CN107971001A - It is a kind of containing rich in mesoporous assistant for calalytic cracking of Beta molecular sieves and preparation method thereof - Google Patents

Abstract

The invention discloses a catalytic cracking additive containing mesoporous-rich Beta molecular sieves and a preparation method thereof, based on the weight of the additive on a dry basis, and the additive contains 10-75% by weight of mesoporous-rich Beta molecular sieve, 0-60% by weight of clay on a dry basis, 15-60% by weight of an inorganic oxide binder on a dry basis, P ₂ O ₅ 0-25% by weight of phosphorus additives and 0-15% by weight of group VIII metal additives in terms of oxides, wherein the Al distribution parameter D of the molecular sieve satisfies: 0.4≤D≤0.8; The pore specific surface area is 350-500 ^m2 /g, and the ratio of the mesopore volume to the total pore volume of the molecular sieve is 30-70% by volume. Applying the additive of the invention to catalytic cracking can increase the yield of isobutene and propylene, and increase the octane number of gasoline.

Description

A catalytic cracking aid containing mesoporous-rich Beta molecular sieve and its preparation method

technical field

The invention relates to a catalytic cracking aid containing mesoporous-rich Beta molecular sieve and a preparation method thereof.

Background technique

Low-carbon olefins Olefin is an important organic chemical raw material, and the world's demand for low-carbon olefins is increasing year by year. Fluid catalytic cracking is one of the important processes for producing low-carbon olefins. For most catalytic cracking units, adding additives is an effective technical way to increase the production of low-carbon olefins. However, the prior art has no obvious effect on increasing the concentration of isobutene in liquefied gas. From the perspective of isobutene formation and reaction chemistry in the FCC process, β molecular sieve (also known as β zeolite, beta molecular sieve) is an effective active component. The main problem of β molecular sieve in use is that on the one hand, its structure is easily damaged during the process of removing its template agent, and on the other hand, it is easy to dealuminate during the reaction process, so the activity stability is poor.

Early patents disclosed some cracking catalysts or additives containing zeolite beta, which can increase the octane number of gasoline, increase the production of light olefins and liquefied gas, such as US patents US4740292, US4898846, US4911823 and WO95026533. Some of the beta zeolites used in these patents are emphasized as low-sodium hydrogen zeolites, and some are emphasized as high-silicon-aluminum ratio zeolites. β with a high silicon-aluminum ratio can be synthesized directly, or obtained by hydrothermal treatment or acid treatment.

US Patent No. 4,837,396 discloses a catalyst, which contains zeolite beta and zeolite Y, and contains a metal ion compound as a stabilizer to improve the hydrothermal stability and mechanical strength of the catalyst. The stabilizer can be [Al ₂ (OH) ₅ Cl] _x , or Al ₃ Zr(OH) ₉ Cl ₄ . The stabilizer can directly interact with the β zeolite, or it can be added during the preparation of the catalyst.

U.S. Patent No. 6,355,591 discloses a catalytic cracking additive containing 4-20% of aluminum phosphate, 1-40% of ZSM-5, β and mixtures thereof, and 40-90% of clay, which can increase the output of LPG. The preparation method of aluminum phosphate is: add concentrated phosphoric acid to dilute in deionized water, add aluminum powder to dissolve, wherein the molar ratio of Al to PO ₄ is 1:3, and the pH is less than 2.0. The prepared aluminum phosphate and kaolin are evenly mixed, then mixed into the molecular sieve slurry, and finally sprayed into shape. According to the patent claims, the additive does not contain other binders and other inorganic oxides except aluminum phosphate. In addition, the preparation method and properties of additives containing zeolite beta are not given in the examples of this patent.

Chinese patent CN 1043450A proposes a method for modifying β molecular sieves. The method involves roasting Naβ molecular sieves, removing part of the skeleton aluminum with acid, and then performing potassium exchange to make the potassium content of the zeolite 0.5-2.5% by weight. After drying, After roasting, soak for 4-10 hours at room temperature in a near-neutral phosphate buffer solution including potassium hydrogen phosphate-potassium dihydrogen phosphate, hypophosphorous acid-potassium hypophosphite, phosphorous acid-potassium phosphite, and wash or The phosphorus content on the zeolite is kept at 0.01-0.5% by weight without washing, and then dried and roasted; the β molecular sieve modified by this method is suitable as a hydrocarbon processing catalyst involving hydroisomerization reaction.

Chinese patent CN 1179994A proposes a method for modifying β molecular sieves. In this method, Na β molecular sieves are exchanged with ammonium ions and the Na ₂ O content on the zeolite is less than 0.1% by weight; removing part of the skeleton aluminum so that the silicon-aluminum ratio is greater than 50; mixing the above-mentioned dealuminated β molecular sieve with phosphoric acid or phosphate evenly and then drying, so that the amount of _P2O5 on the obtained zeolite is _2-5 % by weight; finally Under the steam atmosphere, it is hydrothermally calcined at 450-650°C for 0.5-4 hours. When the β molecular sieve modified by the method is used for the cracking reaction of hydrocarbons, a higher yield of olefins, especially isomeric olefins, and a lower yield of coke can be obtained.

Chinese patent CN1205249A discloses a method for modifying zeolite beta, which includes mixing the raw powder of zeolite beta with a compound containing Al ₂ O ₃ source, P ₂ O ₅ source, SiO ₂ source, H ₂ O ₂ and water. The mixture is according to β zeolite: Al ₂ O ₃ : P ₂ O ₅ : SiO ₂ : H ₂ O ₂ : H ₂ O = 1: (0.001～0.02): (0.01～0.30): (0～0.05): (0～ 0.10): (1.0-3.0) weight ratio mixed evenly, after drying, then heating up to 400-650°C and roasting for 1-5 hours, and then using conventional methods for ammonium ion exchange until the _Na2O content is less than 0.1% by weight, The method can significantly improve the activity stability of the beta zeolite, and at the same time improve the crystallization retention.

Chinese patent CN1616351 discloses a preparation method of phosphorus-containing β zeolite, which is to prepare a working solution in water with an aluminum source, an alkali source and a tetraethylammonium cation solution, and to use silica gel with a particle size of 20-300 mesh as the silica source. Mix with the working solution to wet the surface of the silica gel particles with the working solution, and keep at 80-140°C for 20-80 hours to prepare the seed glue; then add the seed glue to the prepared seed glue and feed Aluminum phosphate with a weight of 5-30% is uniformly mixed and then crystallized at 140-170° C. for 50-100 hours, the solid product is separated, washed until the Na ₂ O content is less than 0.1% by weight, and then dried. The method can prepare zeolite beta with a phosphorus content as high as 5% by weight, and has high catalytic selectivity when used in an alkylation reaction.

Chinese patent CN1872685A discloses a modified β molecular sieve, which is characterized in that the anhydrous chemical expression of the β molecular sieve is (0-0.3)Na ₂ O·(0.5-10)Al ₂ O ₃ in terms of the mass of the oxide ·(1.3-10)P ₂ O ₅ ·(0.7-15)M _x O _y ·(70-97)SiO ₂ , wherein M is selected from one of Fe, Co, Ni, Cu, Mn, Zn and Sn kind. The zeolite is used in catalytic cracking and can be used as an active component of a catalyst or an auxiliary agent.

Chinese patent CN101434401A discloses a phosphorus-containing β molecular sieve, which is characterized in that the phosphorus content of said β molecular sieve is 0.01-10% by weight based on P ₂ O ₅ , and a weight loss peak appears at 220±25°C in the thermogravimetric characterization spectrum . The molecular sieve is obtained by roasting the beta molecular sieve in the air atmosphere to remove the organic template agent, and then treating it with an aqueous solution of a phosphorus compound at a temperature of 100-250°C.

Chinese patent CN101450318A discloses a modification method of a β molecular sieve, which is characterized in that the sodium type β molecular sieve is prepared at room temperature according to the weight ratio of molecular sieve:ammonium salt:H ₂ O=1:(0.1～1):(5～10) Exchange at 100°C for 0.3 to 1 hour, filter, then impregnate and modify the molecular sieve with a solution containing a phosphorus compound and a solution containing a metal compound, wherein the pH of the impregnating solution is adjusted to 6 to 8, and then dried and roasted.

Chinese patents CN102971065A and CN105312081A disclose a novel metal-containing zeolite beta for _NOx reduction. No organic structure directing agent (SDA) is required in its preparation. The metal may include 1-10 wt% Fe or Cu. Also disclosed are methods of selectively catalytically reducing nitrogen oxides in exhaust gases using the disclosed zeolites.

Chinese patent CN103447068A discloses a catalyst additive for catalytic cracking containing β zeolite and its application. The patent relates to a catalyst additive for zeolite β which is suitable for catalytic cracking reaction and can increase liquid recovery, reduce coke, and increase propylene production. Catalyst additives were prepared by modifying, demoulding and aging kaolin microspheres in situ crystallized β zeolite, and applied to catalytic cracking reactions. The in-situ crystallized microspherical zeolite beta catalyst additive replaces 2 to 50 wt% of the base catalyst. Increased propylene production, anti-coking and increased liquid recovery capacity.

Chinese patent CN103771437A discloses a phosphorus-containing modified β molecular sieve, which is characterized in that the phosphorus content is 3-10% by weight based on P ₂ O ₅ , and in the ²⁷ Al MAS NMR of the molecular sieve, the chemical shift is 40±3ppm resonance The ratio of the signal peak area to the resonance signal peak area with a chemical shift of 54ppm±3ppm is greater than or equal to 1. The phosphorus in the molecular sieve is fully coordinated with the framework aluminum, the framework aluminum is fully protected, and has excellent hydrothermal stability and better product selectivity.

