MOR and ANA coexisting molecular sieve, and preparation method and application thereof

Abstract

The application discloses a MOR and ANA symbiotic molecular sieve, a preparation method and application thereof. The symbiotic molecular sieve has a schematic chemical composition as shown in a formula "SiO2*1 / nAl2O3*pR" before calcination, wherein 10<=n<=30, and R is an organic structure directing agent. The preparation method of the symbiotic molecular sieve is simple, and the cost is low. The symbiotic molecular sieve can be used as an adsorbent or a catalyst for organic compound conversion.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of molecular sieves, in particular to a MOR and ANA symbiotic molecular sieve, a preparation method and application thereof. BACKGROUND

[0002] MOR type molecular sieve has eight-membered ring and twelve-membered ring (0.67nm*0.70nm) straight pore channels along

[001] direction, and also has eight-membered ring (0.26nm*0.57nm) straight pore channels along

[010] direction between the eight-membered ring and the twelve-membered ring. The main pore channel of the MOR molecular sieve is the twelve-membered ring structure, which has good catalytic stability, and has been widely used in processes such as hydrocracking, isomerization, alkylation and reforming, and can also be used for separating gas or liquid mixtures. For dimethyl ether carbonylation reaction, the MOR molecular sieve also has very high industrial application prospect. ANA type molecular sieve is a zeolite molecular sieve material with small pore channels, which has eight-membered ring structure, unique internal structure and crystal chemical properties. Due to its special selective adsorption and heterogeneous catalytic properties, it has wide application in medical treatment and other aspects. If the two molecular sieves are organically symbiotic and composite, and are endowed with reasonable acid distribution, good shape selection, long and short, it may have unique application effect on some catalytic reactions or adsorption, separation.

[0003] The above two kinds of molecular sieve materials all have the problems of uniform and single pore size, weak acidity, low activity and poor selectivity, and are difficult to handle complex components alone, and they have different catalytic properties for the same reactants. The porous symbiotic molecular sieve containing two or more components contains a multi-level pore structure, a wide range of strong and weak acid distribution, and can handle complex components with different molecular diameters. In the application of catalysis, adsorption and other applications, it can exert its own advantages and cooperatively realize the treatment of complex components with different molecular sizes.

[0004] CN101279743B discloses a symbiotic molecular sieve and a synthesis method thereof, by adding seed crystals containing beta zeolite precursors in the synthesis process of the symbiotic molecular sieve, controlling the nucleation and growth process of the molecular sieve, and preparing a symbiotic molecular sieve, which is a ZSM-5 / mordenite / β symbiotic molecular sieve material. CN100586858 discloses a porous symbiotic material and a synthesis method thereof, by controlling the nucleation and growth process of the molecular sieve in the synthesis process of the porous material, and preparing a porous symbiotic material, which has adjustable symbiotic phase ratio and is a ZSM-5 / mordenite / β symbiotic molecular sieve material, and can be used in the industrial production of naphtha catalytic cracking to produce ethylene and propylene. CN101514010B discloses a mordenite / β zeolite / cubic zeolite porous symbiotic material and a preparation method thereof, which is realized by controlling the nucleation and growth process of the molecular sieve in the synthesis process, but the synthesis method needs to add a large amount of organic structure directing agent suitable for the growth of two or more phases, and needs to strictly control the pH value, silicon-aluminum ratio and crystallization temperature of the synthesis system to synthesize the symbiotic molecular sieve, and the synthesis method is relatively complex.

[0005] At present, the symbiotic zeolite molecular sieve commonly used with MOR molecular sieve is combined with MFI molecular sieve or β molecular sieve. There are few reports on MOR and ANA symbiotic molecular sieve. CN104556137B discloses a MOR / ANA type porous zeolite symbiotic material and a preparation method thereof, wherein a quaternary ammonium salt is added in the preparation of seed crystals, and the seed crystal induction whole crystal transformation method is used to prepare the symbiotic molecular sieve material. CN106672993B discloses a MOR and ANA symbiotic zeolite and a preparation method thereof, wherein a double-group double-function organic template agent is used as a reaction raw material, and a MOR and ANA symbiotic molecular sieve with good dispersity, large specific surface area and pore volume is obtained by hydrothermal crystallization, which is beneficial to the application in petroleum chemical industry, catalysis, ion adsorption and purification. The above method uses a large amount of seed crystals to synthesize two-phase molecular sieves with a similar core-shell structure, which is not a true two-phase symbiotic molecular sieve, or the organic structure directing agent used is a compound similar to dibromo(chloro 1-nitrogen methyl pyrrole-3-nitrogen methyl piperidyl propane), which has a very complex structure and high preparation cost. Directly preparing a MOR and ANA type porous symbiotic molecular sieve by using a low-cost method will help to expand its application scenarios. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a CHA and MOR symbiotic molecular sieve, a preparation method thereof and an application thereof. The preparation method of the symbiotic molecular sieve is simple and has low cost, and the symbiotic molecular sieve can be used as an adsorbent or a catalyst for organic compound conversion.

