, CeO2 and water were mixed in a mass ratio of 1:0.06:0.01:6. The ion-exchanged auxiliary microspheres, deionized water, 55.8 g of diammonium hydrogen phosphate and 10.8 g of cerium chloride (CeCl3·7H2O) were stirred at room temperature for 60 minutes and filtered. The resulting filter cake was dried at 120°C for 12 hours and calcined at 500°C for 1 hour to obtain catalytic cracking auxiliary C4 (composition and properties are shown in Table 1).

[0124] (4) The catalytic cracking additive C4 and the industrial agent (the main properties are listed in Table 2) are mixed at a mass ratio of 3:7 to obtain the catalytic cracking composition.

[0125] Example 5

[0126] (1) Add 1101 g of aluminum isopropoxide to 500 g of deionized water, then add acetic acid to the obtained slurry to adjust the pH of the slurry to 2.5, stir for 3 h, then add 127 g of kaolin, stir for 1 h, then add 450 g of water glass solution, stir for 3 h, then add 92.7 g of magnesium nitrate, stir for 1 h, to obtain a silica-alumina-magnesium gel with a solid content of 21 wt%.

[0127] (2) Add ammonia to the obtained silica-alumina-magnesium gel slurry to adjust the pH of the slurry to 9.6, age it at 60°C for 6 hours, and then spray dry the stabilized silica-alumina gel to form it. The tail gas temperature of the spray drying is 160°C, and the gel is calcined at 200°C for 1 hour to obtain the additive microspheres.

[0128] (3) The additive microspheres (on a dry basis), ammonium sulfate (as oxide) and water were mixed in a mass ratio of 1:0.05:12 for ion exchange. The mixture was stirred at 65°C for 30 minutes, filtered, and repeated three times. 16.2 g of ammonium dihydrogen phosphate was dissolved in 400 g of deionized water to prepare an impregnation solution in a mass ratio of 1:0.02 of additive microspheres (on a dry basis) and P2O5. The impregnation solution was then contacted with the ion-exchanged additive microspheres and kept at room temperature for 24 h. The mixture was then dried at 120°C for 12 h and calcined at 500°C for 2 h to obtain catalytic cracking additive C5 (composition and properties are shown in Table 1).

[0129] (4) The catalytic cracking additive C5 and the industrial agent (the main properties are listed in Table 2) are mixed at a mass ratio of 3:7 to obtain the catalytic cracking composition.

[0130] Example 6

[0131] (1) Add 727 g of aluminum sol and 222 g of kaolin to 300 g of deionized water and mix. Stir for 0.5 h. Then add hydrochloric acid to the obtained slurry to adjust the pH of the slurry to 3. Then add 800 g of water glass solution and stir for 3 h. Then add 15.4 g of magnesium sulfate and stir for 1 h to obtain a silica-alumina-magnesium gel with a solid content of 25 wt%.

[0132] (2) Add ammonia to the obtained silica-alumina-magnesium gel slurry to adjust the pH of the slurry to 11, age it at 60°C for 6 hours, and then spray dry the stabilized silica-alumina gel to form it. The tail gas temperature of the spray drying is 155°C, and the gel is calcined at 200°C for 1.5 hours to obtain the additive microspheres.

[0133] (3) The auxiliary microspheres (on a dry basis), ammonium sulfate (as oxide) and water were mixed in a mass ratio of 1:0.15:10 for ion exchange, stirred at 60°C for 30 minutes, filtered, and repeated twice; the auxiliary microspheres (on a dry basis), P2O5 and water were mixed in a mass ratio of 1:0.005:5, deionized water and 4.6 g of diammonium hydrogen phosphate were mixed and stirred at 60°C for 30 minutes, filtered; the resulting filter cake was dried at 120°C for 12 h and calcined at 500°C for 2 h to obtain catalytic cracking auxiliary C6 (composition and properties are shown in Table 1).

[0134] (4) The catalytic cracking additive C6 and the industrial agent (the main properties are listed in Table 2) are mixed at a mass ratio of 3:7 to obtain the catalytic cracking composition.

[0135] Example 7

[0136] The method described in Example 1 is different,

[0137] In step (1), the amount of kaolin used was increased from 190 g to 211 g; the amount of magnesium oxide used was reduced from 20 g to 3 g; and catalytic cracking aid C7 was obtained (the composition and properties are shown in Table 1).

[0138] Example 8

[0139] The method described in Example 1 is different,

[0140] In step (1), the amount of kaolin used is reduced from 190 grams to 158 grams;

[0141] In step (3), 152.7 g of yttrium nitrate (Y(NO3)3·6H2O) was used to replace 37.2 g of diammonium hydrogen phosphate; catalytic cracking aid C8 was obtained (the composition and properties are shown in Table 1).