Chinese patent CN103785455A discloses a cracking aid for increasing the concentration of low-carbon olefins in catalytic cracking, including 10-75% by weight of phosphorus and transition metal-modified β molecular sieves, 0-60% by weight of clay, 15-60% by weight of Inorganic oxide binder, 0.5-15% by weight of group VIII metal additives and 2-25% by weight of phosphorus additives; the transition metal is selected from Fe, Co, Ni, Cu, Mn, Zn, Sn and Bi One or more of them; the β molecular sieve containing phosphorus and transition metals has a phosphorus content of 1-10% by weight based on P ₂ O ₅ and a metal content of 0.5-10% by weight based on metal oxides. The molecular sieve In the ²⁷ Al MASNMR, the ratio of the peak area of the resonance signal with a chemical shift of 40±3ppm to the peak area of the resonance signal with a chemical shift of 54ppm±3ppm is greater than 1, and the resonance signal peak with a chemical shift of 0±3ppm and a chemical shift of -12ppm±3ppm The sum of the areas accounts for less than 10% of the total peak area. The cracking catalyst composition is applied to the catalytic cracking of petroleum hydrocarbons, which can increase the yield of catalytic cracking liquefied gas, increase the concentration of low-carbon olefins in the liquefied gas, especially the concentration of isobutene, increase the ratio of ethylene to dry gas, and increase the octane number of gasoline .

Chinese patent CN103785456A discloses a cracking aid for increasing the concentration of low-carbon olefins, which contains modified β molecular sieves, phosphorus-aluminum inorganic binders containing the first clay, other inorganic binders and Group VIII metal additives, with or without The second clay; the phosphorus-aluminum inorganic binder containing the first clay includes an aluminum component, a phosphorus component and the first clay; the phosphorus and transition metal modified β molecular sieve, calculated as P ₂ O ₅ The phosphorus content accounts for 1-10% by weight, and the metal content accounts for 0.5-10% by weight in terms of metal oxides. In the ²⁷ Al MAS NMR of the molecular sieve, the chemical shift is 40±3ppm, the resonance signal peak area and the chemical shift are 54ppm±3ppm resonance The signal peak area ratio is greater than or equal to 1, and the sum of the resonance signal peak areas with a chemical shift of 0±3ppm and a chemical shift of -12ppm±3ppm accounts for less than or equal to 10% of the total peak area. The cracking catalyst composition is applied to the catalytic cracking of petroleum hydrocarbons, which can increase the yield of catalytic cracking liquefied gas, increase the concentration of low-carbon olefins in the liquefied gas, especially the concentration of isobutene, increase the ratio of ethylene to dry gas, and increase the octane number of gasoline , the heavy oil conversion ability of the main catalyst will not be affected when a large proportion of additives are blended.

Chinese patent CN103785457A discloses a cracking aid for increasing the concentration of low-carbon olefins, including 10-75% by weight of β molecular sieves containing phosphorus and transition metals, 0-60% by weight of clay, and 15-60% by weight of inorganic oxides A binder, wherein, the phosphorus content in the β molecular sieve containing phosphorus and transition metals is 1-10% by _weight as _P2O5 , and the metal content is 0.5-10% by weight as metal oxides; the phosphorus-containing In ^{the 27} Al MAS NMR of β molecular sieves with transition metals, the ratio of the peak area of the resonance signal with a chemical shift of 40±3ppm to the peak area of the resonance signal with a chemical shift of 54ppm±3ppm is greater than 1, the chemical shift is 0±3ppm and the chemical shift is - The percentage of the sum of the peak areas of the resonance signals at 12ppm±3ppm to the total peak area is less than 10%. The additive used in catalytic cracking can increase the concentration of ethylene in the dry gas of catalytic cracking and increase the concentration of propylene and isobutene in the liquefied gas.

Chinese patent CN103785458A discloses a cracking aid for increasing the concentration of low-carbon olefins, which contains phosphorus and transition metals, a phosphorus-aluminum inorganic binder containing the first clay, other inorganic binders, and the second clay; wherein, the The phosphor-aluminum inorganic binder containing the first clay includes 15-40% by weight _{of aluminum} components based on _Al2O3 , 45-80% by weight of phosphorus components based on _P2O5 , and 1 ～40% by weight of the first clay, and its P/Al weight ratio is 1～6; the β molecular sieve containing phosphorus and transition metals, the phosphorus content is 1～10% by weight based on P ₂ O ₅ , and the content based on metal The metal content of the oxide accounts for 0.5 to 10% by weight. In the ²⁷ Al MAS NMR of the molecular sieve, the ratio of the peak area of the resonance signal with a chemical shift of 40±3ppm to the peak area of the resonance signal with a chemical shift of 54ppm±3ppm is greater than 1, and the chemical shift is The sum of peak areas of resonance signals with 0±3ppm and chemical shifts of -12ppm±3ppm accounted for less than 10% of the total peak area. The additive is used in catalytic cracking, which can increase the concentration of ethylene in dry gas of catalytic cracking and the concentration of propylene and isobutene in liquefied gas.

Chinese patent CN103787357A discloses a modified β molecular sieve, the phosphorus content is 1-10% by weight based on P ₂ O ₅ , and the metal content is 0.5-10% by weight based on metal oxide. It is characterized in that the ²⁷ Al MAS In NMR, the ratio of the peak area of the resonance signal with a chemical shift of 40±3ppm to the peak area of the resonance signal with a chemical shift of 54ppm±3ppm is greater than or equal to 1, and the peak area of the resonance signal with a chemical shift of 0±3ppm and a chemical shift of -12ppm±3ppm The percentage of the sum to the total peak area is less than or equal to 10%. The molecular sieve has excellent hydrothermal stability, and has better product selectivity when used as an active component of a catalyst or auxiliary agent in a catalytic cracking or catalytic cracking process.

Chinese patent _CN103787358A discloses a β molecular sieve containing phosphorus and metal, which is characterized in that the phosphorus content is 1-10% by weight based on _P2O5 , and the metal content is 0.5-10% by weight based on metal oxides. The molecular sieve In the ²⁷ Al MAS NMR, the ratio of the peak area of the resonance signal with a chemical shift of 40±3ppm to the peak area of the resonance signal with a chemical shift of 54ppm±3ppm is greater than or equal to 1.

Chinese patent CN103787359A discloses a phosphorus-containing silicon-rich β molecular sieve, which is characterized in that the phosphorus content is 1-10% by weight based on P ₂ O ₅ , and in the ²⁷ Al MAS NMR of the molecular sieve, the chemical shift is 40±3ppm resonance The ratio of the signal peak area to the peak area of the resonance signal with a chemical shift of 54ppm±3ppm is greater than or equal to 1, and the sum of the peak areas of the resonance signal with a chemical shift of 0±3ppm and a chemical shift of -12ppm±3ppm accounts for a percentage of the total peak area of less than or equal to 10%. The patent also provides a preparation method of the above-mentioned phosphorus-containing silicon-rich β molecular sieve, which is characterized in that the original powder of the β molecular sieve is subjected to temperature-programmed roasting to remove the template agent, then extracts aluminum, and then performs phosphorus modification.

Due to its unique pore structure, high acidity and good hydrothermal stability, β molecular sieve has broad prospects for industrial application and has been successfully used in petrochemical fields such as isomerization, catalytic cracking and alkylation of aromatics. However, due to the shape-selective effect of the molecular sieve, when the kinetic size of the reactant molecules exceeds the pore size of the microporous molecular sieve, the reactant molecules cannot diffuse into the interior of the molecular sieve; Reactions are selected, affecting product distribution. In order to overcome the weakness of microporous materials with smaller pore size and more acidic surface, catalytic materials with silicon-rich and mesoporous surfaces have attracted increasing attention.

Chinese patent CN1769169A discloses a method for preparing a β molecular sieve with a multi-level pore structure, which mainly includes the following steps: directly treating the molecular sieve with low-temperature nucleation and high-temperature crystallization with ammonium salt in crystal form, filtering and drying, and controlling the crystal form in three stages. Warm roasting and demoulding, then acid treatment under mild conditions, and then pressurized hydrothermal, the silicon-aluminum ratio of the obtained β molecular sieve is 80-120, and has 0.1-1.7nm, 1.7-6.0nm and 10-90.0nm The distribution of three pore sizes improves the surface utilization of the β molecular sieve.

Chinese patent CN101003378 discloses a preparation method of multi-stage channel β zeolite, which is to impregnate a silica gel monolithic column with sucrose solution, dry, polymerize, and carbonize to obtain a carbon-silicon composite. The carbon-silicon composite is made of aluminum source, inorganic alkali, After the mixed solution composed of organic amine and water is wetted, it crystallizes and recovers the product. In the method, the carbon material effectively protects the pore structure of the silica gel monolithic column during the crystallization process, so as not to be damaged during the crystallization process. The beta zeolite material prepared by this method has multi-level channels such as micron-scale macropores, mesopores and micropores, which overcomes the limitation of the catalytic performance of the zeolite molecular sieve micropores, and the existence of transparent macropores can shorten the diffusion of reaction molecules. The distance of the device can reduce the pressure drop of the device, thereby improving the unit processing capacity of the device, and can make the selectivity of the product easy to adjust and control. The mesopore can provide a rich internal specific surface area, which is very important for the catalytic reaction of macromolecules. meaning.

Chinese patent CN101538049 discloses a method for preparing a multi-stage channel beta zeolite, which belongs to the technical field of preparation and application of zeolite. It is characterized in that carbon particles generated under the constraints of ordered mesoporous channels are used as hard templates, and then small molecular organic ammonium soft templates are added to convert the mesoporous silica-alumina wrapped carbon particles into microporous β zeolite in situ, and the soft and hard templates are removed by roasting After that, zeolite beta with hierarchical pores can be obtained. Compared with the direct application of mesoporous carbon as a template, the multi-stage pore β zeolite synthesized by the method provided by this patent does not need to remove the mesoporous silica-alumina, and then reintroduce the silica-alumina species of the synthetic zeolite, which not only reduces the complicated process, but also saves A preparation method of a multi-stage channel beta zeolite as a raw material. It can greatly reduce diffusion resistance, reduce secondary reactions, have better catalytic performance, and has great potential application value in petrochemical and fine chemical fields.