[0007] The first aspect of the present application provides a MOR and ANA coexisting molecular sieve, the coexisting molecular sieve has a schematic chemical composition as shown in the formula "SiO2·1 / nAl2O3·pR" before calcination, wherein 10≤n≤30, R is an organic structure directing agent, the MOR and ANA coexisting molecular sieve comprises an X-ray diffraction pattern as shown in the following table,

[0008]

[0009] a: ±0.30°, b: varies with 2θ.

[0010] Further, the organic structure directing agent R is a quaternary ammonium salt or quaternary ammonium base compound containing dimethyldiethylammonium ion.

[0011] Further, 0.02≤p≤0.07.

[0012] Further, the X-ray diffraction pattern further comprises X-ray diffraction peaks as shown in the following table,

[0013]

[0014]

[0015] a: ±0.30°, b: varies with 2θ.

[0016] Further, after the MOR and ANA coexisting molecular sieve is calcined, the total specific surface area is not less than 350 m 2 / gram, preferably 350-550 m 2 / gram; the external specific surface area is not less than 20 m 2 / gram, preferably 20-60 m 2 / gram; the total pore volume is not less than 0.25 cm 3 / gram, preferably 0.25-0.50 cm 3 / gram; the micropore (pore <2 nm) pore volume is not less than 0.15 cm 3 / gram, preferably 0.15-0.30 cm 3 / gram.

[0017] The second aspect of the present application provides a preparation method of a MOR and ANA coexisting molecular sieve, comprising the following steps:

[0018] Mixing a silicon source, an aluminum source, an alkali source, an organic structure directing agent R and water, and performing crystallization treatment to obtain the coexisting molecular sieve; the organic structure directing agent R is a quaternary ammonium salt or quaternary ammonium base compound containing dimethyldiethylammonium ion;

[0019] The silicon source is calculated as SiO2, the aluminum source is calculated as Al2O3, the alkali source is calculated as OH -further, the silicon source is a silica sol, the aluminum source is sodium aluminate, the alkali source is potassium hydroxide and / or sodium hydroxide, and the organic structure directing agent R is at least one of dimethyldiethylammonium hydroxide, dimethyldiethylammonium chloride, dimethyldiethylammonium bromide, or dimethyldiethylammonium iodide, preferably dimethyldiethylammonium hydroxide. - : R: H2O = 1 : 0.030-0.110 : 0.39-0.55 : 0.02-0.12 : 10-50.

[0020] Further, the organic structure directing agent R is at least one of dimethyldiethylammonium hydroxide, dimethyldiethylammonium chloride, dimethyldiethylammonium bromide, or dimethyldiethylammonium iodide, preferably dimethyldiethylammonium hydroxide.

[0021] Further, the silicon source is a silica sol, the aluminum source is sodium aluminate, the alkali source is potassium hydroxide and / or sodium hydroxide, and the organic structure directing agent R is at least one of dimethyldiethylammonium hydroxide, dimethyldiethylammonium chloride, dimethyldiethylammonium bromide, or dimethyldiethylammonium iodide, preferably dimethyldiethylammonium hydroxide. - : R: H2O = 1 : 0.030-0.110 : 0.39-0.55 : 0.02-0.12 : 10-50.

[0022] Further, the silicon source is a silica sol, the aluminum source is sodium aluminate, the alkali source is potassium hydroxide and / or sodium hydroxide, and the organic structure directing agent R is at least one of dimethyldiethylammonium hydroxide, dimethyldiethylammonium chloride, dimethyldiethylammonium bromide, or dimethyldiethylammonium iodide, preferably dimethyldiethylammonium hydroxide.

[0023] Further, the content of Al2O3 in the sodium aluminate is 35% to 43%, preferably 38% to 43%, and the content of Na2O is 25% to 33%, preferably 28% to 33%, by weight.

[0024] Further, the crystallization treatment is carried out at 150 to 180°C for 0.5 to 8.0 days, preferably at 155 to 175°C for 1.0 to 7.5 days.

[0025] Further, the crystallization treatment is carried out at 150 to 180°C for 0.5 to 8.0 days, preferably at 155 to 175°C for 1.0 to 7.5 days.

