Coexisting molecular sieve of mtw and mfi and preparation method and application and catalyst thereof

Abstract

The present application relates to the field of molecular sieve synthesis, in particular to a kind of symbiotic molecular sieve of MTW and MFI and its preparation method and application and catalyst, the symbiotic molecular sieve has chemical composition as shown in formula "SiO2·1 / nAl2O3·pR", wherein 50≤n≤80, 0.04<p≤0.07, R is methyl triethyl ammonium ion, the present application provides a kind of new symbiotic molecular sieve of MTW and MFI, with unique chemical composition and XRD diffraction pattern.This molecular sieve contains multistage pore structure, strong acid weak acid distribution range is wider, has potential advantage in catalysis, adsorption and other applications.

Description

Technical Field

[0001] This invention relates to the field of molecular sieve synthesis, specifically to a symbiotic molecular sieve of MTW and MFI, its preparation method, applications, and catalysts. Background Technology

[0002] MTW-type molecular sieves possess one-dimensional twelve-membered ring (0.57nm × 0.61nm) straight channels, exhibiting high acid resistance, good thermal stability, and hydrothermal stability. With a pore size between mesoporous and macroporous zeolites, MTW-type molecular sieves can effectively achieve the catalytic conversion of most organic molecules. They demonstrate excellent catalytic performance in reactions such as hydrocarbon cracking, isomerization, dehydration, and reforming, and show promising application prospects in the catalytic conversion of heavy components and large-molecule feedstocks in petroleum refining and chemical industries.

[0003] MFI molecular sieves possess two sets of intersecting ten-membered ring channels: one is a straight channel parallel to the b-axis with a pore size of approximately 0.54 nm × 0.56 nm; the other is an elliptical channel (Z-type channel) parallel to the a-axis, with a major axis pore size of approximately 0.57 nm × 0.58 nm and a minor axis pore size of approximately 0.51 nm × 0.52 nm. Typical materials include ZSM-5, Silicalite-1, and TS-1 molecular sieves. MFI molecular sieves are currently widely used in petroleum, chemical, and other fields.

[0004] Both types of molecular sieve materials suffer from problems such as uniform and uniform pore size, weak acidity, low activity, and poor selectivity, making it difficult to process complex components individually. Furthermore, their catalytic performance differs for the same reactants. Porous symbiotic molecular sieves containing two or more components, with hierarchical pore structures and a wide distribution of strong and weak acids, can process complex components with varying molecular diameters. In catalysis, adsorption, and other applications, they can leverage their respective advantages to synergistically treat complex components with diverse molecular sizes.

[0005] CN108275698B discloses a Beta / ZSM-12 symbiotic zeolite molecular sieve and its preparation method. The method uses tetraethylammonium bromide or tetraethylammonium hydroxide as organic structure directing agents and adds seed crystals to prepare BEA type molecular sieves with a particle size of about 300 nm and MTW type molecular sieves with a particle size of 1-4 μm.

[0006] CN106946266B discloses a SAPO-34 / ZSM-12 composite molecular sieve and its synthesis method. First, alumina is prepared by crystallization; then, a second organic structure directing agent is added, and ZSM-12 molecular sieve is obtained by crystallization; then, ZSM-12 molecular sieve is mixed with phosphorus source, silicon source, aluminum source, water and template agent to finally obtain SAPO-34 / ZSM-12 composite molecular sieve.

[0007] CN101279743B discloses a symbiotic molecular sieve and its synthesis method. By adding seeds containing β-zeolite precursors during the synthesis of the symbiotic molecular sieve and controlling the nucleation and growth process of the molecular sieve, a symbiotic molecular sieve, namely ZSM-5 / mordenite / β symbiotic molecular sieve material, is prepared.

[0008] CN100586858 discloses a porous symbiotic material and its synthesis method. By controlling the nucleation and growth process of the molecular sieve during the synthesis of the porous material, a porous symbiotic material is prepared. The proportion of its symbiotic phases can be adjusted, which is ZSM-5 / mordenite / β symbiotic molecular sieve material and can be used in the industrial production of catalytic cracking of naphtha to produce ethylene and propylene.

[0009] CN1242918C discloses the synthesis of a composite structure molecular sieve with two structures of TON and MFI under static conditions. A small amount of seeds and salts are added during the preparation process, and by controlling the crystallization parameters, molecular sieves with different proportions of two crystal forms are obtained. The obtained composite molecular sieve can be used in the reaction process of mixtures such as petroleum fractions.

[0010] Currently, there are few reports on MTW and MFI symbiotic molecular sieves.

[0011] CN104591216B discloses a ZSM-5 and ZSM-12 composite molecular sieve and its synthesis method. First, the ZSM-12 molecular sieve is added to a glucose solution for ultrasonic treatment, and then the precrystallized colloid and the treated ZSM-12 molecular sieve are mixed and crystallized to obtain the ZSM-5 / ZSM-12 composite molecular sieve. This method involves adding the ZSM-12 molecular sieve into the crystallization solution to prepare a molecular sieve with a core-shell structure similar to ZSM-5 and ZSM-12. In addition, the synthesized symbiotic molecular sieve has a silica-alumina ratio higher than 200, close to the pure silica composition. There is no report on the in-situ synthesis of MTW and MFI symbiotic molecular sieves with a relatively low silica-alumina ratio. Directly synthesizing MTW and MFI symbiotic molecular sieves using a simple preparation method will help expand their application scenarios. Summary of the Invention

[0012] The object of the present invention is to overcome the problem of the single pore size structure of the molecular sieve existing in the prior art, and to provide a symbiotic molecular sieve of MTW and MFI, its preparation method, application and catalyst. The symbiotic molecular sieve of MTW and MFI has a hierarchical pore structure.