Chinese patent CN102050463A discloses a mesoporous β molecular sieve and its silicification preparation method, wherein the preparation method includes: dealuminating the calcined Hβ molecular sieve in an acid solution; mixing the dealuminated sample with a template agent-silicon source solution Mix and crystallize; filter, dry, and roast to obtain the product.

Chinese patent CN102826564A discloses a preparation method of β molecular sieve with multi-level pore structure, which uses ethyl orthosilicate as silicon source, sodium metaaluminate as aluminum source, and hexammonium cationic quaternary ammonium salt surfactant As a template, hierarchically porous molecular sieves containing mesopores and β micropores were prepared by hydrothermal synthesis under alkaline conditions.

Chinese patent CN102826565A discloses a method for preparing a multi-stage channel β molecular sieve. In the absence of a second template, a multi-stage channel Beta molecular sieve is synthesized in one step through a "pseudo-solid phase" aluminosilicate, which contains a "honeycomb" The structure or particle size is 5-60 micron large particles, the "honeycomb" structure or large particles are aggregated from small nano-sized molecular sieve crystals, the size of nano-sized molecular sieve small crystals is 10-100 nanometers, composed of nano-sized molecular sieves The diameter of the mesopores formed by the polymerization of small grains is 3-45 nanometers, and the diameter of the micropores is 0.6-0.8 nanometers.

Chinese patent CN103318911A discloses a preparation method of multi-stage pore β zeolite: mix silicon source, tetraethylammonium hydroxide solution, sodium hydroxide and completely dissolved aluminum source evenly, then stir at a certain temperature at a constant temperature until dry coagulation is formed. Glue; the obtained xerogel is subjected to the first hydrothermal treatment at 120-180°C, and an appropriate amount of silane coupling agent is added after cooling and grinding; the second hydrothermal treatment is performed at 120-180°C, and it can be obtained after cooling, filtering and roasting Beta zeolite with multi-stage channels; the preparation method and post-treatment method are simple, the yield is high, and industrial scale-up production can be easily realized.

Chinese patent CN103964458A discloses a beta molecular sieve with high silicon-aluminum ratio multi-stage channels and a preparation method thereof. The pores of the molecular sieve have pore size distribution below 2nm, 5-11nm and above 50nm, in which the volume of micropores is above 0.19cm ³ /g, the total volume of mesopores and macropores is above 0.35cm ³ /g, and its silicon-aluminum ratio 90 or more, and the specific surface area is 400 m ² /g or more. The preparation method comprises the following steps: performing the first acid treatment on the raw material zeolite beta; performing the first roasting on the beta zeolite after the first acid treatment; performing the second acid treatment on the beta zeolite after the first roasting, to obtain The high silicon-aluminum ratio multi-stage zeolite beta.

Chinese patent CN104261423A discloses a preparation method of a single crystal multi-level porous β molecular sieve. First, add inorganic alkali source and aluminum source to the aqueous solution of microporous template agent (TEA+), then add appropriate amount of N-methyl-2-pyrrolidone (NMP) and silicon source and stir evenly, and synthesize single crystal by simple hydrothermal method Hierarchical Beta Molecular Sieves.

Chinese patent CN104321280A discloses a β-type zeolite and a manufacturing method thereof. It is characterized in that: (i) the SiO ₂ /Al ₂ O ₃ ratio is 8-30, and the SiO ₂ /ZnO ratio is 8-1000; (ii) the micropore surface area is 300m ² /g-800m ² /g; (iii) ) the pore volume is 0.1cm ³ /g to 0.3cm ³ /g; (iv) having a diameter of 2nm to 6nm and a volume of 0.001cm ^{3 /g} to 0.3cm ³ /g in the original state after synthesis Mesopores. The zeolite beta can be suitably produced by adding zinc silicate zeolite beta as a seed crystal to a reaction mixture containing a silica source, an alumina source, an alkali source, and water, and performing a reaction.

Chinese patent CN104353484A discloses a preparation method of cheap strongly acidic hierarchically porous Beta zeolite. The method comprises: 1. calcining Beta zeolite to obtain microporous hydrogen Beta zeolite; 1. Adding sodium-type desiliconized hierarchically porous Beta zeolite to ammonium nitrate aqueous solution for exchange, and calcining to obtain hydrogen-type desiliconized hierarchically porous Beta zeolite; 4. Adding hydrogen-type desiliconized hierarchically porous Beta zeolite to the acid solution and stirring, Washing, drying, and repeating step three, the strongly acidic hierarchically porous Beta zeolite is obtained.

Chinese patent CN104402020A discloses a medium and micro double-porous β molecular sieve and its preparation method and application. In this method, sodium metaaluminate is the best aluminum source, tetraethyl orthosilicate is the best silicon source, and eight-headed Bola type quaternary ammonium salt surfactants with different carbon chain lengths are used as templates. Preparation of β-hierarchical zeolite molecular sieves with both mesoporous and microporous structures by hydrothermal method.

Chinese patents CN104418345A, CN104418346A, CN104418347A, CN104418348A, CN104418349A, CN104418350A, CN104418351A, CN104418352A, CN104418353A disclose a group of polyquaternary salts with multi-level channel structure-6 synthesis process of β-molecular sieve and its preparation method. Ammonium-7, Polyquaternium-10, Polyquaternium-11, Polyquaternium-22, Polyquaternium-32, Polyquaternium-37, Polyquaternium-39, Polyquaternium Salt-44 and other high molecular polymers are used as the directing agent of micropores and mesopores at the same time, and the synthesized β molecular sieve has mesopores of 8-20nm and macropores of 50-200nm at the same time.

Chinese patent CN105692644A discloses a method for preparing hierarchically porous zeolites, that is, various alkali vapors are used as zeolitic mineralizers, amorphous mesoporous/macroporous materials are used as precursors, and the method is prepared by alkali vapor heat treatment Hierarchical zeolite materials. The amorphous mesoporous/macroporous materials applicable to this patent are amorphous porous inorganic precursors whose precursors involve various mesoporous or macroporous molecular sieves. 1 zeolite. This is the first example of the preparation of hierarchically porous zeolite by the alkali metal steam thermal method, which has comparable or higher HF and wider applicability to the preparation of zeolite than the prior art.

The above-mentioned methods for preparing hierarchically porous β all have problems such as the use of organic ammonium salt sewage is not easy to treat, the preparation process is long, the molecular sieve pore structure is destroyed, and the aluminum distribution on the surface cannot be adjusted.

Contents of the invention

The purpose of the present invention is to provide a kind of catalytic cracking additive containing Beta molecular sieve rich in mesoporous and its preparation method, applying the additive of the present invention to catalytic cracking can improve the productive rate of isobutene and propylene, improve gasoline octane number .

In order to achieve the above object, the present invention provides a kind of catalytic cracking additive that contains the Beta molecular sieve that is rich in mesoporous, by weight and based on the dry basis weight of described auxiliary agent, described auxiliary agent contains in dry basis 10-75% by weight of mesoporous-rich Beta molecular sieve, 0-60% by weight of clay based on dry basis, 15-60% by weight of inorganic oxide binder based on dry basis, P ₂ O ₅ 0-25% by weight of phosphorus additives and 0-15% by weight of group VIII metal additives in terms of oxides, wherein the Al distribution parameter D of the molecular sieve satisfies: 0.4≤D≤0.8, wherein, D=Al (S)/Al(C), Al(S) means the aluminum content in any region greater than 100 square nanometers within the distance H from the edge of the molecular sieve crystal grains measured by the TEM-EDS method, and Al(C) means the aluminum content in the region using TEM -The aluminum content of any area greater than 100 square nanometers within the distance H from the geometric center of the crystal plane of the molecular sieve crystal grain measured by the EDS method, wherein the H is the distance from a certain point on the edge of the crystal plane to the geometric center of the crystal plane 10%; the micropore specific surface area of the molecular sieve is 350-500 m2 ^/ g, and the ratio of the mesopore volume to the total pore volume of the molecular sieve is 30-70% by volume.

Preferably, the Al distribution parameter D of the molecular sieve satisfies: 0.55≤D≤0.75; the micropore specific surface area of the molecular sieve is 370-450 m2 ^/ g, and the ratio of the mesopore volume to the total pore volume of the molecular sieve is 35-60 body %.

Preferably, by weight and based on the dry basis weight of the auxiliary agent, the auxiliary agent contains 20-60% by weight of mesoporous-rich Beta molecular sieves on a dry basis, 10- 45% by weight clay, 25-50% by weight inorganic oxide binder on dry basis, _5-15 % by weight phosphorus additive as _P2O5 and 1-10% by weight as oxide Group VIII metal additives.

Preferably, the clay comprises at least one selected from the group consisting of kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, letronite, diatomaceous earth, halloysite, saponite, bentonite and hydrotalcite , the inorganic oxide binder includes at least one selected from pseudo-boehmite, alumina sol, silica-alumina sol and water glass.

Preferably, the phosphorus additive is introduced into the auxiliary agent in the form of phosphorus-containing compounds, and the phosphorus-containing compounds include phosphorus oxides, phosphates, phosphites, alkali phosphates and acid phosphates. At least one; the Group VIII metal includes at least one selected from Fe, Co and Ni, the Group VIII metal additive is introduced into the auxiliary agent in the form of a metal-containing compound, and the metal-containing compound includes an oxide selected from At least one of compounds, hydroxides, chlorides, nitrates, sulfates, phosphates and organic compounds.