[0026] Further, after the crystallization treatment, the product can be obtained from the mixture by any separation method known in the art. As the separation method, for example, a method in which the obtained mixture is filtered, washed, and dried can be mentioned. Here, the filtration, washing, and drying can be carried out in any manner known in the art. Specifically, as the filtration, for example, the obtained product mixture can be simply suction-filtered. As the washing, for example, washing with deionized water and / or ethanol can be mentioned. As the drying temperature, for example, 40 to 250°C, preferably 60 to 150°C can be mentioned, and as the drying time, for example, 8 to 30 hours, preferably 10 to 20 hours can be mentioned. The drying can be carried out under normal pressure or under reduced pressure.

[0027] Further, the MOR and ANA coexisting molecular sieve obtained after the crystallization treatment can be further treated by calcination to obtain a sodium type coexisting molecular sieve, which can be carried out in any manner known in the art, such as a calcination temperature of generally 300-800°C, preferably 400-650°C, and a calcination time of generally 1-10 hours, preferably 3-6 hours. In addition, the calcination is generally carried out in an oxygen-containing atmosphere, such as an air or oxygen atmosphere.

[0028] The third aspect of the present application further provides a molecular sieve composition comprising the MOR and ANA coexisting molecular sieve according to any one of the preceding first aspect or prepared by the preparation method according to any one of the preceding second aspect, and a binder.

[0029] The fourth aspect of the present application further provides the use of the MOR and ANA coexisting molecular sieve according to any one of the preceding first aspect or prepared by the preparation method according to any one of the preceding second aspect, or the molecular sieve composition according to the preceding third aspect as an adsorbent or a catalyst for organic compound conversion.

[0030] The molecular sieve of the present application is a MOR and ANA structure coexisting composition, which has a unique chemical composition and XRD diffraction pattern. The present application provides a simple and feasible preparation method of the MOR and ANA coexisting molecular sieve, which uses a small amount of organic structure directing agent, has a simple synthesis method, and has a good crystallization condition of the coexisting molecular sieve. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 X-ray diffraction spectrum (XRD) of the sample in Example 1;

[0032] Figure 2 X-ray diffraction spectrum (XRD) of the sample in Example 2;

[0033] Figure 3 X-ray diffraction spectrum (XRD) of the sample in Example 3;

[0034] Figure 4 X-ray diffraction spectrum (XRD) of the sample in Example 4;

[0035] Figure 5 X-ray diffraction spectrum (XRD) of the sample in Example 5;

[0036] Figure 6 X-ray diffraction spectrum (XRD) of the sample in Comparative Example 1;

[0037] Figure 7X-ray diffraction pattern (XRD) of the sample in Comparative Example 2;

[0038] Figure 8 X-ray diffraction pattern (XRD) of the sample in Comparative Example 3;

[0039] Figure 9 X-ray diffraction pattern (XRD) of the sample in Comparative Example 4. DETAILED DESCRIPTION

[0040] According to the present application, the molecular sieve obtained as described above can be used in any physical form, such as powder, granule or molded product (such as strip, clover, etc.). These physical forms can be obtained in any manner known in the art and are not particularly limited.

[0041] In the context of the present specification, the structure of the molecular sieve of MOR and ANA is determined by X-ray diffraction pattern (XRD), which is measured by X-ray powder diffractometer using Cu-Ka radiation source, nickel filter. Before the sample is tested, the crystallization of the molecular sieve sample is observed by scanning electron microscope (SEM) to confirm that the sample contains only one crystal, i.e. the molecular sieve sample is in pure phase, on which basis the XRD test is carried out to ensure that there is no interference peak of other crystals in the diffraction peak in the XRD pattern.

[0042] In the context of the present specification, in the XRD data of the molecular sieve, w, m, s, vs represent the intensity of the diffraction peak, w is weak, m is moderate, s is strong, and vs is very strong, which is well known to those skilled in the art. Generally, w is less than 20; m is 20-40; s is 40-70; vs is greater than 70.

[0043] In the context of the present specification, including in the following examples and comparative examples, the model of the X-ray powder diffractometer for the molecular sieve is Panalytical X PER PRO X-ray powder diffractometer, the sample is analyzed for phase, Cu Kα radiation source Nickel filter, 2θ scanning range 2-50°, operating voltage 40KV, current 40mA, scanning rate 10° / min.

[0044] In the context of the present specification, including in the examples and comparative examples below, the micropore size, pore volume, specific surface area, external specific surface area of the molecular sieve are measured by nitrogen physisorption-desorption method (BET method): nitrogen physisorption-desorption isotherm of the molecular sieve is measured by using a physisorption instrument (Micromeretic ASAP 2020M physisorption instrument), and then calculated by BET equation and t-plot equation. The experimental conditions for the molecular sieve are: measurement temperature -196°C, and the molecular sieve is first heat-treated at 550°C in air atmosphere for 6 hours, and then pretreated at 350°C under vacuum for 4 hours.