[0142] Comparative Example 1

[0143] The method described in Example 1 is different except that in step (2), no aging treatment is performed, and step (2) is not performed. The silica-alumina-magnesium gel is directly spray-dried and shaped to obtain catalytic cracking aid DC1 (composition and properties are shown in Table 1).

[0144] Comparative Example 2

[0145] The method described in Example 1 differs in that, in step (3), the additive microspheres, ammonium sulfate and water are mixed in a mass ratio of 1:0.15:10 for ion exchange, stirred at 80°C for 30 minutes, filtered, and repeated twice; the resulting filter cake is dried at 120°C for 12 hours and calcined at 500°C for 1 hour to obtain catalytic cracking additive DC2 (composition and properties are shown in Table 1).

[0146] Comparative Example 3

[0147] The method of Example 1 is followed, except that the catalytic cracking aid DC3 is prepared according to the method of Example 1 of CN114272919A, and DC3 is used to replace C1.

[0148] Comparative Example 4

[0149] The method described in Example 1 is different,

[0150] In step (1), 909 g of aluminum sol and 190 g of kaolin were mixed with 300 g of deionized water. Then, hydrochloric acid was added to the resulting slurry to adjust the pH of the slurry to 2.5. The mixture was stirred for 1 h. Then, 550 g of water glass solution was added and stirred for 2 h. Finally, 20 g of magnesium oxide and 37.2 g of diammonium hydrogen phosphate were added and stirred for 1 h to obtain a silica-alumina-magnesium gel with a solid content of 24.4 wt%.

[0151] In step (3), the auxiliary microspheres (on a dry basis), ammonium sulfate (as an oxide) and water are mixed in a mass ratio of 1:0.15:10 for ion exchange. The mixture is stirred at 80°C for 30 minutes, filtered, and repeated twice. The resulting filter cake is dried at 120°C for 12 hours and calcined at 500°C for 1 hour to obtain auxiliary microspheres DC4 (composition and properties are shown in Table 1).

[0152] Table 1

[0153]

[0154] Table 1 (continued)

[0155]

[0156]

[0157] As can be seen from the results in Table 1, compared with the comparative example, the catalytic cracking aid provided by the present invention has a significantly increased total pore volume, a significantly improved pore distribution of 10-100 nm, reaching more than 80% of the total pore volume, a high amount of Brønsted acid, and excellent activity. The microreactor activity retention rate before and after treatment at 800℃ and 100% steam for 17 hours reaches more than 60%.

[0158] Test case

[0159] The catalytic cracking compositions prepared in the embodiments and comparative examples of the present invention were aged at 800°C and 100% steam for 12 hours in a fixed-bed aging unit, and then evaluated in an ACE unit. The properties of the feedstock used for evaluation are shown in Table 3, and the reaction temperature, reactant-to-oil weight ratio and evaluation results are shown in Table 4. In the table, the conversion rate (%) = gasoline yield (%) + liquefied petroleum gas yield (%) + dry gas yield (%) + coke yield (%); coke selectivity (%) = coke yield (%) / conversion rate (%) × 100%.

[0160] Table 2 Properties of Industrial Catalysts

[0161]

[0162]

[0163] Table 3 Properties of Feed Oil

[0164]

[0165] Table 4

[0166]

[0167]

[0168] Table 4 (continued)

[0169]

[0170] As can be seen from the results in Table 4, when the catalytic cracking composition described in this invention is applied to the heavy oil catalytic cracking process, the ratio of diesel to heavy oil yield increases, while increasing the yield of light oil and greatly reducing coke selectivity, demonstrating excellent catalytic effect.

[0171] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A catalytic cracking composition, characterized in that, The catalytic cracking composition includes a catalytic cracking aid and a catalytic cracking catalyst; Based on the dry weight of the catalytic cracking promoter, the catalytic cracking promoter comprises: 5-50 wt% clay, 5-40 wt% silicon species (calculated as SiO2), 30-80 wt% aluminum species (calculated as Al2O3), 0.5-15 wt% magnesium (calculated as oxides), and 0.5-10 wt% activity regulating element (calculated as oxides); the SiO2 / Al2O3 molar ratio of the silicon species and aluminum species is 0.05-2; the activity regulating element is selected from at least one of P, B, Group IIIB elements, and Group IVB elements. The content of base centers in the catalyst was determined to be 0.05-0.5 mmol / g by CO2-TPD method; The microreaction activity retention of the catalytic cracking aid before and after treatment at 800℃ and 100% steam for 17 hours is not less than 60%. The total pore volume of the catalytic cracking aid, as determined by the low-temperature nitrogen adsorption method, is not less than 0.5 mL / g, wherein the pore volume of pores with a diameter of 10-100 nm accounts for more than 80% of the total pore volume.