The present invention also provides a preparation method of catalytic cracking additive, the preparation method comprising: mixing Beta molecular sieve rich in mesoporous, inorganic oxide binder and water, adding or not adding clay, beating, and spray drying; wherein , introducing or not introducing phosphorus additives, introducing or not introducing Group VIII metal additives; by weight and based on the dry basis weight of the preparation raw materials of the auxiliary agent, the preparation raw materials of the auxiliary agent contain 10 - 75% by weight of mesoporous rich Beta molecular sieve, 0-60% by weight of clay on dry basis, 15-60% by weight of inorganic oxide binder _on dry basis, calculated as _P2O5 0-25% by weight of phosphorus additives and 0-15% by weight of group VIII metal additives in terms of oxides; the Al distribution parameter D of the molecular sieve satisfies: 0.4≤D≤0.8, wherein, D=Al(S) /Al(C), Al(S) means the aluminum content in any region greater than 100 square nanometers within the distance H from the edge of the molecular sieve crystal plane measured by the TEM-EDS method, and Al(C) means the TEM-EDS method The measured aluminum content in any area greater than 100 square nanometers within a distance H from the geometric center of the crystal plane of the molecular sieve grain, wherein the H is 10% of the distance from a certain point on the edge of the crystal plane to the geometric center of the crystal plane; The micropore specific surface area of the molecular sieve is 350-500 m2 ^/ g, and the ratio of the mesopore volume to the total pore volume of the molecular sieve is 30-70% by volume.

Preferably, the preparation step of the mesoporous-rich Beta molecular sieve comprises: a, carrying out alkali treatment on the sodium-type Beta molecular sieve in an alkaline solution, and after filtering and washing, to obtain the alkali-treated molecular sieve; b, performing step a The alkali-treated molecular sieve obtained in the method is dealuminated in a complex acid dealumination agent solution composed of fluosilicic acid, organic acid and inorganic acid, and after filtering and washing, the mesoporous-rich Beta molecular sieve is obtained.

Preferably, the alkaline solution is at least one selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, ammonia water and peralkaline sodium metaaluminate solution; The sodium content of the sodium metaaluminate solution is 270-310 g/liter, the aluminum content is 30-50 g/liter, and the density of the high alkali sodium metaaluminate solution is 1.25-1.45 g/ml.

Preferably, the conditions of the alkali treatment described in step a include: the weight ratio of the molecular sieve in dry basis weight and the alkali in the alkaline solution is 1: (0.02-0.3); wherein, in the sodium hydroxide solution The weight of the alkali is in the weight of sodium hydroxide, the weight of the alkali in the potassium hydroxide solution is in the weight of potassium hydroxide, and the weight of the alkali in the lithium hydroxide solution is in the weight of lithium hydroxide, The weight of the alkali in the ammonia water is calculated by the weight of ammonia monohydrate, and the weight of the alkali in the high alkali sodium metaaluminate solution is calculated by the weight of sodium oxide.

Preferably, the conditions of the alkali treatment in step a include: the temperature of the alkali treatment is 25-100° C., and the time of the alkali treatment is 0.5-6 hours.

Preferably, the organic acid in step b is at least one selected from ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid is at least one selected from hydrochloric acid, sulfuric acid and nitric acid A sort of.

Preferably, the conditions of the dealumination treatment described in step b include: the weight ratio of molecular sieve, fluosilicic acid, organic acid and inorganic acid on a dry weight basis is 1: (0.03-0.5): (0.05-0.4) :(0.05-0.5); the treatment temperature is 25-100°C, and the treatment time is 0.5-6 hours.

Preferably, the conditions of the dealumination treatment described in step b include: the weight ratio of molecular sieve, fluosilicic acid, organic acid and inorganic acid on a dry weight basis is 1: (0.05-0.3): (0.1-0.3) :(0.1-0.3).

Preferably, the clay comprises at least one selected from the group consisting of kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, letronite, diatomaceous earth, halloysite, saponite, bentonite and hydrotalcite , the inorganic oxide binder includes at least one selected from pseudo-boehmite, alumina sol, silica-alumina sol and water glass.

Preferably, the phosphorus additive is introduced into the auxiliary agent in the form of phosphorus-containing compounds, and the phosphorus-containing compounds include phosphorus oxides, phosphates, phosphites, alkali phosphates and acid phosphates. At least one; the Group VIII metal includes at least one selected from Fe, Co and Ni, the Group VIII metal additive is introduced into the auxiliary agent in the form of a metal-containing compound, and the metal-containing compound includes an oxide selected from At least one of compounds, hydroxides, chlorides, nitrates, sulfates, phosphates and organic compounds.

The cracking aid provided by the present invention adopts mesoporous-rich β molecular sieve as an active component, and can also introduce an appropriate amount of phosphorus additives and group VIII metal additives, which improves the yield and selectivity of isobutylene, propylene and ethylene, and improves Improve the octane number of catalytic cracking gasoline, and increase the liquid yield of catalytic cracking reaction.

Other features and advantages of the present invention will be described in detail in the following detailed description.

Detailed ways

Specific embodiments of the present invention will be described in detail below. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.

The present invention provides a kind of catalytic cracking additive containing Beta molecular sieve rich in mesoporous, by weight and based on the dry basis weight of said assistant, said assistant contains 10-75% by weight on dry basis Mesoporous-rich Beta molecular sieve, 0-60% by weight of clay based on dry basis, 15-60% by weight of inorganic oxide binder based on dry basis, 0-25% by weight of P ₂ O ₅ % by weight of phosphorus additives and 0-15% by weight of Group VIII metal additives in terms of oxides, preferably containing 20-60% by weight of mesoporous-rich Beta molecular sieves on a dry basis, 10- 45% by weight clay, 25-50% by weight inorganic oxide binder on dry basis, _5-15 % by weight phosphorus additive as _P2O5 and 1-10% by weight as oxide Group VIII metal additives; wherein, the Al distribution parameter D of the molecular sieve satisfies: 0.4≤D≤0.8, wherein, D=Al(S)/Al(C), and Al(S) means that measured by TEM-EDS method The aluminum content of any area larger than 100 square nanometers within the distance H from the edge of the crystal plane of the molecular sieve grain, Al(C) means that the geometric center of the crystal plane of the molecular sieve grain measured by the TEM-EDS method is arbitrary within the distance H from the outside The aluminum content in the area greater than 100 square nanometers, wherein the H is 10% of the distance from a certain point on the edge of the crystal plane to the geometric center of the crystal plane; the micropore specific surface area of the molecular sieve is 350-500 ^m2 /g, so The ratio of the mesopore volume of the molecular sieve to the total pore volume is 30-70% by volume. Preferably, the Al distribution parameter D of the molecular sieve satisfies: 0.55≤D≤0.75; the micropore specific surface area of the molecular sieve is 370-450 m2 ^/ g, and the ratio of the mesopore volume to the total pore volume of the molecular sieve is 35-60 body %.

According to the present invention, adopting TEM-EDS method to measure the aluminum content of molecular sieve is well known to those skilled in the art, wherein said geometric center is also well known to those skilled in the art, can be calculated according to the formula, the present invention will not go into details, generally The geometric center of the symmetrical figure is the intersection point of the lines connecting opposite vertices, for example, the geometric center of the square crystal face of the conventional cubic Beta molecular sieve is at the intersection point of the lines connecting opposite vertices. The crystal plane is a plane of a regular crystal grain, and the inward and outward directions both refer to the inward and outward directions on the crystal plane.

According to the present invention, clays and inorganic oxide binders are well known to those skilled in the art. For example, the clays may include clays selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, and accumulite. , diatomite, halloysite, saponite, bentonite and hydrotalcite, preferably including at least one selected from kaolin, metakaolin, diatomite, sepiolite, attapulgite, montmorillonite and accumulite The inorganic oxide binder may include at least one selected from pseudo-boehmite, alumina sol, silica-alumina sol and water glass, preferably including pseudo-boehmite and/or alumina sol.

According to the present invention, the phosphorus additive can be introduced into the auxiliary agent in the form of a phosphorus-containing compound, and the phosphorus-containing compound includes one or more of phosphorus-containing inorganic compounds and organic compounds, and can be easily soluble in water, It can also be a water-insoluble or water-insoluble phosphorus compound, such as at least one selected from phosphorus oxides, phosphates, phosphites, alkali phosphates and acid phosphates; preferred phosphorus compounds are One or more of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate and aluminum phosphate sol. The phosphorus additive can exist in any possible position of the additive, such as the inside of the channel of the zeolite, the surface of the zeolite, the matrix material, or the inside of the channel of the zeolite, the surface of the zeolite and the matrix in the material. The phosphorus additive exists in the form of phosphorus compounds (such as phosphorus oxides, phosphates, phosphites, basic phosphates, acid phosphates).

According to the present invention, the Group VIII metal may include at least one selected from Fe, Co and Ni, more preferably Fe, and the Group VIII metal additive may be introduced into the additive in the form of a metal-containing compound, the The metal compound may include at least one selected from oxides, phosphates, phosphites, alkali phosphates, and acid phosphates. The metal additive can exist in any possible position of the additive, such as the inside of the channel of the zeolite, the surface of the zeolite, the matrix material, or the inside of the channel of the zeolite, the surface of the zeolite and the matrix. material, preferably present in the matrix material. The form of the Group VIII metal additive in the auxiliary agent can be in any possible form, for example, it can be one of the metal oxide, phosphate, phosphite, alkali phosphate or acid phosphate or more.

According to the present invention, the ratio of the micropore specific surface area and mesopore volume to the total pore volume of the molecular sieve is measured by nitrogen adsorption BET specific surface area method, and the mesopore volume refers to the pore volume with a pore diameter greater than 2 nanometers and less than 100 nanometers.