[0013] To achieve the above object, in the first aspect of the present invention, a symbiotic molecular sieve of MTW and MFI is provided. The symbiotic molecular sieve has a chemical composition shown by the formula "SiO2·1 / nAl2O3·pR", where 50 ≤ n ≤ 80, 0.04 < p ≤ 0.07, and R is methyltriethylammonium ion.

[0014] A second aspect of this invention provides a method for preparing the symbiotic molecular sieve described herein, the method comprising mixing a silicon source, sodium aluminate, sodium hydroxide, an organic structure-directing agent, and water, crystallizing, filtering, washing, and drying to obtain the symbiotic molecular sieve; wherein,

[0015] The sodium aluminate contains 35%-43% Al2O3 by weight, preferably 38%-43%, and 25%-33% Na2O by weight, preferably 28%-33%.

[0016] The organic structure directing agent is selected from at least one of methyltriethylammonium hydroxide, methyltriethylammonium chloride, methyltriethylammonium bromide, and methyltriethylammonium iodide;

[0017] The molar ratio of the silicon source (SiO2), sodium aluminate (Al2O3), sodium hydroxide, organic structure directing agent (methyltriethylammonium ion), and water is 1:0.012-0.020:0.15-0.25:0.07-0.12:10-50.

[0018] A third aspect of the present invention provides the application of the symbiotic molecular sieve described herein in the preparation of adsorbents or catalysts.

[0019] A fourth aspect of the present invention provides a catalyst comprising the symbiotic molecular sieve described in the present invention.

[0020] Through the above technical solution, the present invention has the following beneficial effects:

[0021] This invention provides a novel symbiotic molecular sieve composed of MTW and MFI, exhibiting a unique chemical composition and XRD diffraction pattern. This molecular sieve contains a hierarchical pore structure and exhibits a wide distribution of strong and weak acids, offering potential advantages in catalysis, adsorption, and other applications. This invention also provides a simple and feasible method for preparing the symbiotic molecular sieve of MTW and MFI, resulting in a straightforward synthesis and well-crystallized symbiotic molecular sieve. Attached Figure Description

[0022] Figure 1 The X-ray diffraction (XRD) pattern of the sample in Example 1;

[0023] Figure 2 The X-ray diffraction (XRD) pattern of the sample in Example 2;

[0024] Figure 3 The X-ray diffraction (XRD) pattern of the sample in Example 3;

[0025] Figure 4 The X-ray diffraction (XRD) pattern of the sample in Example 4;

[0026] Figure 5 is the X-ray diffraction pattern (XRD) of the sample in Example 5;

[0027] Figure 6 is the X-ray diffraction pattern (XRD) of the sample in Comparative Example 1;

[0028] Figure 7 is the X-ray diffraction pattern (XRD) of the sample in Comparative Example 2;

[0029] Figure 8 is the X-ray diffraction pattern (XRD) of the sample in Comparative Example 5. Detailed implementation manners

[0030] In the ranges disclosed herein, the endpoints and any values are not limited to the exact ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, between the endpoint values of each range, between the endpoint values of each range and individual point values, and between individual point values can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be regarded as specifically disclosed herein.

[0031] The first aspect of the present invention provides a symbiotic molecular sieve of MTW and MFI, and the symbiotic molecular sieve has a chemical composition shown by the formula "SiO2·1 / nAl2O3·pR", where 50 ≤ n ≤ 80, 0.04 < p ≤ 0.07, and R is methyltriethylammonium ion.

[0032] The present invention provides a new symbiotic molecular sieve composed of MTW and MFI, which has a unique chemical composition and XRD diffraction pattern. The molecular sieve contains a hierarchical pore structure, and the distribution range of strong and weak acids is relatively wide, having potential advantages in applications such as catalysis and adsorption.

[0033] According to a preferred embodiment of the present invention, the symbiotic molecular sieve includes an X-ray diffraction pattern as shown in the following table,

[0034]

[0035] a: ±0.30°, b: varies with 2θ.

[0036] According to a preferred embodiment of the present invention, the symbiotic molecular sieve further includes an X-ray diffraction pattern as shown in the following table,

[0037]

[0038] a: ±0.30°, b: varies with 2θ.

[0039] According to a preferred embodiment of the present invention, after the symbiotic molecular sieve is calcined at 300-800℃, preferably 400-650℃, for 1-10 hours, preferably 3-6 hours, the total specific surface area of ​​the symbiotic molecular sieve is not less than 360 m². 2 / gram, preferably 360-550 meters 2 / gram.

[0040] According to a preferred embodiment of the present invention, after the symbiotic molecular sieve is calcined at 300-800℃, preferably 400-650℃, for 1-10 hours, preferably 3-6 hours, the external specific surface area of ​​the symbiotic molecular sieve is not less than 30 m². 2 / gram, preferably 30-60 meters 2 / gram.

