m-xylene adsorbent and method for preparing the same

Abstract

An m-xylene adsorbent comprising 94 to 99.9 mass % Y molecular sieve and 0.1 to 6 mass % substrate, the Y molecular sieve consisting of an amorphous transition Y molecular sieve and a Y molecular sieve produced by crystal transformation, the amorphous transition Y molecular sieve being a mesoporous nano-Y molecular sieve having a crystal size of 20 to 450 nanometers, and two types of mesoporous pores having most likely pore diameters of 5 to 20 nanometers and 25 to 50 nanometers, respectively. The adsorbent is used for the adsorptive separation of m-xylene from mixed C8 aromatic hydrocarbons, and has good mass transfer performance, relatively high m-xylene adsorption selectivity and adsorption capacity.

Description

[Technical Field]

[0001] The present invention relates to molecular sieve adsorbents and methods for preparing the same, and more specifically, to m-xylene adsorbents and methods for preparing the same. [Background technology]

[0002] m-xylene (MX) is an important organic chemical industrial raw material widely used in synthetic resins, agrochemicals, pharmaceuticals, paints, dyes, and other fields. Industrially, highly pure m-xylene is usually obtained by separating it from a mixed C8 aromatic hydrocarbon containing ethylbenzene, p-xylene, m-xylene, and o-xylene using adsorption separation techniques.

[0003] Adsorbents are the foundation and core of adsorption separation technology, and many of their active ingredients are zeolite materials. CN1136549A and US6137024 disclose adsorbents using Silicalite-1 and hydrogen-type β-zeolite as active ingredients, respectively, but Silicalite-1 and β-zeolite have relatively low adsorption capacities, limiting their use. Relatively speaking, Y molecular sieves have relatively high adsorption capacities and therefore offer broader applicability.

[0004] US4306107 discloses a method for separating xylene and ethylbenzene from a mixed C8 aromatic hydrocarbon. In this method, NaY zeolite is used as the active adsorbent and toluene is used as the desorbent. By taking advantage of the characteristics of NaY zeolite, which has the strongest adsorption capacity for m-xylene, moderate adsorption capacity for p-xylene and o-xylene, and weakest adsorption capacity for ethylbenzene, a mixed C8 aromatic hydrocarbon is fed into a simulated moving bed for a backflow operation, yielding m-xylene, p-xylene, o-xylene, and ethylbenzene at different positions on the simulated moving bed, respectively.

[0005] US4326092 discloses a method for separating m-xylene from mixed C8 aromatic hydrocarbons. Higher m-xylene selectivity can be obtained by preparing an adsorbent using NaY zeolite with a molar ratio of silica to alumina of 4.5–5.0.

[0006] US5900523 reports that by using an adsorbent containing NaY zeolite with a molar ratio of silica to alumina of 4.0 to 6.0 as the active ingredient, and with a water content of 1.5 to 2.5% by mass corresponding to the LOI at 500°C, good separation effects were obtained by using indan as a desorbent for liquid-phase adsorption separation of m-xylene at 100 to 150°C.

[0007] CN1939883A discloses a method for separating m-xylene from isomers of C8 aromatic hydrocarbons. The adsorbent is prepared by using NaY zeolite having a molar ratio of silica to alumina of 5-6, the zeolite having a water content of 0-8% by mass and an adsorption temperature of 25-250°C, and the desorbent is selected from tetralin and its alkylated derivatives. [Overview of the project]

[0008] The object of the present invention is to provide an m-xylene adsorbent and a method for preparing the same, which can be used for the adsorption separation of m-xylene from mixed C8 aromatic hydrocarbons. The adsorbent has good mass transfer performance, relatively high m-xylene adsorption selectivity and adsorption capacity.

[0009] The m-xylene adsorbent provided by the present invention comprises 94-99.9% by mass of Y molecular sieves and 0.1-6% by mass of a substrate, wherein the Y molecular sieves consist of amorphous transition Y molecular sieves and Y molecular sieves produced by crystalline transition, and the amorphous transition Y molecular sieves are mesoporous nano-Y molecular sieves having a crystal grain size of 20-450 nanometers and containing two types of mesoporous pores, each having the most likely pore diameters of 5-20 nanometers and 25-50 nanometers, respectively.

[0010] The amorphous transition Y molecular sieve in the active component Y molecular sieve of the adsorbent of the present invention is a self-aggregated body formed by the self-aggregation of nanoscale Y molecular sieve crystal grains, and is a mesoporous nano Y molecular sieve containing two types of mesoporous pores. The adsorbent is used for the adsorption separation of m-xylene from mixed C8 aromatic hydrocarbons, exhibits relatively high adsorption selectivity for m-xylene, relatively high adsorption capacity and mass transfer rate, and can significantly improve the processing capacity of the adsorbent for adsorption separation raw materials. [Brief explanation of the drawing]

[0011] [Figure 1] This is the X-ray diffraction (XRD) spectrum of the mesoporous nano-Y molecular sieve prepared in Example 1 of the present invention. [Figure 2] This is a scanning electron microscope (SEM) image of a mesoporous nano-Y molecular sieve prepared in Example 1 of the present invention. [Figure 3] This is the pore size distribution curve of the mesoporous nano-Y molecular sieve prepared in Example 1 of the present invention. [Figure 4] This is the pore size distribution curve of the mesoporous nano-Y molecular sieve prepared in Example 2 of the present invention. [Figure 5] This is the pore size distribution curve of the mesoporous nano-Y molecular sieve prepared in Example 3 of the present invention. [Figure 6] This is the pore size distribution curve of the mesoporous nano-Y molecular sieve prepared in Example 4 of the present invention. [Figure 7] This is the pore size distribution curve of the mesoporous nano-Y molecular sieve prepared in Example 5 of the present invention. [Figure 8] This is the XRD spectrum of the Y molecular sieve prepared in Comparative Example 1. [Figure 9] This is an SEM image of the Y molecular sieve prepared in Comparative Example 1. [Figure 10] This is the pore size distribution curve of the Y molecular sieve prepared in Comparative Example 1. [Figure 11] This is the pore size distribution curve of the Y molecular sieve prepared in Comparative Example 3. [Figure 12] This is a schematic diagram of adsorption separation in a small-scale simulated mobile bed.