The present invention also provides a preparation method of catalytic cracking additive, the preparation method comprising: mixing Beta molecular sieve rich in mesoporous, inorganic oxide binder and water, adding or not adding clay, beating, and spray drying; wherein , introducing or not introducing phosphorus additives, introducing or not introducing Group VIII metal additives; by weight and based on the dry basis weight of the preparation raw materials of the auxiliary agent, the preparation raw materials of the auxiliary agent contain 10 - 75% by weight of mesoporous rich Beta molecular sieve, 0-60% by weight of clay on dry basis, 15-60% by weight of inorganic oxide binder _on dry basis, calculated as _P2O5 0-25% by weight of phosphorus additives and 0-15% by weight of group VIII metal additives in terms of oxides; the Al distribution parameter D of the molecular sieve satisfies: 0.4≤D≤0.8, wherein, D=Al(S) /Al(C), Al(S) means the aluminum content in any region greater than 100 square nanometers within the distance H from the edge of the molecular sieve crystal plane measured by the TEM-EDS method, and Al(C) means the TEM-EDS method The measured aluminum content in any area greater than 100 square nanometers within a distance H from the geometric center of the crystal plane of the molecular sieve grain, wherein the H is 10% of the distance from a certain point on the edge of the crystal plane to the geometric center of the crystal plane; The micropore specific surface area of the molecular sieve is 350-500 ^m2 /g, and the ratio of the mesopore volume to the total pore volume of the molecular sieve is 30-70% by volume.

According to the present invention, the preparation steps of the mesoporous-rich Beta molecular sieve may include: a. carrying out alkali treatment on the sodium-type Beta molecular sieve in an alkaline solution, and after filtering and washing, to obtain the alkali-treated molecular sieve; b. The alkali-treated molecular sieve obtained in step a is dealuminated in a complex acid dealumination agent solution composed of fluosilicic acid, organic acid and inorganic acid, and filtered and washed to obtain the mesoporous-rich Beta molecular sieve.

According to the present invention, the sodium-type Beta molecular sieve is well known to those skilled in the art. For details, please refer to U.S. Patent No. 3,308,069 and Chinese Patent CN 00107486.5. It can be obtained by crystallization without amine, or it can be roasted by the molecular sieve prepared by the template method. The latter obtained, the sodium content in the sodium-type Beta molecular sieve can be 4-6% by weight in terms of sodium oxide.

According to the present invention, alkali treatment is used to remove part of the skeleton silicon atoms of the molecular sieve to produce more secondary pores, and the alkaline solution can be selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, ammonia water and At least one of the high alkali sodium metaaluminate solution, preferably a high alkali sodium metaaluminate solution; in terms of oxides, the sodium content of the high alkali sodium metaaluminate solution can be 270-310 grams per liter, aluminum The content can be 30-50 g/liter, and the density of the high alkali sodium metaaluminate solution can be 1.25-1.45 g/ml; the conditions of alkali treatment described in step a can include: molecular sieve and alkaline The ratio of the weight of the alkali in the solution can be 1:(0.02-0.3), preferably 1:(0.03-0.25); wherein, the weight of the alkali in the sodium hydroxide solution is based on the weight of sodium hydroxide, so The weight of the alkali in the potassium hydroxide solution is based on the weight of potassium hydroxide, the weight of the alkali in the lithium hydroxide solution is based on the weight of lithium hydroxide, and the weight of the alkali in the ammonia solution is based on the weight of ammonia monohydrate The weight of the alkali in the high alkali sodium metaaluminate solution is calculated by the weight of sodium oxide; the temperature of the alkali treatment can be 25-100°C, and the time of the alkali treatment can be 0.5-6 hours.

According to the present invention, dealumination is well known to those skilled in the art, but it has not been reported that inorganic acid, organic acid and fluorosilicic acid are used together for dealumination. The dealumination can be carried out once or several times. First, the organic acid can be mixed with the alkali-treated molecular sieve, and then fluosilicic acid and inorganic acid can be mixed with the alkali-treated molecular sieve, that is, adding the organic acid first Alkali is used to treat the molecular sieve, and then the fluosilicic acid and the inorganic acid are slowly added in parallel flow, or the fluosilicic acid is added first and then the inorganic acid is added, preferably the fluosilicic acid and the inorganic acid are slowly added in parallel flow. The organic acid described in step b can be at least one selected from ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably oxalic acid or citric acid, more preferably oxalic acid; the inorganic acid can be selected from At least one of hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid or sulfuric acid, more preferably hydrochloric acid; the conditions of the dealumination treatment described in step b can include: molecular sieves, fluosilicic acid, organic acid by weight on a dry basis The weight ratio with inorganic acid can be 1:(0.03-0.5):(0.05-0.4):(0.05-0.5), preferably 1:(0.05-0.3):(0.1-0.3):(0.1-0.3) ; The treatment temperature can be 25-100° C., and the treatment time can be 0.5-6 hours.

The washing in the present invention is well known to those skilled in the art, and generally refers to washing with water. For example, water at 30-60°C that is 5-10 times the weight of the molecular sieve can be used to rinse the molecular sieve.

In the method for preparing catalytic cracking additives provided by the present invention, when the additives contain phosphorus additives, the phosphorus additives can be introduced by one of the following methods or a combination of several methods, but are not limited to these methods. middle:

1. Add phosphorus compound to the slurry before the additive is spray-dried and formed;

2. After the auxiliary agent is spray-dried and shaped, it is impregnated or chemically adsorbed with phosphorus compounds, introduced through solid-liquid separation (if necessary), drying and roasting. The drying temperature can be from room temperature to 400°C, preferably 100-300°C , the firing temperature can be 400-700°C, preferably 450-650°C, and the firing time can be 0.5-100 hours, preferably 0.5-10 hours. The phosphorus compound may be selected from one or more of various inorganic and organic compounds of phosphorus. The phosphorus compound may be easily soluble in water, or poorly soluble in water or insoluble in water. Examples of phosphorus compounds include phosphorus oxides, phosphoric acid, orthophosphates, phosphites, hypophosphites, phosphorus-containing organic compounds, and the like. Preferred phosphorus compounds are selected from one or more of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, aluminum phosphate and

Therefore, the phosphorus additive can exist in any possible position of the auxiliary agent, such as the inside of the channel of the zeolite, the surface of the zeolite, the matrix material, and the inside of the channel of the zeolite, the surface of the zeolite. and matrix material. The phosphorus additive exists in the form of phosphorus compounds (such as phosphorus oxides, orthophosphates, phosphites, alkali phosphates, acid phosphates).

According to the present invention, the metal additive can be introduced in the form of a metal compound, and the metal additive can be introduced by adding the metal compound to the slurry in any step before the spray drying molding of the auxiliary agent preparation process; it can also be introduced in the auxiliary agent spray After drying and molding, it is introduced by impregnating or chemisorbing metal compounds and then roasting. This method includes impregnating or chemisorbing the additives with an aqueous solution containing metal compounds, followed by solid-liquid separation (if necessary), drying and calcination. The temperature ranges from room temperature to 400°C, preferably 100-300°C, the firing temperature is 400-700°C, preferably 450-650°C, and the firing time is 0.5-100 hours, preferably 0.5-10 hours. The metal compound is selected from one or more of their inorganic compounds and organic compounds, and may be easily soluble in water, or poorly soluble in water or insoluble in water. Examples of metal compounds include oxides, hydroxides, chlorides, nitrates, sulfates, phosphates, organic compounds of metals, and the like of metal compounds. Preferred metal compounds are selected from one or more of their chlorides, nitrates, sulfates and phosphates.

The catalytic cracking aid provided by the invention is suitable for catalytic cracking of various hydrocarbon oils. When used in the catalytic cracking process, it can be added to the catalytic cracking reactor alone or mixed with the catalytic cracking catalyst. Generally, the auxiliary agent provided by the present invention accounts for no more than 30% by weight of the FCC catalyst and the auxiliary agent mixture provided by the present invention, preferably 1-25% by weight, more preferably 3-15% by weight, and the hydrocarbon oil Selected from various petroleum fractions, such as crude oil, atmospheric residue, vacuum residue, atmospheric gas oil, vacuum gas oil, straight run gas oil, propane light/heavy deoiling, coker gas oil and coal liquefaction products one or more of . The hydrocarbon oil may contain heavy metal impurities such as nickel and vanadium and impurities such as sulfur and nitrogen. For example, the content of sulfur can be as high as 3.0% by weight, the content of nitrogen can be as high as 2.0% by weight, and the content of metal impurities such as vanadium and nickel can be as high as 3000ppm.

When the catalytic cracking aid provided by the invention is used in the catalytic cracking process, the hydrocarbon oil catalytic cracking conditions can be conventional catalytic cracking conditions. Generally speaking, the hydrocarbon oil catalytic cracking conditions include a reaction temperature of 400-600° C., preferably 450-550° C., a weight hourly space velocity of 8-120 hours ⁻¹ , preferably 8-80 hours ⁻¹ , and a catalyst-to-oil ratio ( weight ratio) is 1-20, preferably 3-15. The catalytic cracking additive provided by the present invention can be used in various existing catalytic cracking reactors, such as fixed bed reactors, fluidized bed reactors, riser reactors, multi-reaction zone reactors and the like.

The present invention will be further illustrated by the following examples, but the present invention is not thereby subject to any limitation, and the instruments and reagents used in the examples of the present invention, if not otherwise specified, are commonly used instruments and reagents by those skilled in the art .

The properties of some raw materials used in the embodiments of the present invention and comparative examples are as follows: Pseudoboehmite is an industrial product produced by Shandong Aluminum Company, with a solid content of 61% by weight; aluminum sol is an industrial product produced by Sinopec Catalyst Qilu Branch, Al _2O The content is _21.5 % by weight; water glass is an industrial product produced by Sinopec Catalyst Qilu Branch, SiO ₂ content is 28.9% by weight, Na ₂ O content is 8.9% by weight; kaolin is the special kaolin for cracking catalyst produced by Suzhou Kaolin Company, solid Content 78% by weight.

For the TEM-EDS determination method of the present invention, refer to the research method of solid catalyst, Petrochemical Industry, 29(3), 2000:227.

Micropore specific surface area of the present invention, mesopore volume, the measuring method of total pore volume are as follows:

Measured by AS-3 and AS-6 static nitrogen adsorption instruments produced by Quantachrome Instruments.