[0045] In the context of the present specification, including in the examples and comparative examples below, the content of silicon and aluminum in the molecular sieve is determined by inductively coupled plasma atomic emission spectrometer (ICP), and the inductively coupled plasma atomic emission spectrometer (ICP) is of the model Varian 725-ES. The analysis sample is dissolved with hydrofluoric acid to detect the content of elements in moles.

[0046] In the context of the present specification, including in the examples and comparative examples below, the content of organic matter in the molecular sieve is determined by a thermal gravimetric analyzer, and the thermal gravimetric analyzer is of the model SDT Q600 V20.9 Build 20. The sample is heated from 50°C to 800°C at a rate of 10°C / min under air or oxygen atmosphere to detect the weight loss, and the weight loss percentage of the sample in the range of 200-700°C is the content of organic matter of the sample.

[0047] The present application is further illustrated in detail by the following examples, but the present application is not limited to these examples.

[0048] Example 1

[0049] A mixture was prepared by stirring 11.18 g of deionized water, 1.697 g of sodium aluminate (containing Al2O3 40.5% by weight, Na2O 30.6% by weight), 0.717 g of sodium hydroxide, 1.29 g of dimethyldiethylammonium hydroxide (containing dimethyldiethylammonium hydroxide 25% by weight) (organic structure directing agent R), and 10.12 g of silica sol (containing SiO2 40.0% by weight) at room temperature for 3 hours, and the final material ratio (molar ratio) was:

[0050] SiO2 / Al2O3 = 10;

[0051] NaOH / SiO2 = 0.50;

[0052] R / SiO2 = 0.04;

[0053] H2O / SiO2 = 15.

[0054] The mixture was charged into a stainless steel autoclave and crystallized at 165°C with stirring at 50 rpm for 5 days. After crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product is shown in Fig. 1 and Table 1, and is a MOR and ANA structure coexisting molecular sieve. Figure 1 and Table 1, and is a MOR and ANA structure coexisting molecular sieve.

[0055] Table 1

[0056]

[0057] The molar chemical composition of the sample was "1 SiO2-0.097 Al2O3-0.022 R". After calcination of the sample at 550°C in air for 6 hours, the specific surface area of the molecular sieve was 396 m2 / g, the external specific surface area was 34 m2 / g, the total pore volume was 0.41 cm3 / g, and the micropore volume was 0.17 cm3 / g. 2 2 3 3

[0058] Example 2

[0059] A mixture was prepared by stirring 48.50 g of deionized water, 0.706 g of sodium aluminate (containing Al2O3 40.5 wt%, Na2O 30.6 wt%), 1.151 g of sodium hydroxide, 2.01 g of dimethyldiethylammonium hydroxide (containing dimethyldiethylammonium hydroxide 25 wt%) (organic structure directing agent R), and 12.63 g of silica sol (containing SiO2 40.0 wt%) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0060] SiO2 / Al2O3 = 30;

[0061] NaOH / SiO2 = 0.42;

[0062] R / SiO2 = 0.05;

[0063] H2O / SiO2 = 38.

[0064] The mixture was charged into a stainless steel autoclave and crystallized at 160°C with stirring at 40 rpm for 4 days. After crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product is shown in Fig. 2 and Table 2, and is a MOR and ANA structure coexisting molecular sieve. Figure 2 and Table 2, and is a MOR and ANA structure coexisting molecular sieve.

[0065] Table 2

[0066]

[0067] ​​​​

[0068] The molar chemical composition of the sample was "1 SiO2-0.034 Al2O3-0.025 R". The specific surface area of the molecular sieve obtained after calcination of the sample in air at 550°C for 6 hours was 416 m2 / g, the external specific surface area measured by the BET method was 29 m2 / g; the total pore volume was 0.48 cm3 / g, and the micropore volume was 0.16 cm3 / g. 2 2 3 3

[0069] Example 3

[0070] A mixture was prepared by stirring 8.76 g of deionized water, 0.954 g of sodium aluminate (containing Al2O3 40.5% by weight, Na2O 30.6% by weight), 1.010 g of sodium hydroxide, 2.89 g of dimethyldiethylammonium hydroxide (containing dimethyldiethylammonium hydroxide 25% by weight) (organic structure directing agent R), and 11.39 g of silica sol (containing SiO2 40.0% by weight) at room temperature for 3 hours, and the final material ratio (molar ratio) was:

[0071] SiO2 / Al2O3 = 20;

[0072] NaOH / SiO2 = 0.45;

[0073] R / SiO2 = 0.08;

[0074] H2O / SiO2 = 13.