[0041] According to a preferred embodiment of the present invention, after calcining the symbiotic molecular sieve at 300-800℃, preferably 400-650℃, for 1-10 hours, preferably 3-6 hours, the total pore volume of the symbiotic molecular sieve is not less than 0.35 cm³. 3 / gram, preferably 0.35-0.60 cm 3 / gram.

[0042] According to a preferred embodiment of the present invention, after calcining the symbiotic molecular sieve at 300-800℃, preferably 400-650℃, for 1-10 hours, preferably 3-6 hours, the micropore volume of the symbiotic molecular sieve is not less than 0.12 cm³. 3 / gram, preferably 0.12-0.20 cm 3 / gram.

[0043] In this invention, the aforementioned calcination is carried out in an oxygen-containing atmosphere, such as air or an oxygen atmosphere.

[0044] According to a preferred embodiment of the present invention, after the symbiotic molecular sieve undergoes ammonium ion exchange to form hydrogen, the total acid content of the symbiotic molecular sieve is not less than 500 μmol / g, preferably 500-900 μmol / g.

[0045] According to a preferred embodiment of the present invention, after the symbiotic molecular sieve undergoes ammonium ion exchange to form hydrogen, the amount of strong acid in the symbiotic molecular sieve is not less than 150 μmol / g, preferably 150-300 μmol / g.

[0046] A second aspect of this invention provides a method for preparing the symbiotic molecular sieve described herein. The method includes mixing a silicon source, sodium aluminate, sodium hydroxide, an organic structure directing agent, and water; crystallizing; filtering; washing; and drying to obtain the symbiotic molecular sieve. The sodium aluminate contains 35%-43% Al₂O₃ by weight, preferably 38%-43%, and 25%-33% Na₂O by weight, preferably 28%-33%. The organic structure directing agent is selected from at least one of methyltriethylammonium hydroxide, methyltriethylammonium chloride, methyltriethylammonium bromide, and methyltriethylammonium iodide. The molar ratio of the silicon source (SiO₂), sodium aluminate (Al₂O₃), sodium hydroxide, organic structure directing agent (methyltriethylammonium ions), and water is 1:0.012-0.020:0.15-0.25:0.07-0.12:10-50.

[0047] The preparation method provided by the present invention can prepare symbiotic molecular sieves of MTW and MFI having the aforementioned characteristics of the present invention.

[0048] According to a preferred embodiment of the present invention, the organic structure directing agent is methyltriethylammonium hydroxide.

[0049] In this invention, there are no particular restrictions on the ratio of each raw material used, as long as it is within the aforementioned range. According to a preferred embodiment of this invention, the molar ratio of the silicon source (SiO2), sodium aluminate (Al2O3), sodium hydroxide, organic structure directing agent (methyltriethylammonium ion), and water is 1:0.013-0.019:0.16-0.24:0.08-0.12:14-45.

[0050] In this invention, the silicon source can be a conventional choice in the art. According to a preferred embodiment of the invention, the silicon source is silica sol.

[0051] In this invention, the crystallization conditions can be conventionally selected in the art. According to a preferred embodiment of the invention, the crystallization conditions include: a crystallization temperature of 150-180°C, preferably 155-175°C; and / or a crystallization time of 1.0-8.0 days, preferably 1.5-7.5 days.

[0052] In this invention, the crystallization method is dynamic crystallization by rotation or stirring, with a rotation speed of 10-60 rpm and a stirring speed of 30-300 rpm.

[0053] In this invention, the methods and conditions for filtration, washing, and drying can be conventional choices in the field, as long as they can achieve the purpose of this invention.

[0054] According to a preferred embodiment of the present invention, the filtration method is vacuum filtration.

[0055] According to a preferred embodiment of the present invention, the washing method is to use deionized water and / or ethanol for washing.

[0056] According to a preferred embodiment of the present invention, the conditions include: a drying temperature of 40-250°C, preferably 60-150°C; and / or a drying time of 8-30 hours, preferably 10-20 hours.

[0057] According to the present invention, the drying can be carried out under normal pressure or under reduced pressure.

[0058] According to a preferred embodiment of the present invention, the preparation method further includes calcining the dried symbiotic molecular sieve, exchanging ammonium ions, and then calcining it into a hydrogen-type molecular sieve.

[0059] According to a preferred embodiment of the present invention, the conditions for the ammonium ion exchange include: the concentration of ammonium ions in the ammonium salt solution is 0.1-1 mol / L, the solid-liquid ratio is 1:5-1:20, the ammonium exchange temperature is 30-80℃, and the ammonium exchange time is 1-8 hours; preferably, the number of ammonium exchanges is 1-2 times, and the ammonium salt is selected from at least one of ammonium chloride, ammonium nitrate, ammonium carbonate, and ammonium sulfate.

[0060] According to a preferred embodiment of the present invention, the conditions for re-calcining into hydrogen-type molecular sieves include: a calcination temperature of 300-800℃, preferably 400-650℃, and a calcination time of 1-10 hours, preferably 3-6 hours.

[0061] A third aspect of the present invention provides the application of the symbiotic molecular sieve described herein in the preparation of adsorbents and catalysts for the conversion of organic compounds.