Embodiments for Carrying out the Invention

[0012] The active component Y molecular sieve in the adsorbent of the present invention consists of an amorphous transition Y molecular sieve and a Y molecular sieve generated by crystal transition. The amorphous transition Y molecular sieve is an aggregate formed by self-aggregation of nanoscale Y molecular sieve crystallites, and the aggregate has a relatively large particle size. The above-mentioned nanoscale Y molecular sieve is advantageous for improving mass transfer performance, and the relatively large particle size can better solve the problem of difficult solid-liquid separation caused by the generation of nanoscale molecular sieve crystallites during molecular sieve synthesis. In addition, the nano Y molecular sieve aggregate contains two types of mesoporous pores, which further gives good mass transfer performance, and the improvement of mass transfer performance can further improve the adsorption selectivity of mesoporous nano Y molecular sieve for m-xylene.

[0013] In the present invention, the mesoporous nano Y molecular sieve (amorphous transition Y molecular sieve) is mixed with kaolin mineral as a binder, a shaping aid and a silicon source, and then ball-rolled and formed, and fired at a high temperature to convert the kaolin mineral into metakaolin. Then, through in-situ crystallization by alkali treatment, metakaolin is converted into Y molecular sieve, and then dried and fired to obtain an adsorbent.

[0014] Preferably, the adsorbent in the present invention contains 98 to 99.9% by mass of Y molecular sieve and 0.1 to 2% by mass of a substrate.

[0015] The adsorbent in the present invention comprises two types of Y molecular sieves. One is an amorphous transition Y molecular sieve, which is a mesoporous nano-Y molecular sieve having two types of mesoporous pores, and the other is a binder used in the adsorbent molding process, which is generally a Y molecular sieve formed by in-situ crystallization of kaolin mineral and a silicon source added in the molding process. Preferably, the adsorbent comprises 84-93% by mass of amorphous transition Y molecular sieves, 1-15.9% by mass of Y molecular sieves produced by crystalline transitions, and 0.1-6% by mass of a substrate, and more preferably, the adsorbent comprises 84-93% by mass of amorphous transition Y molecular sieves, 5-15.9% by mass of Y molecular sieves produced by crystalline transitions, and 0.1-2% by mass of a substrate.

[0016] The mesoporous nano-Y molecular sieve in the present invention is preferably a self-aggregate of nanoscale Y molecular sieve crystal grains, the self-aggregate preferably having a particle size of 0.5 to 1.5 microns, and the nanoscale Y molecular sieve crystal grains in the self-aggregate preferably having a particle size of 20 to 400 nanometers, more preferably 50 to 300 nanometers. The nano-Y molecular sieve self-aggregate contains two types of mesoporous pores, each having a pore diameter of 5 to 20 nanometers and 25 to 50 nanometers, preferably 10 to 20 nanometers and 30 to 50 nanometers, respectively.

[0017] The molar ratio of SiO2 / Al23 in the mesoporous nano-Y molecular sieve is preferably 4.0 to 5.5.

[0018] The mesoporous nano-Y molecular sieve is preferably 740-1000 m 2 / g, more preferably 750-900m 2 Specific surface area per g, preferably 0.40 to 0.65 cm² 3 / g, more preferably 0.40~0.55cm 3 Total pore volume per g, preferably 0.08 to 0.35 cm³ 3 / g, more preferably 0.10~0.25cm 3 It has a mesoporous pore volume of / g.

[0019] The substrate in the adsorbent is the residue of kaolin mineral after crystallization by in-situ crystallization. The kaolin mineral is preferably selected from at least one of kaolinite, dickite, perlite, ovenstone, and halloysite.

[0020] The adsorbent in the present invention is preferably in the form of pellets, and its particle size is preferably 300 to 850 microns.

[0021] The method for preparing the adsorbent of the present invention includes the following steps: (1) Amorphous transition NaY molecular sieve, kaolin mineral, silicon source, and molding aid are uniformly mixed, ball-rolled into pellets, dried, and then calcined at 530-600°C. The mass ratio of the amorphous transition NaY molecular sieve to the kaolin mineral is 85-94:6-15, and the mass ratio of silicon dioxide contained in the added silicon source to the kaolin mineral is 0.1-3.6; (2) The pellets obtained after firing in step (1) are subjected to in-situ crystallization at 85-100°C using sodium hydroxide or a mixed solution of sodium hydroxide and water glass so that the kaolin minerals within them are crystallized in-situ to form a Y molecular sieve, and then washed and dried.

[0022] Step (1) of the above method involves mixing an amorphous transition NaY molecular sieve, a kaolin mineral, a silicon source, and a molding aid, and then ball rolling the mixture. The crystalline material contained in the kaolin mineral is preferably selected from kaolinite, dickite, pearlite, ovenstone, halloysite, or a mixture thereof. The mass percentage of crystalline material in the kaolin mineral is at least 90%.

[0023] The silicon source in step (1) is preferably selected from one or more of ethyl orthosilicate, silica sol, water glass, sodium silicate, silica gel, and white carbon black. Preferably, the mass ratio of silicon dioxide contained in the added silicon source to kaolin mineral is 0.2 to 3.0. The molding aid is preferably selected from at least one of lignin, sesbania powder, dried starch, carboxymethylcellulose, and activated carbon. The amount of molding aid added is preferably 1 to 6% by mass of the total amount of solid powder.

[0024] As the molding method in step (1), ball rolling or spray molding is preferred. In the ball rolling method, the apparatus used may be a turntable, a coating kettle, or rollers. During ball rolling, uniformly mixed solid powder is placed in a rotating apparatus, and water is sprayed while rolling to fix the solid powder and agglomerate it into pellets. The amount of water used during rolling is preferably 6 to 30%, more preferably 6 to 20%, of the total mass of the solid. If the added silicon source is solid, it can be mixed with amorphous transition NaY molecular sieves or kaolin minerals; if the added silicon source is liquid, it can be mixed with amorphous transition NaY molecular sieves or kaolin minerals, or added to the water used for ball rolling, or the silicon source can be added to both the solid powder and the water.

[0025] The pellets formed by rolling in step (1) are sieved to select pellets having a certain particle size range, preferably pellets having a particle size of 300 to 850 microns, which are then dried and calcined. The drying temperature is preferably 60 to 110°C and the time is preferably 2 to 12 hours; the calcination temperature is preferably 530 to 700°C and the time is preferably 1 to 6 hours. After calcination, the kaolin minerals in the pellets are converted to metakaolin in step (2) for crystallization into NaY molecular sieves.

[0026] Step (2) of the above method is in-situ crystallization of the molded pellets. In-situ crystallization can be carried out in a sodium hydroxide solution or a mixed solution of sodium hydroxide and water glass. The liquid / solid ratio during in-situ crystallization is preferably 1.5 to 5.0 L / kg, the in-situ crystallization temperature is preferably 90 to 100°C, and the time is preferably 0.5 to 8 hours.