[0075] The mixture was loaded into a stainless steel autoclave and heated for crystallization at 155°C with a stirring speed of 10 rpm for 6 days. After crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD spectrum of the product is shown in Figure 3 and Table 3, and is a molecular sieve with MOR and ANA structures coexisting.

[0076] Table 3

[0077]

[0078]

[0079] The molar chemical composition of the sample was "1 SiO2-0.049 Al2O3-0.043 R". The specific surface area of the molecular sieve obtained after calcination of the sample in air at 550°C for 6 hours was 431 m2 / g, the external specific surface area measured by the BET method was 35 m2 / g; the total pore volume was 0.44 cm3 / g, and the micropore volume was 0.15 cm3 / g. 2 2 3 3 ​​​​​​​​

[0080] Example 4

[0081] A mixture was prepared by stirring 38.52 g of deionized water, 1.573 g of sodium aluminate (containing Al2O340.5 wt%, Na2O 30.6 wt%), 0.915 g of sodium hydroxide, 4.92 g of dimethyldiethylammonium hydroxide (containing dimethyldiethylammonium hydroxide 25 wt%) (organic structure directing agent R), and 14.08 g of silica sol (containing SiO240.0 wt%) at room temperature for 3 hours, and the final material ratio (molar ratio) was as follows:

[0082] SiO2 / Al2O3 = 15;

[0083] NaOH / SiO2 = 0.40;

[0084] R / SiO2 = 0.11;

[0085] H2O / SiO2 = 30.

[0086] The mixture was charged into a stainless steel autoclave and heated for crystallization at 150°C for 7 days with stirring at 30 rpm. After crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product is shown in Figure 4 and Table 4, and the product was a molecular sieve in which MOR and ANA structures coexisted. Figure 4

[0087] Table 4

[0088]

[0089]

[0090] The molar chemical composition of the sample was "1SiO2·0.066Al2O3·0.065R". After calcination of the sample at 550°C in air for 6 hours, the specific surface area of the molecular sieve was 389 m2 / g, the external specific surface area was 41 m2 / g as measured by the BET method, the total pore volume was 0.38 cm3 / g, and the micropore volume was 0.18 cm3 / g. 2 2 3 3

[0091] Example 5

[0092] ​​​​​A mixture was prepared by stirring 16.46 g of deionized water, 0.836 g of sodium aluminate (containing Al2O340.5 wt%, Na2O 30.6 wt%), 1.283 g of sodium hydroxide, 3.96 g of dimethyldiethylammonium hydroxide (containing dimethyldiethylammonium hydroxide 25 wt%) (organic structure directing agent R), and 12.46 g of silica sol (containing SiO240.0 wt%) at room temperature for 3 hours, and the final material ratio (molar ratio) was:

[0093] SiO2 / Al2O3 = 25;

[0094] NaOH / SiO2 = 0.48;

[0095] R / SiO2 = 0.10;

[0096] H2O / SiO2 = 18.

[0097] The mixture was charged into a stainless steel autoclave and heated for crystallization at 170°C for 3 days under stirring at a rotation speed of 20 rpm. After the crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD spectrum of the product is shown in Fig. 2 and Table 5, and the product is a molecular sieve in which MOR and ANA structures coexist. Figure 5

[0098] Table 5

[0099]

[0100]

[0101] The molar ratio of the chemical composition of the sample was "1SiO2·0.040Al2O3·0.054R". After the sample was calcined at 550°C for 6 hours in air, the specific surface area of the molecular sieve was 377 m2 / g, the external specific surface area was 38 m2 / g, the total pore volume was 0.36 cm3 / g, and the micropore volume was 0.17 cm3 / g. 2 2 3 3

[0102] Example 6

[0103] A mixture was prepared by stirring 27.30 g of deionized water, 1.535 g of sodium aluminate (containing Al2O340.5 wt%, Na2O 30.6 wt%), 1.537 g of sodium hydroxide, 3.14 g of dimethyldiethylammonium hydroxide (containing dimethyldiethylammonium hydroxide 25 wt%) (organic structure directing agent R), and 16.49 g of silica sol (containing SiO240.0 wt%) at room temperature for 3 hours, and the final material ratio (molar ratio) was:

[0104] ​​​​​SiO2 / Al2O3 = 18;

[0105] NaOH / SiO2 = 0.48;

[0106] R / SiO2 = 0.06;

[0107] H2O / SiO2 = 20.

[0108] The mixture was charged into a stainless steel autoclave and crystallized at 175°C for 2 days with stirring at 10 rpm. After crystallization, the product was filtered, washed and dried in an oven at 100°C overnight. The XRD pattern and SEM photograph of the product are shown in Figs. 1 and 2, respectively. Figure 1 Similarly, a mixture for coexisting MOR and ANA structure zeolite was prepared as shown in Table 6.