[0062] A fourth aspect of the present invention provides a catalyst comprising the symbiotic molecular sieve described in the present invention.

[0063] The present invention will be described in detail below through embodiments. Unless otherwise specified, the raw materials used in the following embodiments are all commercially available products.

[0064] According to the present invention, the aforementioned molecular sieves can be used in any physical form, such as powder, granules, or molded forms (e.g., strips, clover shapes, etc.). These physical forms can be obtained in any manner conventionally known in the art, without particular limitation.

[0065] In the context of this specification, the structures of the molecular sieves of MTW and MFI are determined by X-ray diffraction (XRD), which is measured using an X-ray powder diffractometer with a Cu-Kα ray source and a nickel filter. Before sample testing, the crystallinity of the molecular sieve samples is observed using a scanning electron microscope (SEM) to confirm that the samples contain only one type of crystal, i.e., the molecular sieve samples are pure phases. XRD testing is then performed to ensure that there are no interfering peaks from other crystals in the diffraction patterns of the XRD patterns.

[0066] In the context of this specification, in XRD data of molecular sieves, w, m, s, and vs represent diffraction peak intensities, with w being weak, m being moderate, s being strong, and vs being very strong, as is well known to those skilled in the art. Generally, w is less than 20; m is 20-40; s is 40-70; and vs is greater than 70.

[0067] In the context of this specification, including in the following examples and comparative examples, the X-ray powder diffractometer used for the molecular sieves is a Panalytical X-PERPRO type X-ray powder diffractometer, used to analyze the phase composition of the samples, and a CuKα ray source. Nickel filter, 2θ scanning range 2-50°, operating voltage 40KV, current 40mA, scanning rate 10° / min.

[0068] In the context of this specification, including in the following examples and comparative examples, the micropore size, pore volume, specific surface area, and external specific surface area of ​​the molecular sieve were measured by the nitrogen physical adsorption-desorption method (BET method): the nitrogen physical adsorption-desorption isotherm of the molecular sieve was measured using a Micromeretic ASAP2020M physical adsorption instrument, and then calculated using the BET equation and t-plot equation. The experimental conditions for this molecular sieve were: measurement temperature -196℃, and before measurement, the molecular sieve was heat-treated at 550℃ in air for 6 hours, followed by pretreatment in vacuum at 350℃ for 4 hours.

[0069] In the context of this specification, including in the following examples and comparative examples, the molecular sieve was analyzed using an inductively coupled plasma atomic emission spectrometer (ICP) model Varian 725-ES, and the elemental content, in molar terms, was determined by dissolving the analytical sample in hydrofluoric acid.

[0070] In the context of this specification, including the following examples and comparative examples, the acid content of the molecular sieve was determined using an Altamira AMI-3300 instrument with NH3-TPD chemisorption-desorption curves. Before testing, the sample was activated at 550°C for 1 hour, ammonia was adsorbed at 100°C for 20 minutes, and then desorbed and detected at 100-600°C. Quantitative analysis was performed by quantitatively analyzing the peak area using a cyclic pulse of ammonia. Peak separation was performed using a Gaussian distribution, and the acid content corresponding to desorption temperatures above 300°C was considered the acid content of a strong acid.

[0071] In the context of this specification, including in the following examples and comparative examples, the organic content in the molecular sieves was determined by thermogravimetric analysis (TGA) using an SDT Q600 V20.9 Build 20 thermogravimetric analyzer. The sample was heated from 50°C to 800°C at a rate of 10°C / min in air or oxygen atmosphere to detect weight loss. The percentage of weight loss of the sample within the range of 200-700°C was taken as the organic content of the sample.

[0072] Example 1

[0073] A mixture was prepared by stirring 16.71 g of deionized water, 0.361 g of sodium aluminate (containing 40.5 wt% Al₂O₃ and 30.6 wt% Na₂O), 0.417 g of sodium hydroxide, 4.59 g of methyltriethylammonium hydroxide (containing 25 wt% methyltriethylammonium hydroxide), and 12.93 g of silica sol (containing 40.0 wt% SiO₂) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0074] SiO2 / Al2O3 = 60;

[0075] NaOH / SiO2 = 0.16;

[0076] R / SiO2 = 0.10;

[0077] H2O / SiO2 = 18.

[0078] The mixture was placed in a stainless steel reactor and heated to crystallize at 170°C with a stirring speed of 20 rpm for 3 days. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product is shown below. Figure 1 As shown in Table 1, these are molecular sieves with MTW and MFI structures coexisting.

[0079] Table 1

[0080]

[0081]

[0082] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 59.6 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.017Al2O3·0.051R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​432 m² was obtained. 2 / gram, with an external specific surface area of ​​51 m² measured by the BET method. 2 / g; Total pore volume 0.39cm 3 / gram, micropore volume is 0.16 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 659 μmol / g, and the strong acid content was 211 μmol / g.

[0083] Example 2

[0084] A mixture was prepared by stirring 11.72 g of deionized water, 0.436 g of sodium aluminate (containing 40.5 wt% Al2O3 and 30.6 wt% Na2O), 0.486 g of sodium hydroxide, 3.84 g of methyltriethylammonium hydroxide (containing 25 wt% methyltriethylammonium hydroxide), and 13.52 g of silica sol (containing 40.0 wt% SiO2) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0085] SiO2 / Al2O3 = 52;

[0086] NaOH / SiO2 = 0.18;

[0087] R / SiO2 = 0.08;

[0088] H2O / SiO2 = 14.