Instrument parameters: put the sample in the sample processing system, evacuate to 1.33×10 ^-2 Pa at 300°C, keep the temperature and hold the pressure for 4 hours, and purify the sample. At the temperature of liquid nitrogen at -196°C, the adsorption and desorption of nitrogen by the purified samples were tested under different specific pressures P/P ₀ , and the N ₂ adsorption-desorption isotherm curve was obtained. Then use the two-parameter BET formula to calculate the total specific surface area, micropore specific surface area and mesoporous specific surface area, take the adsorption capacity below the specific pressure P/P ₀ =0.98 as the total pore volume of the sample, and use the BJH formula to calculate the pore diameter of the mesoporous part distribution, and the integral method was used to calculate the mesoporous volume (2-100 nm) and the mesoporous volume of 2-20 nm.

The calculation method of the D value is as follows: a polygon is formed by selecting a crystal grain and a certain crystal face of the crystal grain in the transmission electron microscope, and the polygon has a geometric center, an edge, and a 10% distance H from the geometric center to a certain point on the edge (different The edge point of the crystal plane, the H value is different), select any area larger than 100 square nanometers within the distance H from the edge of the crystal plane and any area larger than 100 square nanometers within the distance H from the geometric center of the crystal plane to determine the aluminum content , that is, Al(S1) and Al(C1), and calculate D1=Al(S1)/Al(C1), select different crystal grains and measure 5 times, and calculate the average value as D.

Examples 1-6 prepared molecular sieves provided by the present invention; Comparative Examples 1-8 prepared comparative molecular sieves.

Example 1

Add 100g of Beta molecular sieve (manufactured by Catalyst Qilu Branch, SiO ₂ /Al ₂ O ₃ =25, sodium oxide content 4.5% by weight, the same below; on a dry basis) with water to obtain a molecular sieve slurry with a solid content of 10% by weight, and add 11.4g High alkali sodium metaaluminate solution (Na ₂ O is 290g/L, Al ₂ O ₃ is 40g/L, solution density is 1.353g/mL), heated to 50°C and stirred at constant temperature for 0.5h, filtered and washed until neutral; The filter cake is beaten with water to obtain a molecular sieve slurry with a solid content of 20% by weight, 5.3g of oxalic acid is added during stirring, and then 51g of hydrochloric acid (10% by mass fraction) and 17g of fluosilicic acid (20% by mass) are slowly added dropwise at the same time, and the temperature is raised to 50°C Stir at constant temperature for 1 hour, filter, wash and dry to obtain molecular sieve sample A. The physical and chemical properties of molecular sieve sample A are listed in Table 1.

Comparative example 1

100g of Beta molecular sieve (mass on a dry basis) was beaten with water to obtain a molecular sieve slurry with a solid content of 10% by weight, and 22.4g of high alkali sodium metaaluminate solution (Na ₂ O was 290g/L, Al ₂ O ₃ was 40g/L, and the solution Density is 1.353g/mL), heated to 50°C and stirred at constant temperature for 0.5h, filtered and washed until neutral; the filter cake was beaten with water to obtain a molecular sieve slurry with a solid content of 20% by weight, and 240g of fluosilicic acid (concentration 20% ), heated to 50° C. and stirred for 1 h, filtered, washed and dried to obtain molecular sieve sample DB1. The physical and chemical properties of molecular sieve sample DB1 are listed in Table 1.

Comparative example 2

Add water to 100g Beta molecular sieve (mass on a dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 25g of high alkali sodium metaaluminate solution ( _Na2O is 280g/L, _Al2O3 is _40g /L, and the solution density is 1.25g/mL), heated to 50°C and stirred at a constant temperature for 0.5h, filtered and washed until neutral, and dried to obtain molecular sieve sample DB2. The physical and chemical properties of molecular sieve sample DB2 are listed in Table 1.

Comparative example 3

100g Beta molecular sieve (mass on a dry basis) was added with water to be prepared into a molecular sieve slurry with a solid content of 10% by weight, 5.3g oxalic acid was added during stirring, and then 51g hydrochloric acid (mass fraction 10%) and 17g fluosilicic acid (concentration 20%) were slowly added dropwise, The temperature was raised to 50° C. and stirred for 1 hour, filtered, washed and dried to obtain a molecular sieve sample DB3. The physical and chemical properties of the molecular sieve sample DB3 are listed in Table 1.

Comparative example 4

Add water to 100g Beta molecular sieve (mass on dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 16.42g NaOH (purity 96%), heat up to 50°C and stir at a constant temperature for 0.5h, filter and wash until neutral; add water to beat the filter cake to obtain Molecular sieve slurry with a solid content of 20% by weight, 12g of oxalic acid was added during stirring, and then 280g of hydrochloric acid (mass fraction 10%) was added, the temperature was raised to 50°C and stirred at a constant temperature for 1h, filtered, washed and dried to obtain molecular sieve sample DB4, the physicochemical properties of molecular sieve sample DB4 were listed in Table 1.

Comparative example 5

Add 100g of Beta molecular sieve (mass on a dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 10.42g of NaOH (purity 96%), heat up to 50°C and stir at a constant temperature for 0.5h, filter and wash until neutral; add water to beat the filter cake to obtain Add 40 g of oxalic acid to the molecular sieve slurry with a solid content of 20% by weight, heat up to 50° C. and stir for 1 hour, filter, wash and dry to obtain molecular sieve sample DB5. The physical and chemical properties of molecular sieve sample DB5 are listed in Table 1.

Comparative example 6

Add water to 100g Beta molecular sieve (mass on a dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 10.42g of NaOH (purity: 96%), heat up to 50°C and stir at a constant temperature for 0.5h; add water to the filter cake to obtain a solid content of 20% by weight Add 300g hydrochloric acid (mass fraction 10%) to the molecular sieve slurry, heat up to 50°C and stir for 1h at a constant temperature, filter, wash and dry to obtain molecular sieve sample DB6, the physicochemical properties of molecular sieve sample DB6 are listed in Table 1.

Comparative example 7

Add water to 100g of Beta molecular sieve (mass on a dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 10.42g of LiOH (purity: 96%), heat up to 50°C and stir at a constant temperature for 0.5h; add water to the filter cake to obtain a solid content of 20% by weight Add 30g of oxalic acid to the molecular sieve slurry during stirring, then slowly dropwise add 100g of fluosilicic acid (concentration: 20%), heat up to 50°C and stir at a constant temperature for 1h, filter, wash and dry to obtain molecular sieve sample DB7, the physical and chemical properties of molecular sieve sample DB7 are listed in Table 1 .

Comparative example 8

Add water to 100g Beta molecular sieve (mass on a dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 10.42g of NaOH (purity: 96%), heat up to 50°C and stir at a constant temperature for 0.5h; add water to the filter cake to obtain a solid content of 20% by weight Molecular sieve slurry, add 180g hydrochloric acid (mass fraction 10%) during stirring, then slowly dropwise add 100g fluosilicic acid (concentration 20%), heat up to 50°C and stir at constant temperature for 1h, filter, wash and dry to obtain molecular sieve sample DB8, molecular sieve sample DB8 physical and chemical The properties are listed in Table 1.

Example 2

Add water to 100g Beta molecular sieve (mass on dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 16g NaOH (purity 96%), heat up to 50°C and stir at a constant temperature for 0.5h, filter and wash until neutral; add water to beat the filter cake to obtain a solid Molecular sieve slurry with a content of 20% by weight, 16g of oxalic acid was added during stirring, and then 108g of hydrochloric acid (mass fraction 10%) and 26g of fluosilicic acid (concentration of 20%) were slowly added dropwise at the same time, the temperature was raised to 50°C and stirred at a constant temperature for 1 hour, filtered, washed and dried Molecular sieve sample B was obtained, and the physicochemical properties of molecular sieve sample B are listed in Table 2.

Example 3

Add water to 100g Beta molecular sieve (mass on a dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 19g NaOH (purity 96%), heat up to 50°C and stir at a constant temperature for 0.5h, filter and wash until neutral; add water to the filter cake to make a solid Molecular sieve slurry with a content of 20% by weight, 26g of oxalic acid was added during stirring, and then 250g of sulfuric acid (mass fraction 10%) and 95g of fluosilicic acid (concentration of 20%) were slowly added dropwise at the same time, the temperature was raised to 50°C and stirred at a constant temperature for 1 hour, filtered, washed and dried Molecular sieve sample C was obtained, and the physicochemical properties of molecular sieve sample C are listed in Table 2.

Example 4

Add water to 100g Beta molecular sieve (mass on dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 30g NaOH (purity 96%), heat up to 50°C and stir at a constant temperature for 0.5h, filter and wash until neutral; add water to beat the filter cake to obtain a solid Molecular sieve slurry with a content of 20% by weight, 33g of oxalic acid was added during stirring, and then 240g of hydrochloric acid (mass fraction 10%) and 95g of fluosilicic acid (concentration of 20%) were slowly added dropwise at the same time, the temperature was raised to 50°C and stirred at a constant temperature for 1 hour, filtered, washed and dried The molecular sieve sample D was obtained, and the physicochemical properties of the molecular sieve sample D are listed in Table 2.

Example 5

Add water to 100g Beta molecular sieve (mass on dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 22g NaOH (purity 96%), heat up to 50°C and stir at a constant temperature for 0.5h, filter and wash until neutral; add water to beat the filter cake to obtain a solid Molecular sieve slurry with a content of 20% by weight, 5g of citric acid was added during stirring, and then 250g of hydrochloric acid (mass fraction 10%) and 130g of fluosilicic acid (concentration of 20%) were slowly added dropwise at the same time, the temperature was raised to 50°C and stirred for 1 hour, filtered and washed Molecular sieve sample E was obtained by drying, and the physicochemical properties of molecular sieve sample E are listed in Table 2.