[0109] Table 6

[0110]

[0111]

[0112] The chemical composition of the sample in terms of molar ratio was "1 SiO2-0.055 Al2O3-0.027 R". The specific surface area of the zeolite obtained after calcination of the sample at 550°C for 6 hours in air was 408 m2 / g, the external specific surface area was 27 m2 / g, the total pore volume was 0.43 cm3 / g and the micropore volume was 0.16 cm3 / g. 2 2 3 3

[0113] Example 7

[0114] A mixture was prepared by stirring 40.36 g of deionized water, 0.970 g of sodium aluminate (containing Al2O3 40.5 wt%, Na2O 30.6 wt%), 1.132 g of sodium hydroxide, 5.25 g of dimethyldiethylammonium bromide (containing dimethyldiethylammonium bromide 25 wt%) (organic structure directing agent R) and 12.74 g of silica sol (containing SiO2 40.0 wt%) at room temperature for 3 hours. The final material ratio (molar ratio) was as follows:

[0115] SiO2 / Al2O3 = 22;

[0116] NaOH / SiO2 = 0.44;

[0117] R / SiO2 = 0.085;

[0118] H2O / SiO2 = 34.

[0119] ​​​​The mixture was charged into a stainless steel autoclave and heated at 155°C with stirring at 30 rpm for 4.5 days. After the crystallization was completed, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product and the SEM photograph of the product are shown in Figs. 1 and 2, respectively. Figure 1 Similarly, the molecular sieve coexisting with MOR and ANA structures was prepared as shown in Table 7.

[0120] Table 7

[0121]

[0122]

[0123] The chemical composition of the sample in terms of molar ratio was "1 SiO2-0.045 Al2O3-0.041 R". The specific surface area of the molecular sieve was 423 m2 / g, the external specific surface area was 33 m2 / g, the total pore volume was 0.34 cm3 / g, and the micropore volume was 0.16 cm3 / g after the sample was calcined at 550°C in air for 6 hours. 2 2 3 3

[0124] Example 8

[0125] A mixture was prepared by stirring 33.54 g of deionized water, 1.525 g of sodium aluminate (containing Al2O3 40.5 wt%, Na2O 30.6 wt%), 1.216 g of sodium hydroxide, 4.16 g of dimethyldiethylammonium hydroxide (containing dimethyldiethylammonium hydroxide 25 wt%) (organic structure directing agent R), and 14.56 g of silica sol (containing SiO2 40.0 wt%) at room temperature for 3 hours. The final material ratio (molar ratio) was as follows:

[0126] SiO2 / Al2O3 = 16;

[0127] NaOH / SiO2 = 0.46;

[0128] Dimethyldiethylammonium hydroxide / SiO2 = 0.09;

[0129] H2O / SiO2 = 26.

[0130] The mixture was charged into a stainless steel autoclave and heated at 165°C with stirring at 10 rpm for 4 days. After the crystallization was completed, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product and the SEM photograph of the product are shown in Figs. 3 and 4, respectively. Figure 1 Similarly, the molecular sieve coexisting with MOR and ANA structures was prepared as shown in Table 8.

[0131] Table 8

[0132] ​​​​

[0133]

[0134] The chemical composition of the sample's molar ratio is "1SiO2·0.064Al2O3·0.049R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​452 m² was obtained. 2 / gram, with an external specific surface area of ​​44 m² measured by the BET method. 2 / g; Total pore volume 0.39cm 3 / gram, micropore volume is 0.18 cm³ 3 / gram.

[0135] Example 9

[0136] A mixture was prepared by stirring 22.66 g of deionized water, 1.029 g of sodium aluminate (containing 40.5 wt% Al₂O₃ and 30.6 wt% Na₂O), 0.990 g of sodium hydroxide, 3.15 g of dimethyl diethyl ammonium chloride (containing 25 wt% dimethyl diethyl ammonium chloride) (organic structure directing agent R), and 12.27 g of silica sol (containing 40.0 wt% SiO₂) at room temperature for 3 hours. The final material ratio (molar ratio) was:

[0137] SiO2 / Al2O3 = 20;

[0138] NaOH / SiO2 = 0.42;

[0139] R / SiO2 = 0.07;

[0140] H2O / SiO2 = 22.

[0141] 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 coexisting MOR and ANA structures.