[0089] The mixture was placed in a stainless steel reactor and heated at 160°C with a stirring speed of 10 rpm for 5 days to crystallize. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product is shown below. Figure 2 As shown in Table 2, these are molecular sieves with MTW and MFI structures coexisting.

[0090] Table 2

[0091]

[0092]

[0093] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 52.2 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.019Al2O3·0.046R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​446 m² was obtained. 2 / gram, with an external specific surface area of ​​47 m² measured by the BET method. 2 / g; Total pore volume 0.44cm 3 / gram, micropore volume is 0.15 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 734 μmol / g, and the strong acid content was 257 μmol / g.

[0094] Example 3

[0095] A mixture was prepared by stirring 51.37 g of deionized water, 0.299 g of sodium aluminate (containing 40.5 wt% Al2O3 and 30.6 wt% Na2O), 0.553 g of sodium hydroxide, 5.31 g of methyltriethylammonium hydroxide (containing 25 wt% methyltriethylammonium hydroxide), and 12.47 g of silica sol (containing 40.0 wt% SiO2) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0096] SiO2 / Al2O3 = 70;

[0097] NaOH / SiO2 = 0.20;

[0098] R / SiO2 = 0.12;

[0099] H2O / SiO2 = 42.

[0100] The mixture was placed in a stainless steel reactor and heated to crystallize at 155°C with a stirring speed of 30 rpm for 7 days. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product is shown below. Figure 3 As shown in Table 3, these are molecular sieves with MTW and MFI structures coexisting.

[0101] Table 3

[0102]

[0103]

[0104] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 70.4 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.014Al2O3·0.053R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​459 m² was obtained. 2 / gram, with an external specific surface area of ​​39 m² measured by the BET method. 2 / g; Total pore volume 0.48cm 3 / gram, micropore volume is 0.15 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 614 μmol / g, and the strong acid content was 205 μmol / g.

[0105] Example 4

[0106] A mixture was prepared by stirring 46.43 g of deionized water, 0.280 g of sodium aluminate (containing 40.5 wt% Al2O3 and 30.6 wt% Na2O), 0.678 g of sodium hydroxide, 4.26 g of methyltriethylammonium hydroxide (containing 25 wt% methyltriethylammonium hydroxide), and 13.35 g of silica sol (containing 40.0 wt% SiO2) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0107] SiO2 / Al2O3 = 80;

[0108] NaOH / SiO2 = 0.22;

[0109] R / SiO2 = 0.09;

[0110] H2O / SiO2 = 36.

[0111] The mixture was placed in a stainless steel reactor and heated to crystallize at 175°C with a stirring speed of 15 rpm for 1.5 days. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product is shown below. Figure 4 As shown in Table 4, these are molecular sieves with MTW and MFI structures coexisting.

[0112] Table 4

[0113]

[0114]

[0115] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 79.9 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.013Al2O3·0.048R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​409 m² was obtained. 2 / gram, with an external specific surface area of ​​45 m² measured by the BET method. 2 / g; Total pore volume 0.38cm 3 / gram, micropore volume is 0.14 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 568 μmol / g, and the strong acid content was 179 μmol / g.

[0116] Example 5

[0117] A mixture was prepared by stirring 39.31 g of deionized water, 0.438 g of sodium aluminate (containing 40.5 wt% Al2O3 and 30.6 wt% Na2O), 0.757 g of sodium hydroxide, 5.10 g of methyltriethylammonium hydroxide (containing 25 wt% methyltriethylammonium hydroxide), and 14.39 g of silica sol (containing 40.0 wt% SiO2) at room temperature for 3 hours. The final material ratio (molar ratio) was as follows:

[0118] SiO2 / Al2O3 = 55;

[0119] NaOH / SiO2 = 0.24;

[0120] R / SiO2 = 0.10;

[0121] H2O / SiO2 = 30.

[0122] The mixture was placed in a stainless steel reactor and heated to crystallize at 165°C with a stirring speed of 40 rpm for 4 days. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product is shown below. Figure 5 As shown in Table 5, these are molecular sieves with MTW and MFI structures coexisting.

[0123] Table 5

[0124]

[0125]

[0126] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 55.1 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.018Al2O3·0.047R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​417 m² was obtained. 2 / gram, with an external specific surface area of ​​42 m² measured by the BET method. 2 / g; Total pore volume 0.37cm 3 / gram, micropore volume is 0.16 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 717 μmol / g, and the strong acid content was 245 μmol / g.

[0127] Example 6

[0128] A mixture was prepared by stirring 31.77 g of deionized water, 0.413 g of sodium aluminate (containing 40.5 wt% Al2O3 and 30.6 wt% Na2O), 0.571 g of sodium hydroxide, 6.24 g of methyltriethylammonium hydroxide (containing 25 wt% methyltriethylammonium hydroxide), and 16.00 g of silica sol (containing 40.0 wt% SiO2) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0129] SiO2 / Al2O3 = 65;

[0130] NaOH / SiO2 = 0.17;

[0131] R / SiO2 = 0.11;

[0132] H2O / SiO2 = 24.