[0027] When a sodium hydroxide solution is used for in-situ crystallization in step (2), the concentration of hydroxide ions in the sodium hydroxide solution used is preferably 0.1 to 3.0 mol / L, more preferably 0.5 to 1.5 mol / L. When a mixed solution of sodium hydroxide and water glass is used for in-situ crystallization, the sodium hydroxide content is preferably 2 to 10% by mass, and the silicon dioxide content is preferably 1 to 6% by mass. After washing and drying the in-situ crystallized adsorbent, spherical adsorbents are obtained. The drying temperature is preferably 70 to 110°C, and the drying time is preferably 2 to 20 hours.

[0028] The method for preparing the amorphous transition NaY molecular sieve in step (1) of the present invention includes the following steps: (I) A molecular sieve synthesis system is formed by taking silicon and aluminum sources at 0-5°C, adding sodium hydroxide and water, and mixing them uniformly. Here, the molar ratios of each raw material are SiO2 / Al2O3 = 5.5-9.5, Na2O / SiO2 = 0.1-0.3, and H2O / SiO2 = 5-25, and the temperature of the synthesis system is 1-8°C. (II) The molecular sieve synthesis system from step (I) is statically aged at 20-40°C for 10-48 hours, then statically crystallized at 90-150°C for 2-10 hours, stirred for 2-10 minutes, and then statically crystallized for another 11-20 hours. The resulting solid is then washed and dried.

[0029] Step (I) of the above method is to prepare a molecular sieve synthesis system at a low temperature: a silicon source and an aluminum source at 0-5°C, preferably 0-4°C, are used, and then sodium hydroxide and water are added to prepare the molecular sieve synthesis system. The molar ratios of each raw material in the molecular sieve synthesis system are preferably SiO2 / Al2O3 = 7-9, Na2O / SiO2 = 0.1-0.25, and H2O / SiO2 = 8-20. The temperature of the synthesis system is preferably 1-5°C.

[0030] Step (II) of the above method is a step of preparing molecular sieves by crystallizing the molecular sieve synthesis system, preferably by statically aging the molecular sieve synthesis system at 20 to 40°C for 15 to 30 hours, then statically crystallizing it at 90 to 120°C for 4 to 9 hours, stirring for 2 to 10 minutes, and continuing to statically crystallize it for 11 to 15 hours. The solid obtained after crystallization is washed and dried to obtain mesoporous nano-Y molecular sieves. The drying temperature is preferably 70 to 100°C, more preferably 75 to 90°C, and the drying time is preferably 2 to 20 hours, more preferably 8 to 16 hours.

[0031] The aluminum source in step (I) of the above method is preferably selected from one or more of low-alkali sodium metaaluminate solution, aluminum oxide, aluminum hydroxide, aluminum sulfate solution, aluminum chloride, aluminum nitrate, and sodium aluminate, and more preferably selected from low-alkali sodium metaaluminate solution and / or aluminum sulfate solution. The Al2O3 content in the low-alkali sodium metaaluminate solution is preferably 17 to 28% by mass, the Na2O content is preferably 19 to 30% by mass, and the molar ratio of Na2O to Al2O3 in the low-alkali sodium metaaluminate solution is preferably 1.7 to 2.5, more preferably 1.7 to 2.2. When the aluminum source is selected from low-alkali sodium metaaluminate solution and aluminum sulfate solution, the mass ratio of aluminum sulfate solution to low-alkali sodium metaaluminate solution is 1 to 6:1, the aluminum in aluminum sulfate solution is calculated based on Al2O3, and the Al2O3 content is preferably 5 to 15% by mass.

[0032] In step (I), the silicon source is preferably silica sol or water glass. The SiO2 content in the water glass is preferably 25-38% by mass, and the Na2O content is preferably 9-15% by mass.

[0033] The adsorbent in the present invention is suitable for the adsorption separation of m-xylene from mixed C8 aromatic hydrocarbons.

[0034] Important indicators for evaluating the performance of the adsorbent are the adsorption selectivity and the adsorption and desorption rates of the target component to be adsorbed. The selectivity is the ratio of the concentration ratio of two components in the adsorption phase to the concentration ratio of the two components in the non-adsorption phase at adsorption equilibrium. The adsorption equilibrium refers to the state where there is no net transfer of components between the adsorption phase and the non-adsorption phase after the mixed C8 aromatic hydrocarbons come into contact with the adsorbent. The calculation formula for the adsorption selectivity is as follows:

[0035]

Number

[0036] Here, C and D represent two components to be separated, and A C and A D respectively represent the concentrations of the two components C and D in the adsorption phase at adsorption equilibrium, and U C and U D respectively represent the concentrations of the two components C and D in the non-adsorption phase at adsorption equilibrium. When the selectivity β of the two components is about 1.0, it indicates that the adsorption capacity of the adsorbent for the two components is equivalent and there is no component that is preferentially adsorbed. When β is greater than or less than 1.0, it indicates that one component is preferentially adsorbed. Specifically, when β>1.0, the adsorbent preferentially adsorbs component C, and when β<1.0, the adsorbent preferentially adsorbs component D. From the perspective of the difficulty of separation, the larger the β value, the easier the adsorption separation. Faster adsorption and desorption rates are advantageous for reducing the usage amounts of the adsorbent and the desorbent, improving the product yield, and reducing the operating cost of the adsorption separation device.

[0037] This invention relates to measuring the adsorption selectivity and adsorption and desorption rates of m-xylene using a dynamic pulse experimental apparatus. The apparatus consists of a raw material supply system, an adsorption column, a heating furnace, and a pressure control valve, etc. The adsorption column is a Φ6 × 1800 mm stainless steel tube, and the adsorbent load is 50 ml. The lower inlet of the adsorption column is connected to the raw material supply and nitrogen system, and the upper outlet is connected to the pressure control valve, which is then connected to the effluent collector. The desorbent components used in the experiment are 30 vol% toluene (T) and 70 vol% n-heptane (NC7), and the pulse solution components are 5 vol% ethylbenzene (EB), p-xylene (PX), m-xylene (MX), o-xylene (OX), n-nonane (NC9), and 75 vol% of the aforementioned desorbent, respectively.