2. The catalytic cracking composition according to claim 1, wherein, The content of base centers in the catalyst was determined to be 0.1-0.4 mmol / g by CO2-TPD method; Preferably, the microreaction activity retention of the catalytic cracking aid is 65%-85% before and after treatment at 800°C and 100% steam for 17 hours; Preferably, the total pore volume of the catalytic cracking aid is 0.6-1.5 mL / g, as determined by low-temperature nitrogen adsorption method, wherein the pore volume of pores with a diameter of 10-100 nm accounts for 85%-99% of the total pore volume; Preferably, based on the dry weight of the catalytic cracking aid, the catalytic cracking aid comprises: 10-45 wt% clay, 8-35 wt% silicon species calculated as SiO2, 35-75 wt% aluminum species calculated as Al2O3, 1-10 wt% magnesium calculated as oxides, and 1-8 wt% activity regulating elements calculated as oxides. Preferably, the SiO2 / Al2O3 molar ratio of the silicon species and aluminum species is 0.2-1.5; Preferably, the total amount of the silicon species and the aluminum species, calculated as oxides, is 45-90% by weight, more preferably 50-85% by weight.

3. The catalytic cracking composition according to claim 1 or 2, wherein, The aluminum species exist in the form of aluminum silicate; Preferably, the activity regulating element is selected from at least one of P, B, La, Ce, Y, Zr and Ti, and more preferably from at least one of P, B, La and Ce; Preferably, the clay is selected from at least one of kaolin, bentonite, montmorillonite, sepiolite, diatomite, tartaric acid, attapulgite, halloysite, and hydrotalcite, with kaolin being the most preferred.

4. The catalytic cracking composition according to any one of claims 1-3, wherein, The specific surface area of ​​the catalytic cracking additive is 150-350 m². 2 / g, preferably 180-300m 2 / g; Preferably, the most probable pore size of the catalytic cracking aid is 10-40 nm, and more preferably 15-35 nm; Preferably, the wear index of the catalytic cracking aid is not higher than 2.6 m% / h, and more preferably 0.5-2.5 m% / h; Preferably, the mass ratio of the catalytic cracking catalyst to the catalytic cracking aid is 1:0.05-0.8, more preferably 1:0.15-0.6; Preferably, based on the dry weight of the catalytic cracking catalyst, the catalytic cracking catalyst comprises: 0.1-10 wt% rare earth metal elements as oxides, 40-60 wt% aluminum species as Al2O3, and 20-50 wt% silicon species as SiO2.

5. A method for preparing a catalytic cracking composition, characterized in that, The method includes the following steps: (1) In the presence of a solvent, clay, silicon source, aluminum source and magnesium source are mixed to obtain silicon-aluminum-magnesium mixed gel; (2) Adjust the pH of the silicon-aluminum-magnesium mixed gel to 9-12, and after aging treatment, spray dry to form microspheres of the additive; (3) The additive microspheres are subjected to ammonium exchange and then loaded with activity regulating elements to obtain a catalytic cracking additive; (4) The catalytic cracking promoter and the catalytic cracking catalyst are contacted to obtain a catalytic cracking composition; wherein the amount of clay, silicon source, aluminum source, magnesium source and activity regulating element source added is such that, based on dry weight, the catalytic cracking promoter includes: 5-50% by weight of clay, 5-40% by weight of silicon species (SiO2), 30-80% by weight of aluminum species (Al2O3), 0.5-15% by weight of magnesium (oxides), and 0.5-10% by weight of activity regulating element (oxides); the SiO2 / Al2O3 molar ratio of the silicon species and aluminum species is 0.05-2; the activity regulating element is selected from at least one of P, B, Group IIIB elements and Group IVB elements.

6. The method according to claim 5, wherein, The amounts of clay, silicon source, aluminum source, magnesium source, and active regulating element source added are such that, based on dry weight, the catalytic cracking promoter comprises: 10-45 wt% clay, 8-35 wt% silicon species (calculated as SiO2), 35-75 wt% aluminum species (calculated as Al2O3), 1-10 wt% magnesium (calculated as oxides), and 1-8 wt% active regulating element (calculated as oxides). Preferably, the SiO2 / Al2O3 molar ratio of the silicon species and aluminum species is 0.2-1.5; Preferably, the activity regulating element is selected from at least one of P, B, La, Ce, Y, Zr and Ti, and more preferably from at least one of P, B, La and Ce; Preferably, the source of the activity regulating element is a soluble compound containing the activity regulating element.