[0133] The mixture was placed in a stainless steel reactor and heated to crystallize at 160°C with a stirring speed of 20 rpm for 4 days. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product was then analyzed. Figure 1 Similarly, as shown in Table 6, there are molecular sieves with MTW and MFI structures coexisting.

[0134] Table 6

[0135]

[0136]

[0137] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 64.7 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.015Al2O3·0.042R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​446 m² was obtained. 2 / gram, with an external specific surface area of ​​38 m² measured by the BET method. 2 / g; Total pore volume 0.46cm 3 / gram, micropore volume is 0.14 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 636 μmol / g, and the strong acid content was 224 μmol / g.

[0138] Example 7

[0139] A mixture was prepared by stirring 38.18 g of deionized water, 0.368 g of sodium aluminate (containing 40.5 wt% Al2O3 and 30.6 wt% Na2O), 0.681 g of sodium hydroxide, 5.58 g of methyltriethylammonium chloride (containing 25 wt% methyltriethylammonium chloride), and 15.36 g of silica sol (containing 40.0 wt% SiO2) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0140] SiO2 / Al2O3 = 70;

[0141] NaOH / SiO2 = 0.20;

[0142] R / SiO2 = 0.09;

[0143] H2O / SiO2 = 28.

[0144] The mixture was placed in a stainless steel reactor and heated to crystallize at 155°C with a stirring speed of 10 rpm for 6 days. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product was then analyzed. Figure 1 Similarly, as shown in Table 7, there are molecular sieves with MTW and MFI structures coexisting.

[0145] Table 7

[0146]

[0147]

[0148] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 69.5 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.014Al2O3·0.046R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​428 m² was obtained. 2 / gram, with an external specific surface area of ​​46 m² measured by the BET method. 2 / g; Total pore volume 0.50cm 3 / gram, micropore volume is 0.15 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 575 μmol / g, and the strong acid content was 186 μmol / g.

[0149] Example 8

[0150] A mixture was prepared by stirring 43.38 g of deionized water, 0.414 g of sodium aluminate (containing 40.5 wt% Al2O3 and 30.6 wt% Na2O), 0.675 g of sodium hydroxide, 6.20 g of methyltriethylammonium bromide (containing 25 wt% methyltriethylammonium bromide), and 14.83 g of silica sol (containing 40.0 wt% SiO2) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0151] SiO2 / Al2O3 = 60;

[0152] NaOH / SiO2 = 0.21;

[0153] R / SiO2 = 0.08;

[0154] H2O / SiO2 = 32.

[0155] The mixture was placed in a stainless steel reactor and heated to crystallize at 175°C with a stirring speed of 10 rpm for 2 days. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product was then analyzed. Figure 1 Similarly, as shown in Table 8, there are molecular sieves with MTW and MFI structures coexisting.

[0156] Table 8

[0157]

[0158]

[0159] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 59.8 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.017Al2O3·0.043R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​486 m² was obtained. 2 / gram, with an external specific surface area of ​​36 m² measured by the BET method. 2 / g; Total pore volume 0.49 cm 3 / gram, micropore volume is 0.15 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 651 μmol / g, and the strong acid content was 219 μmol / g.

[0160] Example 9

[0161] A mixture was prepared by stirring 26.62 g of deionized water, 0.476 g of sodium aluminate (containing 40.5 wt% Al2O3 and 30.6 wt% Na2O), 0.571 g of sodium hydroxide, 6.93 g of methyltriethylammonium chloride (containing 25 wt% methyltriethylammonium chloride), and 15.61 g of silica sol (containing 40.0 wt% SiO2) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0162] SiO2 / Al2O3 = 55;

[0163] NaOH / SiO2 = 0.18;

[0164] R / SiO2 = 0.11;

[0165] H2O / SiO2 = 22.

[0166] The mixture was placed in a stainless steel reactor and heated to crystallize at 170°C with a stirring speed of 40 rpm for 2.5 days. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product was then analyzed. Figure 1 Similarly, as shown in Table 9, there are molecular sieves with MTW and MFI structures coexisting.

[0167] Table 9

[0168]

[0169]

[0170] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 55.1 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.018Al2O3·0.051R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​471 m² was obtained. 2 / gram, with an external specific surface area of ​​39 m² measured by the BET method. 2 / g; Total pore volume 0.48cm 3 / gram, micropore volume is 0.16 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 724 μmol / g, and the strong acid content was 239 μmol / g.

[0171] Example 10

[0172] A mixture was prepared by stirring 10.26 g of deionized water, 0.270 g of sodium aluminate (containing 40.5 wt% Al2O3 and 30.6 wt% Na2O), 0.415 g of sodium hydroxide, 7.58 g of methyltriethylammonium bromide (containing 25 wt% methyltriethylammonium bromide), and 12.93 g of silica sol (containing 40.0 wt% SiO2) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0173] SiO2 / Al2O3 = 75;

[0174] NaOH / SiO2 = 0.16;

[0175] R / SiO2 = 0.12;

[0176] H2O / SiO2 = 16.

[0177] The mixture was placed in a stainless steel reactor and heated to crystallize at 165°C with a stirring speed of 50 rpm for 3.5 days. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product was then analyzed. Figure 1 Similarly, as shown in Table 10, there are molecular sieves with MTW and MFI structures coexisting.