[0038] The method for measuring adsorption selectivity is as follows: The adsorption column is packed tightly with weighed adsorbent and activated by dehydration in a nitrogen atmosphere at 160-280°C. Subsequently, a desorbent is supplied to remove gas from the system, the pressure is increased to 0.8 MPa, the temperature is increased to 145°C, the supply of the desorbent is stopped, and the system is operated for 1.0 hour. -1 8 ml of pulsed raw material supply solution is supplied at a volumetric space velocity, then the supply of the pulsed solution is stopped, and the desorbent is supplied at the same space velocity for desorption. Three drops of desorbent solution sample are taken every two minutes and the components are analyzed by gas chromatography. Desorption curves for each component are plotted with the raw material supply volume of the desorbent on the horizontal axis and the raw material concentrations of NC9 and EB, PX, MX, and OX on the vertical axis. As a tracer, NC9 reaches its peak first without being adsorbed, creating dead space in the adsorption system. The midpoint of the tracer's half-peak width is set as the zero point, and the desorbent raw material supply volume from the midpoint of the half-peak width of each raw material EB, PX, MX, and OX to the zero point, i.e., the total corrected holding capacity V, is used. R The ratio of the total corrected retention capacities of the two components is the adsorption selectivity β. For example, the ratio of the total corrected retention capacities of MX to the total corrected retention capacities of EB is the adsorption selectivity of MX to EB, and β MX / EB It is written as follows.

[0039] To enable repeated and continuous use of the adsorbent, selectivity between the extracted component and the desorbent is also an important performance indicator, which can be determined by further analysis of the desorption curve of the extracted component in pulse testing. The volume of desorbent required when the concentration of MX in the effluent ahead of the pulse desorption curve of MX increases from 10% to 90% is the adsorption rate [S A ] 10-90 The desorption rate [S] is defined as the volume of desorbent required when the concentration of MX decreases from 90% to 10% behind the desorption curve. D ] 90-10 This is defined as follows: [S D ] 90-10 / [S A ] 10-90 The ratio of the two is the adsorption selectivity β between MX and the desorbent (T). MX / T It can represent β. MX / T If β is much smaller than 1.0, it indicates that the adsorbent has too strong an adsorption capacity for the desorbent, which is unfavorable for the adsorption process. MX / T If β is much greater than 1.0, it indicates that the adsorption capacity of the desorption agent is too weak, making the desorption process difficult. The ideal case is β MX / T This means that it is approximately equal to 1.0.

[0040] The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

[0041] In the examples and comparative examples, the method for measuring the physical properties of the adsorbent is as follows: The compressive strength of an adsorbent is expressed by the crushing rate of the pellet adsorbent under a constant pressure. The lower the crushing rate, the higher the compressive strength. The method for measuring the compressive strength of an adsorbent is to use a DL-II particle strength analyzer (manufactured by Dalian Chemical Industry Research and Design Institute). After passing the adsorbent pellets through a 300-micron sieve, approximately 1.5 ml of adsorbent is packed into a stainless steel cylinder. For measurement, the stainless steel cylinder is fitted with an interference fit thimble, pressed once at a preset pressure, and then the adsorbent is poured out and weighed using a 300-micron sieve. The amount of adsorbent lost before and after the pressurization test is the crushing rate of the adsorbent at the set pressure.

[0042] The adsorption capacity of molecular sieves or adsorbents is measured by toluene vapor phase adsorption experiments. The specific procedure is as follows: Nitrogen carrying toluene (toluene partial pressure 0.05 MPa) is brought into contact with a constant mass of adsorbent at 35°C until toluene reaches adsorption equilibrium. The adsorption capacity of the adsorbent under test is calculated based on the mass difference of the adsorbent before and after toluene adsorption, according to the following formula.

[0043]

number

[0044] Here, C is the adsorption capacity, in mg / g; m1 is the mass of the adsorbent before adsorbing toluene, in grams; and m2 is the mass of the adsorbent after adsorbing toluene, in grams.

[0045] The method for measuring the calcined bulk density of an adsorbent is as follows: Add 50 mL of adsorbent to a 100 mL graduated cylinder, vibrate it for 5 minutes using a tap densimeter (manufactured by Liaoning Instrument Research Institute Co., Ltd.), then add another 50 mL of adsorbent and vibrate for another 5 minutes. The ratio of the mass of the adsorbent to its volume in the graduated cylinder is the adsorbent bulk density. A certain mass of adsorbent is calcined at 600°C for 2 hours, cooled to room temperature in a dryer, the mass ratio of the adsorbent before and after calcination is the calcined base, and the product of the calcined base and the adsorbent bulk density is the calcined bulk density.

[0046] The specific surface area, total pore volume, pore volume, and mesoporous pore volume of the molecular sieve are measured according to ASTM D4365-95 (2008).

[0047] [Example 1] (1) Preparation of the aluminum source 200 kg of aluminum hydroxide, 181.52 kg of sodium hydroxide, and 214.84 kg of deionized water were added to a reaction vessel, heated to 100°C, and stirred for 6 hours to form a clear, transparent, low-alkalinity sodium metaaluminate solution as aluminum source 1. The Al2O3 content of aluminum source 1 was 21.58% by mass, the Na2O content was 23.59% by mass, and the molar ratio of Na2O to Al2O3 was 1.80. 87.89 kg of aluminum octadecahydrate sulfate was dissolved in 112.11 kg of water and stirred for 1 hour to obtain a clear, transparent aluminum sulfate solution as aluminum source 2. The Al2O3 content of aluminum source 2 was 6.73% by mass.

[0048] (2) Pre-treatment of raw materials The water glass (SiO2 content 37.17% by mass, Na2O content 11.65% by mass) and the aluminum source prepared in step (1) were both cooled to 0°C.

[0049] (3) Preparation of Y molecular sieve Under stirring conditions, 89.68 kg of water glass at 0°C, which had been subjected to temperature reduction treatment in step (2), 49.79 kg of aluminum sulfate solution at 0°C, 18.14 kg of low-alkalinity sodium metaaluminate solution at 0°C, and 5.61 kg of deionized water were added to the reaction vessel to obtain a Y molecular sieve synthesis system with molar ratios of SiO2 / Al2O3 = 7.8, Na2O / SiO2 = 0.25, and H2O / SiO2 = 10. The temperature of the synthesis system was 3°C.

[0050] The molecular sieve synthesis system described above was transferred to a sealed reaction vessel, statically aged at 30°C for 24 hours, then the temperature was raised to 100°C and statically crystallized for 8 hours, stirred for 5 minutes, and then statically crystallized for another 12 hours. After filtration, the obtained solid was washed with deionized water until the pH of the filtrate was 8-9, and dried at 80°C for 12 hours to obtain nano-Y molecular sieve a with an SiO2 / Al2O3 molar ratio of 4.6 (analyzed using X-ray fluorescence analysis; the same method was used hereafter). See Figure 1 for the XRD spectrum, Figure 2 for the SEM image, and Figure 3 for the pore size distribution curve. As can be seen from Figure 2, the nanoscale Y molecular sieve crystal grains form self-aggregates with a particle size of 0.6 microns by self-aggregation, and the nanoscale Y molecular sieve crystal grains have a particle size of 60-150 nanometers. Figure 3 shows that the most likely pore diameters for nano-Y molecular sieve a are 10 nanometers and 37 nanometers, respectively. For specific surface area, total pore volume, pore volume, mesoporous pore volume, and toluene adsorption capacity, please refer to Table 1.