Example 6

Add water to 100g Beta molecular sieve (mass on dry basis) to prepare a molecular sieve slurry with a solid content of 10% by weight, add 25g KOH (purity 96%), heat up to 50°C and stir at a constant temperature for 0.5h, filter and wash until neutral; add water to beat the filter cake to obtain a solid Molecular sieve slurry with a content of 20% by weight, 35g of oxalic acid was added during stirring, and then 190g of nitric acid (mass fraction 10%) and 90g of fluosilicic acid (concentration 20%) were slowly added dropwise at the same time, the temperature was raised to 50°C and stirred at a constant temperature for 1 hour, filtered, washed and dried The molecular sieve sample F was obtained, and the physicochemical properties of the molecular sieve sample F are listed in Table 2.

As can be seen from the data in Table 1, the conventional alkali treatment (DB2) will make the surface of Beta molecular sieve aluminum-rich, using a single organic acid oxalic acid dealumination (DB5), or using a single inorganic hydrochloric acid dealumination (DB6) and using organic Both acid oxalic acid and inorganic hydrochloric acid compound (DB4) cannot effectively remove Al from the molecular sieve, and the surface of the molecular sieve is still rich in aluminum, and only after using fluosilicic acid can a better dealumination effect be obtained, improving the molecular sieve Aluminum distribution. When fluorosilicate dealumination (DB1) is used alone, the aluminum distribution of the molecular sieve can be improved, but the mesopores are relatively few. Fluorosilicic acid composite organic acid oxalate dealumination (DB7) also cannot obtain a higher mesopore ratio. Fluorosilicic acid composite inorganic hydrochloric acid dealumination (DB8), although the mesopore volume has increased, but the conversion rate of ethylcyclohexane and the yield of olefins are not as high as the molecular sieve provided by the present invention. Only using compound acid for treatment (DB3) can not increase the volume of mesoporous pores. The present invention adopts the desiliconization treatment of molecular sieve first, and then uses the compound acid system to carry out dealumination treatment under the synergistic effect of three acids, which can be On the premise of ensuring the integrity of molecular sieve crystal structure and mesoporous channel structure, aluminum distribution and acid distribution are improved.

Examples 7-15 prepare cracking aids provided by the present invention; comparative examples 9-17 prepare comparative aids.

Example 7

Preparation of phosphoaluminum glue: 1.05 kilograms of pseudoboehmite (dry basis) and 3.35 kilograms of decationized water were beaten for 30 minutes, and 4.9 kilograms of concentrated phosphoric acid (chemically pure, containing 85% by weight of phosphoric acid) were added to the slurry under stirring, and the temperature was raised to 70°C, and then react at this temperature for 45 minutes to make a colorless and transparent phosphoraluminum glue (phosphoraluminum sol). Among them, the content of P ₂ O ₅ is 30.6% by weight, the content of Al ₂ O ₃ is 10.5% by weight, and the pH=1.7.

Take molecular sieve A, pseudo-boehmite and kaolin, add decationized water and aluminum sol for beating for 120 minutes, add FeCl ₃ 6H ₂ O aqueous solution ( _FeCl concentration 30% by weight, FeCl ₃ . The aqueous solution concentration of 6H ₂ O has no special instructions, the concentration of FeCl ₃ is 30% by weight), the colloidal solid content is controlled to be 34% by weight, the pH value of the slurry is adjusted to 3.0 by hydrochloric acid, then beating for 45 minutes, adding phosphoraluminum glue, and stirring For 30 minutes, the resulting slurry was then spray dried to obtain microspheres. The microspheres were calcined at 500°C for 1 hour to prepare additive C1. The additive formulations are shown in Table 3.

Comparative example 9-16

The preparation process of Comparative Examples 9-16 is the same as that of Example 7, the difference is that molecular sieves DB1-DB8 are used to replace A to prepare contrast additives D1-D8. See Table 3 for the formulations of the comparative additives.

Comparative example 17

The preparation process of Comparative Example 17 is the same as that of Example 7, except that it is replaced by conventional β molecular sieves (manufactured by Catalyst Qilu Branch, SiO ₂ /Al ₂ O ₃ =25, ammonium exchanged to below 0.1% by weight of sodium oxide, dry basis mass) Molecular sieve A, prepared contrast aid D9. See Table 3 for the formulations of the comparative additives.

Example 8

Take molecular sieve B and kaolin, add decationized water and aluminum sol and beat for 120 minutes to obtain a slurry with a solid content of 40% by weight, and spray dry the obtained slurry to obtain microspheres. The microspheres were calcined at 500° C. for 1 hour to obtain the additive C2 provided by the present invention. The additive formulations are shown in Table 4.

Example 9

Take molecular sieve C, kaolin and pseudo-boehmite, add decationized water and aluminum sol and beat for 120 minutes to obtain a slurry with a solid content of 30% by weight, and add hydrochloric acid with a concentration of 36% by weight under stirring. The amount of hydrochloric acid makes the pH of the slurry 3.0, beating for 45 minutes, then adding phosphoraluminum glue (prepared according to the method in Example 7) to the mixed slurry, stirring for 30 minutes, and spray-drying the obtained slurry to obtain microspheres. The microspheres were calcined at 500°C for 1 hour to prepare additive C3. The additive formulations are shown in Table 4.

Example 10

Take molecular sieve C, kaolin and pseudo-boehmite, add decationized water and aluminum sol for beating for 120 minutes, add an aqueous solution of FeCl ₃ 6H ₂ O under stirring to obtain a slurry with a solid content of 30% by weight, and add a concentration of 36% by weight of Hydrochloric acid, the amount of hydrochloric acid is used to make the pH value of the slurry 3.0, then beating for 45 minutes, and the resulting slurry is spray-dried to obtain microspheres. The microspheres were calcined at 500°C for 1 hour to prepare additive C4. The additive formulations are shown in Table 4.

Example 11

Mix decationized water and aluminum sol, add molecular sieve B, diatomaceous earth and pseudo-boehmite therein, beat for 120 minutes, add FeCl ₃ ·6H ₂ O aqueous solution under stirring to obtain a slurry with a solid content of 35% by weight, Add hydrochloric acid to adjust the pH value of the slurry to 2.8, beat for 30 minutes, add diammonium hydrogen phosphate solid, beat for 30 minutes, then spray dry the obtained slurry to obtain microspheres, and roast the microspheres at 500 ° C for 1 hour to obtain Auxiliary C5. The additive formulations are shown in Table 4.

Example 12

Take molecular sieve A and kaolin, add decationized water and aluminum sol to beat for 120 minutes, add Co(NO ₃ ) ₂ ·6H ₂ O aqueous solution (Co(NO ₃ ) ₂ concentration 20% by weight) under stirring, and obtain a solid content of 38 % by weight of the slurry, the pH value of the slurry was adjusted to 3.3 with hydrochloric acid, then beating for 30 minutes, then adding phosphoraluminum glue (prepared according to the method of Example 7) in the mixed slurry, stirring for 30 minutes, and spraying the obtained slurry to obtain Micro ball. The microspheres were calcined at 500°C for 1 hour to prepare additive C6. The additive formulations are shown in Table 4.

Example 13

Take molecular sieve D and pseudo-boehmite, add decationized water and aluminum sol to beat for 120 minutes, add Ni(NO ₃ ) ₂ ·6H ₂ O aqueous solution (Ni(NO ₃ ) ₂ concentration 20% by weight) under stirring, to obtain Add hydrochloric acid to the slurry with a solid content of 30% by weight to make the pH value of the slurry 3.0, beat for 45 minutes, and spray-dry the obtained slurry to obtain microspheres.

After calcining the obtained microspheres at 500°C for 1 hour, add diammonium hydrogen phosphate aqueous solution, raise the temperature to 60°C under stirring, and react at this temperature for 20 minutes, vacuum filter the slurry, dry it, and then calcinate at 500°C for 1 hour. hours, the auxiliary agent C7 was prepared. The additive formulations are shown in Table 4.

Example 14

Take molecular sieve E, kaolin and water glass, add decationized water and beat for 120 minutes, add FeCl ₃ 6H ₂ O aqueous solution under stirring to obtain a slurry with a solid content of 33% by weight, adjust the pH value of the slurry to 3.0 by hydrochloric acid, and then Beat for 45 minutes, then add phosphoraluminum glue (prepared according to the method described in Example 7) to the slurry, stir for 30 minutes, and spray-dry the obtained slurry to obtain microspheres. The microspheres were calcined at 400°C for 1 hour to prepare additive C8. The additive formulations are shown in Table 4.

Example 15

Take molecular sieve F, kaolin and pseudo-boehmite, add decationized water and aluminum sol and beat for 120 minutes to obtain a slurry with a solid content of 30% by weight, add hydrochloric acid to make the pH of the slurry 3.0, beat for 45 minutes, and then pour into the slurry Add phosphoraluminum glue (prepared according to the method in Example 7), stir for 30 minutes, and spray-dry the obtained slurry to obtain microspheres.

After the obtained microspheres were calcined at 500°C for 1 hour, they were uniformly impregnated with diammonium hydrogen phosphate aqueous solution ( _P2O5 concentration 8% by weight) at a weight ratio of 1:1, dried at 120°C, and calcined at 500°C for 1 hour _. hour, and then impregnated with FeCl ₃ ·6H ₂ O aqueous solution (FeCl ₃ concentration 4% by weight) at a weight ratio of 1:1, dried at 120°C, and then calcined at 500°C for 1 hour to obtain additive C9. The additive formulations are shown in Table 4.

Examples 16-24

The following examples take a fixed fluidized bed reactor as an example to illustrate the cracking reaction effect of the cracking aid provided by the present invention.

30 grams of additives C1-C9 were aged for 12 hours at 800° C. and 100% water vapor atmosphere. Different weights of aging-treated additives C1-C9 were mixed with different weights of industrial FCC equilibrium catalysts (the industrial brand is DVR-3 FCC equilibrium catalysts, the main properties are shown in Table 5). The catalyst mixture was loaded into the reactor of a small-scale fixed fluidized bed reactor, and the raw oil shown in Table 6 was subjected to catalytic cracking. Table 7 and Table 8 show the weight composition of the catalyst mixture used, the reaction conditions and the reaction results.