[0142] Table 9

[0143]

[0144] The SiO2 / Al2O3 molar ratio of the molecular sieve was determined to be 20.3 using inductively coupled plasma atomic emission spectrometry (ICP). The chemical composition of the sample's molar ratio was "1SiO2·0.049Al2O3·0.041R". After calcining the sample in air at 550℃ for 6 hours, a molecular sieve with a specific surface area of ​​420 m² was obtained. 2 / gram, with an external specific surface area of ​​39 m² measured by the BET method. 2cm3 / g; total pore volume 0.32 cm3 / g 3 cm3 / g, micropore volume 0.16 cm3 / g 3 cm3 / g.

[0145] Example 10

[0146] A mixture was prepared by stirring 15.62 g of deionized water, 1.534 g of sodium aluminate (containing Al2O3 40.5 wt%, Na2O 30.6 wt%), 1.075 g of sodium hydroxide, 3.33 g of dimethyldiethylammonium bromide (containing dimethyldiethylammonium bromide 25 wt%) (organic structure directing agent R), and 13.73 g of silica sol (containing SiO2 40.0 wt%) at room temperature for 3 hours, and the final material ratio (molar ratio) was as follows:

[0147] SiO2 / Al2O3 = 15;

[0148] NaOH / SiO2 = 0.45;

[0149] R / SiO2 = 0.05;

[0150] H2O / SiO2 = 16.

[0151] The mixture was charged into a stainless steel autoclave and heated for crystallization at 175°C for 1.5 days under stirring at a rotation speed of 15 rpm. After the crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern and SEM photograph of the product were obtained. Figure 1 Similarly, a molecular sieve with coexisting MOR and ANA structures was obtained, as shown in Table 10.

[0152] Table 10

[0153]

[0154]

[0155] The molar ratio of the chemical composition of the sample was "1 SiO2·0.067 Al2O3·0.024 R". After the sample was calcined at 550°C for 6 hours in air, the specific surface area of the molecular sieve was 414 m2 / g, the external specific surface area was 47 m2 / g, as measured by the BET method, the total pore volume was 0.35 cm3 / g, and the micropore volume was 0.17 cm3 / g. 2 2 3 3

[0156] Comparative Example 1

[0157] The material ratio was the same as in Example 1, except that less sodium hydroxide was added, and the final material ratio (molar ratio) was as follows:

[0158] SiO2 / Al2O3 = 10;​​​​

[0159] NaOH / SiO2= 0.24;

[0160] R / SiO2= 0.04;

[0161] H2O / SiO2= 15.

[0162] The mixture was charged into a stainless steel autoclave and heated at 165°C with stirring at 50 rpm for crystallization for 5 days. After the crystallization was completed, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD spectrum of the product is shown in Fig. 1, indicating that the sample is a MOR structure molecular sieve and does not contain ANA molecular sieve. Figure 6

[0163] Comparative Example 2

[0164] The material ratios were the same as in Example 1, except that less aluminum source was added. The final material ratios (molar ratios) were as follows:

[0165] SiO2 / Al2O3= 40;

[0166] NaOH / SiO2= 0.50;

[0167] R / SiO2= 0.04;

[0168] H2O / SiO2= 15.

[0169] The mixture was charged into a stainless steel autoclave and heated at 165°C with stirring at 50 rpm for crystallization for 5 days. After the crystallization was completed, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD spectrum of the product is shown in Fig. 2, indicating that the sample was not crystallized and was amorphous, and did not contain MOR or ANA molecular sieve. Figure 7

[0170] Comparative Example 3

[0171] The material ratios were the same as in Example 2, except that tetraethylammonium hydroxide was used as the organic structure directing agent R. The final material ratios (molar ratios) were as follows:

[0172] SiO2 / Al2O3= 30;

[0173] NaOH / SiO2= 0.42;

[0174] R / SiO2= 0.05;

[0175] H2O / SiO2= 38.

[0176] ​​The mixture was charged into a stainless steel autoclave and heated at 160°C with stirring at 40 rpm for 4 days. After crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product is shown in Fig. 1, indicating that the sample is a MOR molecular sieve and does not contain an ANA molecular sieve. Figure 8 The mixture was charged into a stainless steel autoclave and heated at 160°C with stirring at 40 rpm for 4 days. After crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product is shown in Fig. 1, indicating that the sample is a MOR molecular sieve and does not contain an ANA molecular sieve.

[0177] Comparative Example 4

[0178] The mixture was charged into a stainless steel autoclave and heated at 160°C with stirring at 40 rpm for 4 days. After crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product is shown in Fig. 1, indicating that the sample is a MOR molecular sieve and does not contain an ANA molecular sieve.

[0179] SiO2 / Al2O3 = 20;

[0180] NaOH / SiO2 = 0.45;

[0181] R / SiO2 = 0.08;

[0182] H2O / SiO2 = 13.