[0051] [Example 2] A Y molecular sieve was prepared based on the method of Example 1, with the following differences: In step (3), under stirring conditions, 89.68 kg of water glass at 0°C (treated to decrease temperature in step (2)), 53.29 kg of aluminum sulfate solution at 0°C, 17.04 kg of low-alkalinity sodium metaaluminate solution at 0°C, and 3.50 kg of deionized water were added to the reaction vessel to obtain a Y molecular sieve synthesis system with molar ratios of SiO2 / Al2O3 = 7.8, Na2O / SiO2 = 0.23, and H2O / SiO2 = 10. The temperature of the synthesis system was 4°C. The molecular sieve synthesis system was transferred to a sealed reaction vessel and subjected to static aging and two-stage static crystallization with stirring in between. The resulting solid was washed with deionized water and dried to obtain nano-Y molecular sieve b with an SiO2 / Al2O3 molar ratio of 4.8. The self-aggregates formed by nanoscale Y molecular sieve crystal grains have a particle size of 0.8 microns, while the nanoscale Y molecular sieve crystal grains have a particle size of 80 to 180 nanometers. The pore size distribution curve is shown in Figure 4. The most likely pore diameters are 12 nanometers and 40 nanometers, respectively. For specific surface area, total pore volume, pore volume, mesoporous pore volume, and toluene adsorption capacity, please refer to Table 1.

[0052] [Example 3] A Y molecular sieve was prepared based on the method of Example 1, with the following differences: In step (3), under stirring conditions, 89.68 kg of water glass at 0°C (treated to decrease temperature in step (2)), 58.56 kg of aluminum sulfate solution at 0°C, 15.04 kg of low-alkalinity sodium metaaluminate solution at 0°C, and 0.32 kg of deionized water were added to the reaction vessel to obtain a Y molecular sieve synthesis system with molar ratios of SiO2 / Al2O3 = 7.8, Na2O / SiO2 = 0.20, and H2O / SiO2 = 10. The temperature of the synthesis system was 5°C. The molecular sieve synthesis system was transferred to a sealed reaction vessel and subjected to static aging and two-stage static crystallization with stirring in between. The resulting solid was washed with deionized water and dried to obtain nano-Y molecular sieve c with an SiO2 / Al2O3 molar ratio of 4.9. The self-aggregates formed by nanoscale Y molecular sieve crystal grains have a particle size of 1.0 micron, while the nanoscale Y molecular sieve crystal grains have a particle size of 90 to 200 nanometers. The pore size distribution curve is shown in Figure 5. The most likely pore diameters are 15 nanometers and 42 nanometers, respectively. For specific surface area, total pore volume, pore volume, mesoporous pore volume, and toluene adsorption capacity, please refer to Table 1.

[0053] [Example 4] A Y molecular sieve was prepared based on the method of Example 1, with the following differences: In step (3), under stirring conditions, 59.79 kg of water glass at 0°C (treated to decrease temperature in step (2)), 39.05 kg of aluminum sulfate solution at 0°C, 10.27 kg of low-alkalinity sodium metaaluminate solution at 0°C, and 33.54 kg of deionized water were added to the reaction vessel to obtain a Y molecular sieve synthesis system with molar ratios of SiO2 / Al2O3 = 7.8, Na2O / SiO2 = 0.20, and H2O / SiO2 = 15. The temperature of the synthesis system was 4°C. The molecular sieve synthesis system was transferred to a sealed reaction vessel and subjected to static aging and two-stage static crystallization with stirring in between. The resulting solid was washed with deionized water and dried to obtain nano-Y molecular sieve d with an SiO2 / Al2O3 molar ratio of 4.9. The self-aggregates formed by nanoscale Y molecular sieve crystal grains have a particle size of 1.1 microns, while the nanoscale Y molecular sieve crystal grains have a particle size of 90 to 220 nanometers. The pore size distribution curve is shown in Figure 6. The most likely pore diameters are 17 nanometers and 43 nanometers, respectively. For specific surface area, total pore volume, pore volume, mesoporous pore volume, and toluene adsorption capacity, please refer to Table 1.

[0054] [Example 5] A Y molecular sieve was prepared based on the method of Example 1, with the following differences: In step (3), under stirring conditions, 44.84 kg of water glass at 0°C (treated to decrease temperature in step (2)), 29.29 kg of aluminum sulfate solution at 0°C, 7.7 kg of low-alkalinity sodium metaaluminate solution at 0°C, and 50.16 kg of deionized water were added to the reaction vessel to obtain a Y molecular sieve synthesis system with molar ratios of SiO2 / Al2O3 = 7.8, Na2O / SiO2 = 0.20, and H2O / SiO2 = 20. The temperature of the synthesis system was 5°C. The molecular sieve synthesis system was transferred to a sealed reaction vessel and subjected to static aging and two-stage static crystallization with stirring in between. The resulting solid was washed with deionized water and dried to obtain nano-Y molecular sieve e with an SiO2 / Al2O3 molar ratio of 5.0. The self-aggregates formed by nanoscale Y molecular sieve crystal grains have a particle size of 1.2 microns, while the nanoscale Y molecular sieve crystal grains have a particle size of 90 to 240 nanometers. The pore size distribution curve is shown in Figure 7. The most likely pore diameters are 19 nanometers and 46 nanometers, respectively. For specific surface area, total pore volume, pore volume, mesoporous pore volume, and toluene adsorption capacity, please refer to Table 1.

[0055] [Comparative Example 1] (1) Preparation of the aluminum source 200 kg of aluminum hydroxide, 232.15 kg of sodium hydroxide, and 652.33 kg of deionized water were added to a reaction vessel, heated to 100°C, and stirred for 6 hours to form a clear, transparent, low-alkalinity sodium metaaluminate solution as an aluminum source. The Al2O3 content of the aluminum source was 11.87% by mass, the Na2O content was 16.59% by mass, and the molar ratio of Na2O to Al2O3 was 2.3.

[0056] (2) Preparation of directional agents Under stirring conditions, 3.81 kg of sodium hydroxide, 8.86 kg of deionized water, 4.48 kg of the aluminum source prepared in step (1), and 23.24 kg of water glass (SiO2 content 20.17 mass%, Na2O content 6.32 mass%) were added to the reaction vessel. Here, the molar ratios of each raw material were SiO2 / Al2O3 = 15, Na2O / SiO2 = 1.07, and H2O / SiO2 = 21. The mixture was left to stand at 35°C for 16 hours to obtain the orientation agent.