[0178] Table 10

[0179]

[0180]

[0181] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 75.3 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.013Al2O3·0.057R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​386 m² was obtained. 2 / gram, with an external specific surface area of ​​47 m² measured by the BET method. 2 / g; Total pore volume 0.43cm 3 / gram, micropore volume is 0.13 cm³ 3 / g. Sodium-type molecular sieves were subjected to ammonium ion exchange with 0.2 mol / L NH4NO3 solution (mass ratio 1:20) at 65℃ for 2 hours, followed by centrifugation and washing. The ammonium ion exchange was repeated twice. The resulting sample was dried overnight at 100℃ and calcined in air at 550℃ for 6 hours to obtain hydrogen-type symbiotic molecular sieve samples. NH3-TPD analysis showed that the total acid content of the molecular sieve was 593 μmol / g, and the strong acid content was 202 μmol / g.

[0182] Comparative Example 1

[0183] The material ratio is the same as in Example 1, except that more sodium aluminate (containing 40.5% by weight of Al2O3 and 30.6% by weight of Na2O) is added. The final material ratio (molar ratio) is:

[0184] SiO2 / Al2O3 = 30;

[0185] NaOH / SiO2 = 0.16;

[0186] R / SiO2 = 0.10;

[0187] H2O / SiO2 = 18.

[0188] The mixture was placed in a stainless steel reactor and heated at 170°C and 20 rpm for 3 days to crystallize. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product is shown below. Figure 6 As shown, the sample did not crystallize and had an amorphous structure, and was not an MTW or MFI molecular sieve.

[0189] Comparative Example 2

[0190] The material ratio is the same as in Example 1, except that less organic structure-directing agent R is added. The final material ratio (molar ratio) is:

[0191] SiO2 / Al2O3 = 60;

[0192] NaOH / SiO2 = 0.16;

[0193] R / SiO2 = 0.03;

[0194] H2O / SiO2 = 18.

[0195] The mixture was placed in a stainless steel reactor and heated at 170°C and 20 rpm for 3 days to crystallize. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product is shown below. Figure 7 As shown, the sample did not crystallize and had an amorphous structure, and did not contain MTW or MFI molecular sieves.

[0196] Comparative Example 3

[0197] The material ratio is the same as in Example 1, except that tetraethylammonium hydroxide is added as the organic structure directing agent R. The final material ratio (molar ratio) is:

[0198] SiO2 / Al2O3 = 60;

[0199] NaOH / SiO2 = 0.16;

[0200] R / SiO2 = 0.10;

[0201] H2O / SiO2 = 18.

[0202] The mixture was placed in a stainless steel reactor and heated at 170°C and 20 rpm for 3 days to crystallize. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product was compared with... Figure 7 Similarly, the sample did not crystallize and had an amorphous structure, and was not an MTW or MFI molecular sieve.

[0203] Comparative Example 4

[0204] The material ratio is the same as in Example 1, except that aluminum chloride is added as the aluminum source. The final material ratio (molar ratio) is:

[0205] SiO2 / Al2O3 = 60;

[0206] NaOH / SiO2 = 0.16;

[0207] R / SiO2 = 0.10;

[0208] H2O / SiO2 = 18.

[0209] The mixture was placed in a stainless steel reactor and heated at 170°C and 20 rpm for 3 days to crystallize. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product was compared with... Figure 7 Similarly, the sample did not crystallize and had an amorphous structure, and was not an MTW or MFI molecular sieve.

[0210] Comparative Example 5

[0211] The material ratio is the same as in Example 1, except that the content of Al2O3 and Na2O in the added sodium aluminate is different. The sodium aluminate composition is 50.6% by weight of Al2O3 and 45.2% by weight of Na2O. The raw materials are prepared in the same amount of substances, and the final material ratio (molar ratio) is:

[0212] SiO2 / Al2O3 = 60;

[0213] NaOH / SiO2 = 0.16;

[0214] R / SiO2 = 0.10;

[0215] H2O / SiO2 = 18.

[0216] The mixture was placed in a stainless steel reactor and heated at 170°C and 20 rpm for 3 days to crystallize. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product is shown below. Figure 8 As shown, the sample is an MTW molecular sieve, which does not contain an MFI molecular sieve phase and is not a symbiotic molecular sieve of MTW and MFI.

[0217] Comparative Example 6

[0218] The material ratio is the same as in Example 1, except that Al2O3 and Na2O are added separately, and the raw materials are prepared in the same amount of each substance. The final material ratio (molar ratio) is:

[0219] SiO2 / Al2O3 = 60;

[0220] NaOH / SiO2 = 0.16;

[0221] R / SiO2 = 0.10;

[0222] H2O / SiO2 = 18.

[0223] The mixture was placed in a stainless steel reactor and heated at 170°C and 20 rpm for 3 days to crystallize. After crystallization, the mixture was filtered, washed, and dried overnight in an oven at 100°C. The XRD pattern of the obtained product was compared with... Figure 7 Similarly, the sample did not crystallize and had an amorphous structure, and was not an MTW or MFI molecular sieve.

[0224] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combining the various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A coexisting molecular sieve of MTW and MFI, characterized in that, The intergrowth molecular sieve has a chemical composition as shown in the formula "SiO2·1 / nAl2O3·pR", wherein 50≤n≤80, 0.04<p≤0.07, and R is a methyl triethyl ammonium ion.