7. The method according to claim 5 or 6, wherein, The solid content of the silicon-aluminum-magnesium mixed gel is 5-40 wt%, preferably 5-35 wt%. Preferably, the preparation method of the silicon-aluminum-magnesium mixed gel includes: first mixing a mixed solution of clay and aluminum source with acid, then adding silicon source for second mixing, and then adding magnesium source for third mixing; Preferably, the magnesium source is a magnesium-containing compound, preferably selected from at least one of magnesium oxide, magnesium sulfate, magnesium nitrate, magnesium chloride, magnesium oxalate, and magnesium acetate, and more preferably selected from at least one of magnesium oxide, magnesium sulfate, magnesium nitrate, and magnesium acetate. Preferably, the aluminum source is selected from at least one of aluminum sol, aluminum sulfate, aluminum isopropoxide, aluminum chloride, aluminum nitrate, boehmite, aluminum oxide, aluminum hydroxide, and sodium aluminate, and is preferably aluminum sulfate and / or aluminum sol; Preferably, the silicon source is selected from at least one of water glass, alkaline silica sol, acidic silica sol, tetraethyl orthosilicate, and tetramethoxysilane, and is more preferably water glass and / or alkaline silica sol; Preferably, the amount of acid used is such that the pH of the mixture obtained after the first mixing is 1-4; Preferably, the acid is an inorganic acid and / or an organic acid, and is preferably selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and citric acid; Preferably, the mixing times for the first mixing, the second mixing, and the third mixing are each 0.5-5 hours independently.

8. The method according to any one of claims 5-7, wherein, The aging treatment conditions include: a temperature of 10-100℃, preferably 20-80℃; and a time of 1-24h, preferably 4-20h. Preferably, in step (2), the silica-alumina-magnesium mixed gel is contacted with an alkali to adjust the pH of the silica-alumina-magnesium mixed gel to 9.5-11.5; Preferably, the alkali is selected from at least one of ammonia, sodium hydroxide, sodium carbonate, and sodium aluminate, with ammonia being the most preferred. Preferably, the exhaust gas temperature of the spray drying process is 100-300℃, more preferably 120-200℃; Preferably, the method in step (2) further includes optionally calcining the spray-dried product; Preferably, the calcination conditions include: a temperature of 300-600℃, a time of 0.5-5h, and a heating rate of 2-10℃ / min.

9. The method according to any one of claims 5-8, wherein, The ammonium exchange process ensures that the sodium oxide content on the surface of the auxiliary microspheres is no more than 0.3% by weight, preferably 0.05-0.25% by weight; Preferably, the mass ratio of the auxiliary microspheres to the ammonium salt, on a dry basis, is 1:0.01-0.6, more preferably 1:0.02-0.5; Preferably, the mass ratio of the auxiliary microspheres to the solvent, on a dry basis, is 1:5-20; Preferably, the ammonium salt for ammonium exchange is selected from at least one of ammonium chloride, ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium carbonate, ammonium bicarbonate, ammonium oxalate, and ammonium phosphate; more preferably, it is selected from at least one of ammonium chloride, ammonium sulfate, and ammonium oxalate. Preferably, the conditions for ammonium exchange include: a temperature of 20-100℃, more preferably 20-80℃; and a time of 10-120 min. Preferably, the loading method includes: in the presence of a solvent, subjecting the active regulating element source to a second contact with the product obtained by ammonium exchange, performing impregnation and / or ion exchange; Preferably, the mass ratio of the auxiliary microspheres to the active regulating element source, based on a dry basis, is 1:0.005-0.1, more preferably 1:0.01-0.08; Preferably, the mass ratio of the auxiliary microspheres to the solvent, on a dry basis, is 1:5-15; Preferably, the conditions for the second contact include: a temperature of 20-100°C, more preferably 20-80°C; Preferably, the method in step (3) further includes: calcining the product loaded with the activity regulating element; Preferably, the calcination conditions include: a temperature of 400-600℃, more preferably 450-550℃; and a time of 0.5-5h.

10. A catalytic cracking aid, characterized in that, Based on the dry weight of the catalytic cracking promoter, the catalytic cracking promoter consists of 5-50 wt% clay, 5-40 wt% silicon species (calculated as SiO2), 30-80 wt% aluminum species (calculated as Al2O3), 0.5-15 wt% magnesium (calculated as oxides), and 0.5-10 wt% activity regulating elements (calculated as oxides); the SiO2 / Al2O3 molar ratio of the silicon and aluminum species is 0.05-2; the activity regulating element is selected from at least one of P, B, Group IIIB elements, and Group IVB elements. The content of base centers in the catalyst was determined to be 0.05-0.5 mmol / g by CO2-TPD method; The microreaction activity retention of the catalytic cracking aid before and after treatment at 800℃ and 100% steam for 17 hours is not less than 60%. The total pore volume of the catalytic cracking aid, as determined by the low-temperature nitrogen adsorption method, is not less than 0.5 mL / g, wherein the pore volume of pores with a diameter of 10-100 nm accounts for more than 80% of the total pore volume.

11. The catalytic cracking composition according to any one of claims 1-4 or the catalytic cracking composition prepared by the method according to any one of claims 5-9, or the application of the catalytic cracking additive according to claim 10 in heavy oil catalytic cracking.

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