[0057] (3) Preparation of Y molecular sieve Under stirring conditions, 50.74 kg of water glass, 42.51 kg of deionized water, 7.56 kg of the directing agent prepared in step (2), 8.66 kg of the aluminum sulfate solution prepared in step (1) of Example 1, and 11.01 kg of the low-alkalinity sodium metaaluminate solution prepared in step (1) were added to the reaction vessel to obtain the Y molecular sieve synthesis system. The molar ratios of each raw material were SiO2 / Al2O3=9.5, Na2O / SiO2=0.43, and H2O / SiO2=30. The molar ratio of Al2O3 in the directing agent to Al2O3 in the Y molecular sieve synthesis system was 5%, and the temperature of the synthesis system was 35°C.

[0058] The molecular sieve synthesis system described above was transferred to a sealed reaction vessel, heated to 100°C, and hydrothermal crystallization was carried out for 28 hours. The resulting solid was filtered, and the obtained solid was washed with deionized water until the filtrate reached a pH of 8-9. It was then dried at 80°C for 12 hours to obtain a Y molecular sieve f with an SiO2 / Al2O3 molar ratio of 4.8. See Figure 8 for the XRD spectrum and Figure 9 for the SEM image. The particle size of the Y molecular sieve was 0.9 microns. Figure 10 shows the pore size distribution curve, indicating the absence of obvious mesopores. See Table 1 for specific surface area, total pore volume, pore volume, mesoporous pore volume, and toluene adsorption capacity.

[0059] [Comparative Example 2] Preparation of Y molecular sieves using a conventional method without directing agents. 5.0 kg of sodium aluminate (containing 30% by mass of Na2O, 44.1% by mass of Al2O3, and 25.9% by mass of H2O) and 27.3 kg of sodium hydroxide were dissolved in 219 kg of water and stirred for 1 hour to obtain a clear solution. Under stirring conditions, 124.2 kg of silica sol (containing 29.5% by mass of SiO2) was added and stirred for another 0.5 hours to obtain a homogeneously mixed synthesis system. Here, the molar ratios of each raw material were SiO2 / Al2O3 = 28.2, Na2O / SiO2 = 0.6, and H2O / SiO2 = 28.7. The above synthesis system was transferred to a sealed reaction vessel and heated to 120°C for hydrothermal crystallization for 3 hours. The mixture was filtered, and the obtained solid was washed with deionized water until the pH of the filtrate was 8-9. The mixture was dried at 80°C for 12 hours to obtain a Y molecular sieve g with an SiO2 / Al2O3 molar ratio of 3.8. For specific surface area, total pore volume, pore volume, mesoporous pore volume, and toluene adsorption capacity, please refer to Table 1.

[0060] [Comparative Example 3] Preparation of a single mesoporous NaY molecular sieve by the method of Example 1 of CN109692656A 10.9 kg of sodium metaaluminate solution (containing 17.3% by mass of Al2O3 and 21.0% by mass of Na2O), 48.3 kg of deionized water, and 13.1 kg of sodium hydroxide were taken and stirred to completely dissolve the solid base. Then 66.8 kg of water glass (containing 28.3% by mass of SiO2 and 8.8% by mass of Na2O) was added and stirred until homogeneously mixed. The mixture was then allowed to stand at 25°C for 20 hours to age and prepare the directing agent. The molar ratios of the raw materials were SiO2 / Al2O3 = 17, Na2O / SiO2 = 0.95, and H2O / SiO2 = 17.6.

[0061] 187.2 kg of water glass, 464.5 kg of deionized water, and 16.3 kg of sodium hydroxide were taken and thoroughly mixed by stirring at 25°C. 90.6 kg of sodium metaaluminate was added while stirring, followed by 0.9 kg of a directing agent. The mixture was then homogenized, and 8.2 kg of an aqueous solution of polydimethyldiallylammonium chloride (R) with a concentration of 20% by mass was added as a template solution. The molecular weight of polydimethyldiallylammonium chloride is 100,000 to 200,000. The mixture was stirred continuously until homogenized and the synthesis system was obtained. Here, the molar ratios of the starting materials were SiO2 / Al2O3 = 5.8, Na2O / SiO2 = 0.88, and H2O / SiO2 = 31, and the mass ratio of R / SiO2 was 0.03. The amount of directing agent added was 0.2% of the mass of SiO2 in the synthesis system, based on its SiO2 content.

[0062] The aforementioned synthesis system was heated to 100°C, and hydrothermal crystallization was carried out under static conditions for 8 hours. The crystallized product was washed with deionized water until the pH of the washing solution was less than 10. The obtained solid was dried at 80°C for 12 hours, then subjected to primary calcination at 200°C for 1 hour in air, secondary calcination at 380°C for 1 hour, and tertiary calcination at 540°C for 4 hours to obtain a mesoporous NaY molecular sieve h with a molar ratio of SiO2 / Al2O3 of 5.1 and a crystal grain size of 1.3 microns. The pore size distribution curve is shown in Figure 11, showing a single mesoporous structure. For its specific surface area, total pore volume, pore volume, mesoporous pore volume, and toluene adsorption capacity, please refer to Table 1.

[0063] [Example 6] Preparation of the adsorbent of the present invention and testing of its adsorption performance. (1) Ball rolling: 92 kg (mass of calcined base, the same applies hereafter) of nano NaY molecular sieve a prepared in Example 1 was uniformly mixed with 8 kg of kaolin (containing 90% by mass of kaolinite), 3 kg of white carbon black, and 3 kg of Sesbania powder. The mixture was placed on a rotating disc, and an appropriate amount of deionized water was sprayed while it was rotating to agglomerate the solid powder into pellets. The amount of water sprayed during rolling was 8% by mass of the solid powder, and the mass ratio of silicon dioxide contained in the white carbon black to kaolin was 0.3. After sieving, pellets with a particle size of 300-850 μm were taken, dried at 80°C for 10 hours, and calcined at 540°C for 4 hours.

[0064] (2) In-situ crystallization: 64 kg of the calcined pellets from step (1) were placed in 200 liters of a mixed solution of sodium hydroxide and water glass (water glass containing 20.17 mass% SiO2 and 6.32 mass% Na2O) for in-situ crystallization of the calcined pellets. The mixed solution contained 5 mass% Na2O and 3 mass% SiO2, and was subjected to in-situ crystallization at 95°C for 4 hours. The crystallized solid was washed until the pH of the washing solution was less than 10, and dried at 80°C for 10 hours to prepare adsorbent A. Adsorbent A contained 89.3 mass% Y molecular sieve a, 9.3 mass% Y molecular sieve produced by crystallization transition, and 1.4 mass% substrate. See Table 2 for adsorption selectivity, adsorption capacity, fragmentation rate under different pressures, and calcined bulk density measured by pulse experiments.