2. The symbiotic molecular sieve of claim 1, wherein, The intergrowth molecular sieve comprises an X-ray diffraction pattern as shown in the following table, a: ±0.30°, b: as a function of 2θ.

3. The intergrown molecular sieve of claims 1 or 2, wherein, The intergrowth molecular sieve further comprises an X-ray diffraction pattern as shown in the following table, a: ±0.30°, b: as a function of 2θ.

4. The intergrowth molecular sieve according to claim 1 or 2, wherein, after calcination of the intergrowth molecular sieve at 300-800 ℃ for 1-10 hours: The total specific surface area of the symbiotic molecular sieve is not less than 360 meters 2 / gram; and / or The external specific surface area of the symbiotic molecular sieve is not less than 30 m2 / g 2 / gram; and / or The total pore volume of the paragenetic molecular sieve is not less than 0.35 cm3 / g 3 / gram; and / or The micropore volume of the symbiotic molecular sieve is not less than 0.12 cm3 / g 3 / gram; and / or after ammonium ion exchange and calcination into a hydrogen type intergrowth molecular sieve: the total acid amount of the intergrowth molecular sieve is not less than 500 μmol / g; and / or the strong acid amount of the intergrowth molecular sieve is not less than 150 μmol / g.

5. The intergrowth molecular sieve according to claim 4, wherein, after calcination of the intergrowth molecular sieve at 400-650 ℃ for 3-6 hours: The total specific surface area of the paragenetic molecular sieve is 360-550 m2 / g 2 / gram; and / or The external specific surface area of the symbiotic molecular sieve is 30-60 m2 / g 2 / gram; and / or The total pore volume of the paragenetic molecular sieve is 0.35-0.60 cm3 / g 3 / gram; and / or The micropore volume of the paragenetic molecular sieve is 0.12-0.20 cm3 / g 3 / gram; and / or after ammonium ion exchange and calcination into a hydrogen type intergrowth molecular sieve: the total acid amount of the intergrowth molecular sieve is 500-900 μmol / g; and / or the strong acid amount of the intergrowth molecular sieve is 150-300 μmol / g.

6. The method of making a symbiotic molecular sieve of any of claims 1-5, wherein, The method comprises mixing a silicon source, sodium aluminate, sodium hydroxide, an organic structure directing agent and water, crystallizing, filtering, washing, and drying to obtain the intergrowth molecular sieve; wherein, the content of Al2O3 in the sodium aluminate is 35%-43% by weight, and the content of Na2O is 25%-33% by weight; the organic structure directing agent is selected from at least one of methyl triethyl ammonium hydroxide, methyl triethyl ammonium chloride, methyl triethyl ammonium bromide, and methyl triethyl ammonium iodide; the molar ratio of the silicon source (calculated as SiO2), sodium aluminate (calculated as Al2O3), sodium hydroxide, the organic structure directing agent (calculated as a methyl triethyl ammonium ion), and water is 1:0.012-0.020:0.15-0.25:0.07-0.12:10-50.

7. The production method according to claim 6, wherein the content of Al2O3 in the sodium aluminate is 38%-43% by weight, and the content of Na2O is 28%-33% by weight.

8. The preparation method according to claim 6, wherein, the organic structure directing agent is methyl triethyl ammonium hydroxide; and / or the molar ratio of the silicon source (calculated as SiO2), sodium aluminate (calculated as Al2O3), sodium hydroxide, the organic structure directing agent (calculated as a methyl triethyl ammonium ion), and water is 1:0.013-0.019:0.16-0.24:0.08-0.12:14-45.

9. The production method according to claim 6, wherein the crystallization conditions comprise a crystallization temperature of 150-180 ℃; and / or a crystallization time of 1.0-8.0 days.

10. The production method according to claim 9, wherein the crystallization conditions comprise a crystallization temperature of 155-175 ℃; and / or a crystallization time of 1.5-7.5 days.

11. The method of making according to any one of claims 6-10, wherein, The preparation method further comprises calcination, ammonium ion exchange, and re-calcination into a hydrogen type molecular sieve on the intergrowth molecular sieve obtained after drying.

12. The preparation method according to claim 11, wherein, The ammonium ion exchange conditions include: the concentration of ammonium ions in the ammonium salt solution is 0.1-1 mol / L, the solid-liquid mass ratio is 1:5-1:20, the ammonium exchange temperature is 30-80℃, and the ammonium exchange time is 1-8 hours; and / or The re-baking into hydrogen type molecular sieve conditions include: the baking temperature is 300-800℃, and the baking time is 1-10 hours.

13. The preparation method of claim 12, wherein, The ammonium ion exchange conditions include: the ammonium exchange times is 1-2 times, and the ammonium salt is at least one selected from the group consisting of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium sulfate; and / or The re-baking into hydrogen type molecular sieve conditions include: the baking temperature is 400-650℃, and the baking time is 3-6 hours.

14. The use of the symbiotic molecular sieve of any one of claims 1-5 in the preparation of an adsorbent or a catalyst.

15. A catalyst characterized by, The catalyst comprises the symbiotic molecular sieve of any one of claims 1-5.

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