Comparative example 18-27

The following comparative examples take a fixed fluidized bed reactor as an example to illustrate the use of contrast aids.

The same stock oil is carried out catalytic cracking by the method for embodiment 16, and difference is that the catalyst used is respectively 100% industrial FCC equilibrium catalyst, according to the method of embodiment 16 through aging comparison additives D1-D9 and industrial FCC equilibrium catalyst mixture. Table 7 shows the composition of the catalyst mixture used, the reaction conditions and the reaction results.

As can be seen from Table 7 and Table 8, compared with the contrast agent, the catalytic aid provided by the present invention can effectively increase the catalytic cracking liquefied gas production rate, especially the productive rate of isobutylene and propylene, significantly improve catalytic cracking liquefaction Increase the concentration of propylene and isobutene in the gas, increase the concentration of ethylene in the dry gas, increase the octane number of gasoline, increase the recovery and conversion rate of catalytic cracking liquid, and improve the selectivity of coke.

Table 1

Table 2

table 3

Table 4

table 5

project Industrial Balance Catalyst DVR-3 Metal content, ppm Ni/V 8762/1387 Fe/Sb 5214/2512 Ca 1516 micro activity index 60

Table 6

Raw oil name Pipeline wax oil mixed with residual oil Density (20℃), g/ ^cm3 0.9070 Viscosity (100℃), ^mm2 /s 10.41 freezing point, ℃ 40 Carbon residue, wt% 3.1 Elemental composition, wt% C/H 86.39/12.53 S/N 0.8/0.29 Four components, wt% saturated hydrocarbon 56.8 Aromatics 24.2 colloid 18.2 Asphaltenes 0.8 Metal content, ppm V/Ni 0.8/7.0 Fe/Cu 7.8/0.1 Na 2.6 Distillation range, ℃ Initial boiling point/5% 241/309 10%/20% 343/387 30%/40% 413/432 50%/60% 450/466 70%/80% 493/535

Table 7

Table 8

Claims (15)

1. A catalytic cracking aid containing a Beta molecular sieve rich in mesoporous, by weight and based on the dry weight of the aid, the aid contains 10-75% by weight on a dry basis Mesoporous-rich Beta molecular sieve, 0-60% by weight clay on dry basis, 15-60% by weight inorganic oxide binder on dry basis, _0-25 % by weight _P2O5 % of phosphorus additives and 0-15% by weight of group VIII metal additives in terms of oxides, wherein the Al distribution parameter D of the molecular sieve satisfies: 0.4≤D≤0.8, wherein, D=Al(S)/Al( C), Al(S) represents the aluminum content in any area greater than 100 square nanometers within the distance H from the edge of the molecular sieve crystal grain measured by the TEM-EDS method, and Al(C) represents the molecular sieve measured by the TEM-EDS method The aluminum content in any area larger than 100 square nanometers within the distance H from the geometric center of the crystal plane of the crystal grain, wherein the H is 10% of the distance from a certain point on the edge of the crystal plane to the geometric center of the crystal plane; the molecular sieve The micropore specific surface area of the molecular sieve is 350-500 ^m2 /g, and the ratio of the mesopore volume to the total pore volume of the molecular sieve is 30-70% by volume. 2. The additive according to claim 1, wherein the Al distribution parameter D of the molecular sieve satisfies: 0.55≤D≤0.75; the micropore specific surface area of the molecular sieve is 370-450 ^m2 /g, and the molecular sieve The proportion of the mesopore volume to the total pore volume is 35-60% by volume. 3. The auxiliary agent according to claim 1, wherein, by weight and based on the dry weight of the auxiliary agent, the auxiliary agent contains 20-60% by weight of mesopore-rich Beta molecular sieve, 10-45% by weight of clay based on dry basis, 25-50% by weight of inorganic oxide binder based on dry basis, _5-15 % by weight of phosphorus additive based on _P2O5 and 1-10% by weight of Group VIII metal additives, calculated as oxides. 4. The auxiliary agent according to claim 1, wherein the clay comprises a compound selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, letronite, diatomite, halloysite, soap At least one of stone, bentonite and hydrotalcite, and the inorganic oxide binder includes at least one selected from pseudo-boehmite, aluminum sol, silica-alumina sol and water glass. 5. The auxiliary agent according to claim 1, wherein the phosphorus additive is introduced into the auxiliary agent in the form of a phosphorus-containing compound, and the phosphorus-containing compound comprises an oxide selected from phosphorus, phosphate, phosphite, At least one of basic phosphate and acid phosphate; The Group VIII metal includes at least one selected from Fe, Co and Ni, and the Group VIII metal additive is introduced into the auxiliary agent in the form of a metal-containing compound, and the metal-containing compound includes a compound selected from the group consisting of oxides, hydroxides At least one of compounds, chlorides, nitrates, sulfates, phosphates and organic compounds. 6. A preparation method for catalytic cracking additive, the preparation method comprising: Mixing mesoporous-rich Beta molecular sieves, inorganic oxide binders and water, adding or not adding clay, beating, and spray drying; wherein, phosphorus additives are introduced or not, and group VIII metal additives are introduced or not; By weight and based on the dry basis weight of the preparation raw material of the auxiliary agent, the preparation raw material of the auxiliary agent contains 10-75% by weight of mesoporous-rich Beta molecular sieves on a dry basis. 0-60% by weight of clay, 15-60% by weight of inorganic oxide binder based on dry basis, 0-25% by weight of phosphorus additives based on P ₂ O ₅ and 0-25% by weight based on oxides. 15% by weight of Group VIII metal additives; The Al distribution parameter D of the molecular sieve satisfies: 0.4≤D≤0.8, wherein, D=Al(S)/Al(C), and Al(S) represents the crystal plane edge direction of the molecular sieve grain measured by the TEM-EDS method The aluminum content in any area greater than 100 square nanometers within the inner H distance, Al(C) means the aluminum content in any area greater than 100 square nanometers within the H distance from the geometric center of the crystal plane of the molecular sieve grain measured by the TEM-EDS method , wherein the H is 10% of the distance from a certain point on the edge of the crystal plane to the geometric center of the crystal plane; the micropore specific surface area of the molecular sieve is 350-500 ^m2 /g, and the mesopore volume of the molecular sieve accounts for the total The proportion of the pore volume is 30-70% by volume. 7. preparation method according to claim 6, wherein, the preparation step of the Beta molecular sieve that is rich in described mesoporous comprises: a, carry out alkali treatment in alkaline solution with sodium Beta molecular sieve, and after filtering and washing, obtain alkali treatment molecular sieve; b. The alkali-treated molecular sieve obtained in step a is dealuminated in a complex acid dealumination agent solution composed of fluosilicic acid, organic acid and inorganic acid, and after filtering and washing, the mesoporous-rich molecular sieve is obtained Beta molecular sieve. 8. The preparation method according to claim 7, wherein the alkaline solution is at least one selected from sodium hydroxide solution, potassium hydroxide solution, lithium hydroxide solution, ammonia and high alkali sodium metaaluminate solution Kind; in terms of oxides, the sodium content of the high alkali sodium metaaluminate solution is 270-310 grams per liter, the aluminum content is 30-50 grams per liter, and the density of the high alkali sodium metaaluminate solution is 1.25-1.45 g/ml. 9. preparation method according to claim 8, wherein, the condition of alkali treatment described in step a comprises: the ratio of the weight of the alkali in the molecular sieve and alkaline solution with dry basis weight is 1:(0.02-0.3 ); wherein, the weight of the alkali in the sodium hydroxide solution is in the weight of sodium hydroxide, the weight of the alkali in the potassium hydroxide solution is in the weight of potassium hydroxide, and the weight of the alkali in the lithium hydroxide solution is in the weight of potassium hydroxide. The weight of the base is calculated by the weight of lithium hydroxide, the weight of the base in the ammonia water is calculated by the weight of ammonia monohydrate, and the weight of the base in the high alkali sodium metaaluminate solution is calculated by the weight of sodium oxide. 10. The preparation method according to claim 7, wherein the conditions of the alkali treatment in step a include: the temperature of the alkali treatment is 25-100° C., and the time of the alkali treatment is 0.5-6 hours. 11. The preparation method according to claim 7, wherein the organic acid in step b is at least one selected from ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid It is at least one selected from hydrochloric acid, sulfuric acid and nitric acid. 12. The preparation method according to claim 7, wherein the conditions of the dealumination treatment described in step b include: the weight ratio of molecular sieve, fluosilicic acid, organic acid and inorganic acid in dry basis weight is 1: (0.03-0.5):(0.05-0.4):(0.05-0.5); the treatment temperature is 25-100°C, and the treatment time is 0.5-6 hours. 13. The preparation method according to claim 7, wherein the conditions of the dealumination treatment described in step b include: the weight ratio of molecular sieve, fluosilicic acid, organic acid and inorganic acid in dry basis weight is 1: (0.05-0.3):(0.1-0.3):(0.1-0.3). 14. The preparation method according to claim 6, wherein the clay comprises a compound selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, letronite, diatomite, halloysite, soap At least one of stone, bentonite and hydrotalcite, and the inorganic oxide binder includes at least one selected from pseudo-boehmite, aluminum sol, silica-alumina sol and water glass. 15. The preparation method according to claim 6, wherein, the phosphorus additive is introduced into the auxiliary agent in the form of a phosphorus-containing compound, and the phosphorus-containing compound comprises an oxide selected from phosphorus, phosphate, phosphite, At least one of basic phosphate and acid phosphate; The Group VIII metal includes at least one selected from Fe, Co and Ni, and the Group VIII metal additive is introduced into the auxiliary agent in the form of a metal-containing compound, and the metal-containing compound includes a compound selected from the group consisting of oxides, hydroxides At least one of compounds, chlorides, nitrates, sulfates, phosphates and organic compounds.