[0065] [Example 7] The adsorbent was prepared according to the method of Example 6, with the following differences: In step (1), the nano NaY molecular sieve b prepared in Example 2 was mixed with kaolin, white carbon black, and sesbania powder, and then ball-rolled. After in-situ crystallization, adsorbent B was prepared containing 89.3 mass% of Y molecular sieve b, 9.6 mass% of Y molecular sieves produced by crystallization transition, and 1.1 mass% of substrate. See Table 2 for adsorption selectivity, adsorption capacity, fracturing rate under different pressures, and calcined bulk density.

[0066] [Example 8] The adsorbent was prepared according to the method of Example 6, with the following differences: In step (1), the nano NaY molecular sieve c prepared in Example 3 was mixed with kaolin, white carbon black, and sesbania powder, and then ball-rolled. After in-situ crystallization, an adsorbent C was prepared containing 89.3 mass% of Y molecular sieve c, 9.8 mass% of Y molecular sieves produced by crystallization transition, and 0.9 mass% of substrate. See Table 2 for adsorption selectivity, adsorption capacity, fracturing rate under different pressures, and calcined bulk density.

[0067] [Example 9] The adsorbent was prepared according to the method of Example 6, with the following differences: In step (1), the nano NaY molecular sieve d prepared in Example 4 was mixed with kaolin, white carbon black, and sesbania powder, and then ball-rolled. After in-situ crystallization, adsorbent D was prepared containing 89.3 mass% of Y molecular sieve d, 9.5 mass% of Y molecular sieve produced by crystallization transition, and 1.2 mass% of substrate. See Table 2 for adsorption selectivity, adsorption capacity, fracture rate under different pressures, and calcined bulk density.

[0068] [Example 10] The adsorbent was prepared according to the method of Example 6, with the following differences: In step (1), the nano NaY molecular sieve e prepared in Example 5 was mixed with kaolin, white carbon black, and sesbania powder, and then ball-rolled. After in-situ crystallization, an adsorbent E was prepared containing 89.3 mass% of Y molecular sieve e, 10.0 mass% of Y molecular sieve produced by crystallization transition, and 0.7 mass% of substrate. See Table 2 for adsorption selectivity, adsorption capacity, fracturing rate under different pressures, and calcined bulk density.

[0069] [Comparative Example 4] The adsorbent was prepared according to the method of Example 6, with the following differences: In step (1), the NaY molecular sieve f prepared in Comparative Example 1 was mixed with kaolin, white carbon black, and sesbania powder, and then ball-rolled. After in-situ crystallization, adsorbent F containing 97.2% by mass of Y molecular sieve and 2.8% by mass of substrate was prepared. See Table 2 for adsorption selectivity, adsorption capacity, crushing rate under different pressures, and calcined bulk density.

[0070] [Comparative Example 5] The adsorbent was prepared according to the method of Example 6, with the following differences: In step (1), the NaY molecular sieve g prepared in Comparative Example 2 was mixed with kaolin, white carbon black, and sesbania powder, and then ball-rolled. After in-situ crystallization, adsorbent G containing 97.6% by mass of Y molecular sieve and 2.4% by mass of substrate was prepared. See Table 2 for adsorption selectivity, adsorption capacity, crushing rate under different pressures, and calcined bulk density.

[0071] [Comparative Example 6] The adsorbent was prepared according to the method of Example 6, with the following differences: In step (1), the NaY molecular sieve h prepared in Comparative Example 3 was mixed with kaolin, white carbon black, and sesbania powder, and then ball-rolled. After in-situ crystallization, adsorbent H containing 97.6% by mass of Y molecular sieve and 2.4% by mass of substrate was prepared. See Table 2 for adsorption selectivity, adsorption capacity, crushing rate under different pressures, and calcined bulk density.

[0072] [Example 11] The adsorption and separation experiment of m-xylene was conducted using adsorbent A on a small simulated moving bed apparatus with continuous backflow.

[0073] The aforementioned small-scale simulated moving bed apparatus included 24 adsorption columns connected in series, each having a length of 195 mm and an inner diameter of 30 mm, with a total adsorbent load of 3300 ml, and was loaded with adsorbent A. The two ends of the 24 columns connected in series were connected by a circulation pump to form a closed circuit as shown in Figure 12. The 24 adsorption columns were divided into four zones by four flows of inflow and outflow materials: adsorption material, desorbent, extract, and raffinate. Specifically, there were 7 adsorption columns as an adsorption zone between the adsorption material (column 15) and raffinate (column 21), 9 adsorption columns as a purification zone between the extract (column 6) and adsorption material (column 14), 5 adsorption columns as a desorption zone between the desorbent (column 1) and extract (column 5), and 3 adsorption columns as a buffer zone between raffinate (column 22) and desorbent (column 24). The adsorption and separation temperatures were controlled to 145°C, and the pressure was 0.8 MPa.

[0074] During the operation, toluene, the desorbent, and the adsorbent material were continuously supplied to the simulated moving bed apparatus at flow rates of 1600 ml / h and 500 ml / h, respectively. The extract was extracted from the apparatus at a flow rate of 761 ml / h, and the raffinate was extracted from the apparatus at a flow rate of 1339 ml / h. The adsorbent material consisted of 14.99% by mass of ethylbenzene, 20.14% by mass of p-xylene, 42.25% by mass of m-xylene, 21.75% by mass of o-xylene, and 0.87% by mass of non-aromatic hydrocarbon components. The circulation pump flow rate was set to 3960 ml / h, and the four flows were moved one adsorption column at a time every 70 seconds in the same direction as the liquid flow (in Figure 12, from the position of the solid line to the position of the dashed line; subsequent movements are inferred from this). The purity of m-xylene obtained under stable operating conditions was 99.58% by mass, and the yield was 97.15% by mass.

[0075] [Example 12] Adsorbent B was loaded into a small simulated mobile bed device, and an adsorption separation experiment of m-xylene was performed according to the method of Example 11. The purity of the m-xylene obtained under stable operating conditions was 99.62% by mass, and the yield was 97.29% by mass.

[0076] [Comparative Example 7] A comparative adsorbent F was loaded into a small simulated mobile bed device, and an adsorption separation experiment of m-xylene was performed according to the method of Example 11. The purity of the m-xylene obtained under stable operating conditions was 99.51% by mass, and the yield was 91.53% by mass.