[0183] The mixture was charged into a stainless steel autoclave and heated at 160°C with stirring at 40 rpm for 4 days. After crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product is shown in Fig. 1, indicating that the sample is a MOR molecular sieve and does not contain an ANA molecular sieve. Figure 9 The mixture was charged into a stainless steel autoclave and heated at 160°C with stirring at 40 rpm for 4 days. After crystallization, the product was filtered, washed, and dried in an oven at 100°C overnight. The XRD pattern of the product is shown in Fig. 1, indicating that the sample is a MOR molecular sieve and does not contain an ANA molecular sieve.

[0184] The above detailed description of the specific embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A symbiotic molecular sieve of MOR and ANA, characterized in that, Before calcination, the symbiotic molecular sieve has a schematic chemical composition as shown in the formula "SiO2•1 / nAl2O3•pR", where 10≤n≤30, R is an organic structure directing agent, and the organic structure directing agent R is a quaternary ammonium salt or quaternary ammonium base compound containing dimethyldiethylammonium ions. The MOR and ANA symbiotic molecular sieves have X-ray diffraction patterns as shown in the table below. a: ±0.30°, b: varies with 2θ.

2. The symbiotic molecular sieve of MOR and ANA according to claim 1, characterized in that, 0.02≤p≤0.07。 3. The symbiotic molecular sieve of MOR and ANA according to claim 1, characterized in that, The X-ray diffraction pattern also includes the X-ray diffraction peaks shown in the table below. a: ±0.30°, b: varies with 2θ.

4. The symbiotic molecular sieve of MOR and ANA according to claim 1, characterized in that, The total specific surface area of ​​the MOR and ANA symbiotic molecular sieve after calcination is not less than 350 m². 2 / gram, external specific surface area not less than 20 m² 2 / gram, total pore volume not less than 0.25 cm³ 3 / gram, micropore volume not less than 0.15 cm³ 3 / gram.

5. The symbiotic molecular sieve of MOR and ANA according to claim 4, characterized in that, The MOR and ANA symbiotic molecular sieves, after calcination, have a total specific surface area of ​​350-550 m². 2 / gram, with an external specific surface area of ​​20~60 m² 2 / gram, total pore volume is 0.25~0.50 cm³ 3 / gram, micropore volume is 0.15~0.30 cm³. 3 / gram.

6. A method for preparing a symbiotic molecular sieve of MOR and ANA, characterized in that, Includes the following steps: The symbiotic molecular sieve is prepared by mixing a silicon source, an aluminum source, an alkali source, an organic structure directing agent R, and water, followed by crystallization treatment; the organic structure directing agent R is a quaternary ammonium salt or a quaternary ammonium base compound containing dimethyl diethylammonium ions. The silicon source is calculated as SiO2, the aluminum source as Al2O3, and the alkali source as OH. - The organic structure-directing agent R, calculated as dimethyldiethylammonium ions and water, is present in a molar ratio of SiO2:Al2O3:OH. - : R: H2O=1: 0.030~0.110: 0.39~0.55: 0.02~0.12: 10~50.

7. The method according to claim 6, characterized in that, The organic structure directing agent R is selected from at least one of dimethyl diethyl ammonium hydroxide, dimethyl diethyl ammonium chloride, dimethyl diethyl ammonium bromide, or dimethyl diethyl ammonium iodide.

8. The method according to claim 7, characterized in that, The organic structure directing agent R is dimethyldiethylammonium hydroxide.

9. The method according to claim 6, characterized in that, The silicon source is silica sol; the aluminum source is sodium aluminate; and the alkali source is potassium hydroxide and / or sodium hydroxide.

10. The method according to claim 9, characterized in that, The alkali source is sodium hydroxide.

11. The method according to claim 9, characterized in that, The sodium aluminate contains 35% to 43% Al2O3 by weight and 25% to 33% Na2O by weight.

12. The method according to claim 11, characterized in that, The sodium aluminate contains 38% to 43% Al2O3 by weight and 28% to 33% Na2O by weight.

13. The method according to claim 6, characterized in that, The crystallization treatment conditions include: crystallization at 150~180℃ for 0.5~8.0 days.

14. The method according to claim 13, characterized in that, The crystallization treatment conditions include: crystallization at 155~175℃ for 1.0~7.5 days.

15. A molecular sieve composition comprising the MOR and ANA symbiotic molecular sieve according to any one of claims 1-5 or the MOR and ANA symbiotic molecular sieve prepared by any one of claims 6-14, and a binder.

16. The MOR and ANA symbiotic molecular sieve according to any one of claims 1-5, or the MOR and ANA symbiotic molecular sieve prepared by any one of claims 6-14, or the molecular sieve composition according to claim 15, as an adsorbent or a catalyst for the conversion of organic compounds.

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