[0077] [Comparative Example 8] A small-scale simulated mobile bed device was loaded with comparative adsorbent H, and an adsorption separation experiment of m-xylene was performed according to the method of Example 11. The purity of the m-xylene obtained under stable operating conditions was 99.52% by mass, and the yield was 89.77% by mass.

[0078] [Table 1]

[0079] [Table 2]

Claims

1. An m-xylene adsorbent comprising 94-99.9% by mass of Y molecular sieves and 0.1-6% by mass of a substrate, wherein the Y molecular sieves consist of amorphous transition Y molecular sieves and Y molecular sieves produced by the crystalline transition of kaolin minerals, and the amorphous transition Y molecular sieves are mesoporous nano Y molecular sieves having a crystal grain size of 20-450 nanometers and containing two types of mesoporous pores, each having the most likely pore diameters of 5-20 nanometers and 25-50 nanometers, respectively.

2. The adsorbent according to claim 1, comprising 98 to 99.9% by mass of Y molecular sieves and 0.1 to 2% by mass of a substrate.

3. The adsorbent according to claim 1, comprising 84 to 93% by mass of amorphous transition Y molecular sieves, 1 to 15.9% by mass of Y molecular sieves produced by crystalline transition, and 0.1 to 6% by mass of a substrate.

4. The adsorbent according to any one of claims 1 to 3, characterized in that the adsorbent comprises 84 to 93% by mass of amorphous transition Y molecular sieves, 5 to 15.9% by mass of Y molecular sieves produced by crystalline transition, and 0.1 to 2% by mass of a substrate.

5. The adsorbent according to any one of claims 1 to 4, characterized in that the mesoporous nano Y molecular sieve is a self-aggregate of nanoscale Y molecular sieve crystal grains, the self-aggregate has a particle size of 0.5 to 1.5 microns, and the nanoscale Y molecular sieve crystal grains in the self-aggregate have a particle size of 20 to 400 nanometers.

6. The SiO of the aforementioned mesoporous nano-Y molecular sieve ２ / Al ２ O ３ The adsorbent according to any one of claims 1 to 4, characterized in that the molar ratio is 4.0 to 5.

5.

7. The aforementioned mesoporous nano-Y molecular sieve has a length of 740 to 1000 m. ２ Specific surface area per g: 0.40–0.65 cm² ３ Total pore volume per g, and 0.08–0.35 cm³ ３ The adsorbent according to any one of claims 1 to 4, characterized by having a mesoporous pore volume of / g.

8. The adsorbent according to any one of claims 1 to 4, characterized in that the mesoporous nano-Y molecular sieve has pore diameters of 10 to 20 nanometers and 30 to 50 nanometers, respectively, which are the most likely to occur.

9. A method for preparing the adsorbent according to any one of claims 1 to 8, comprising the following steps: (1) Amorphous transition NaY molecular sieve, kaolin mineral, silicon source, and molding aid are uniformly mixed, ball-rolled into pellets, dried, and then calcined at 530-600°C. Here, the mass ratio of the amorphous transition NaY molecular sieve to the kaolin mineral is 85-94:6-15, and the mass ratio of silicon dioxide contained in the added silicon source to the kaolin mineral is 0.1-3.

6. (2) The pellets obtained after firing in step (1) are subjected to in-situ crystallization at 85-100°C using sodium hydroxide or a mixed solution of sodium hydroxide and water glass so that the kaolin minerals within them are crystallized in situ to form a Y molecular sieve, and then washed and dried.

10. The method according to claim 9, characterized in that the kaolin mineral in step (1) is selected from the group consisting of kaolinite, dickite, perlite, ovenstone, halloysite, or mixtures thereof.

11. The method according to claim 9, characterized in that the molding aid in step (1) is selected from at least one of lignin, sesbania powder, dried starch, carboxymethylcellulose, and activated carbon.

12. The method according to claim 9, characterized in that the silicon source in step (1) is selected from one or more of ethyl orthosilicate, silica sol, water glass, sodium silicate, silica gel, and white carbon black, and the mass ratio of silicon dioxide contained in the added silicon source to kaolin mineral is 0.2 to 3.

0.

13. The method according to claim 9, characterized in that the liquid / solid ratio of in-situ crystallization in step (2) is 1.5 to 5.0 L / kg.

14. The method according to claim 9, characterized in that, in step (2), when a sodium hydroxide solution is used for in-situ crystallization, the concentration of hydroxide ions in the sodium hydroxide solution used is 0.1 to 3.0 mol / L; and when a mixed solution of sodium hydroxide and water glass is used for in-situ crystallization, the sodium hydroxide content is 2 to 10% by mass and the silicon dioxide content is 1 to 6% by mass.

15. The method according to claim 9, characterized in that the method for preparing the amorphous transition NaY molecular sieve in step (1) includes the following steps: (I) Take a silicon source and an aluminum source at 0 to 5 °C, add sodium hydroxide and water, and mix them uniformly to form a molecular sieve synthesis system. Here, the molar ratio of each raw material is SiO ２ / Al ２ O ３ = 5.5 to 9.5, Na ２ O / SiO ２ = 0.1 to 0.3, H ２ O / SiO ２ = 5 to 25, and the temperature of the synthesis system is 1 to 8 °C. (II) The molecular sieve synthesis system from step (I) is statically aged at 20-40°C for 10-48 hours, then statically crystallized at 90-150°C for 2-10 hours, stirred for 2-10 minutes, and then statically crystallized for another 11-20 hours. The resulting solid is then washed and dried.

16. In step (I), the molar ratio of each raw material in the molecular sieve synthesis system is SiO ２ / Al ２ O ３ = 7-9, Na ２ O / SiO ２ =0.1~0.25,H ２ O / SiO ２ The method according to claim 15, characterized in that the value is 8 to 20.

17. The method according to claim 15, characterized in that in step (II), the molecular sieve synthesis system is statically aged at 20 to 40°C for 15 to 30 hours, then statically crystallized at 90 to 120°C for 4 to 9 hours, stirred for 2 to 10 minutes, and then statically crystallized for 11 to 15 hours.

18. The method according to claim 15, characterized in that the aluminum source in step (I) is selected from one or more of a low-alkalinity sodium metaaluminate solution, aluminum oxide, aluminum hydroxide, aluminum sulfate solution, aluminum chloride, aluminum nitrate, and sodium aluminate.

19. Al in a low-alkali sodium metaaluminate solution ２ O ３ The content is 17-28% by mass, and Na ２ The method according to claim 15, characterized in that the O content is 19 to 30% by mass.

20. The method according to claim 15, characterized in that the silicon source is selected from silica sol or water glass.

21. The SiO in the water glass ２ The content is 25-38% by mass, Na ２ The method according to claim 20, characterized in that the O content is 9 to 15% by mass.

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