Synthesis method and application of high-silica mordenite molecular sieve with better accessibility of reactive sites

Abstract

The present application discloses a method for synthesizing a high-silica mordenite zeolite molecular sieve with better accessibility of reactive sites and its application, belonging to the field of molecular sieves. A method for synthesizing a high-silica mordenite zeolite molecular sieve with better accessibility of reactive sites includes the following steps: S1, obtaining a silicon-boron precursor made from a mother liquor concentrate and a boron source; S2, obtaining an aluminum-containing alkaline solution; S3, hydrothermally crystallizing a mixture containing the silicon-boron precursor and the alkaline solution to obtain a product; S4, performing heat treatment and / or acid treatment on the above product under water vapor to obtain the high-silica mordenite zeolite molecular sieve. This method improves the acid strength and the proportion of 8-membered ring acids while making the low-temperature activity of the reaction better; the solid waste in the molecular sieve synthesis is greatly reduced; the sewage treatment cost in the large-scale production of the molecular sieve is reduced; the initial reaction temperature is significantly lower than the current one under the same conditions; the single-pass life of the catalyst can be greatly improved.

Description

Technical Field

[0001] The present application relates to a method for synthesizing a high-silica mordenite zeolite molecular sieve with better accessibility of reactive sites and its application, belonging to the field of molecular sieves. Background Art

[0002] Mordenite is a crystalline microporous silicoaluminate with a pore structure of dodecasil and octasil rings, suitable acidity and good hydrothermal stability, and has become an important catalytic material in the fields of petrochemical and coal chemical industries, especially recently applied in the reaction of dimethyl ether carbonylation to methyl acetate.

[0003] Methyl acetate is an important chemical product and a good environmental protection organic solvent, widely used in the production of resins and leathers. Its downstream products such as acetic acid, acetate, acetic anhydride and ethanol are all important chemical raw materials. Hydrogenation of methyl acetate can obtain ethanol, which is an important organic solvent and fuel additive. As a gasoline additive, it can increase the octane number, promote combustion and reduce pollutant emissions. The large-scale industrial production of ethanol can effectively alleviate the dilemma of China's high long-term dependence on foreign crude oil.

[0004] The technical route of preparing methyl acetate by dimethyl ether carbonylation and then further hydrogenating it to prepare ethanol opens up an efficient route from non-petroleum-based carbon-containing resources to the preparation of clean energy ethanol. Therefore, studying the catalytic reaction of dimethyl ether carbonylation to methyl acetate is of great significance.

[0005] In 2006, the Iglesia group first reported the acid-catalyzed DME carbonylation reaction under halogen-free and noble-metal-free conditions (Angewandte Chemie, Int. Ed. 2006, 45(10), 1617 - 1620). They characterized the acid distribution of the molecular sieve by infrared spectroscopy, determined the number of molecules in the octasil ring channels using probe molecules with different kinetic diameters, and correlated the acid amount with the carbonyl activity, and found that the carbonylation reaction activity is proportional to the number of acid centers in the octasil ring (Acc. Chem. Res. 2008, 41, 4, 559 - 567). The carbonylation catalytic reaction is a strongly exothermic reaction, and the catalyst needs to have high activity and stability during long-term use. Therefore, controlling the aluminum location in the octasil ring and forming a strong acid center in the octasil ring is crucial.

[0006] The carbonylation catalytic reaction is a strongly exothermic reaction, and the catalyst needs to have high activity and stability during long-term use. Therefore, controlling the aluminum location in the octasil ring and forming a strong The acidic sites will be an effective means to improve the reaction activity and stability of mordenite as a catalyst for dimethyl ether carbonylation. CN 201611135717.2 discloses a method for synthesizing a mordenite (MOR) molecular sieve with adjustable location and distribution of Brønsted acid sites. The prepared MOR zeolite has Brønsted acid sites preferentially located in the "side pockets" of the 8-membered rings connected to the 12-membered ring channels. The catalyst products obtained by this method exhibit excellent performance in adsorption and catalysis.

[0007] CN202011582829.9 discloses a method for preparing a high-silica mordenite and its application. Through precrystallization, a high-silica precursor and the action of a structure-directing sol are obtained, and mordenite with a silica-alumina ratio of 15-50 is obtained, which has excellent performance in the preparation of methyl acetate by dimethyl ether carbonylation.

[0008] Patent CN108160100A uses pyridine and nitrate to modify the 12-membered ring and 8-membered ring of HMOR respectively, improving the stability of the catalyst. CN202111644362.0 discloses a method for synthesizing a mordenite molecular sieve with controlled aluminum location, in which the proportion of aluminum located in the 8-membered ring in the structure is higher than 50%. Patent CN201510117253.1 discloses a method for synthesizing a mordenite with both microporous and mesoporous structures.

[0009] Liu et al. obtained a mordenite with 32% acidic sites in the 8-membered ring through selective ion exchange. The DME conversion rate of the catalyst reached 50%, and the service life exceeded 210 h (Catal. Sci. Technol., 2020, 10, 4663-4672). Liu et al. (Catalysis Communications, 2020, 147, 106161) introduced 1,3-dimethylimidazolium ions into the MOR zeolite, which can selectively remove the acid sites in the 12-membered ring (12MR) channels, thus significantly improving the stability and activity, but the production cost of the catalyst increased significantly. Summary of the Invention

[0010] The present invention provides a method for synthesizing a high-silica mordenite molecular sieve with better accessibility of reaction active sites. This mordenite molecular sieve makes the zeolite molecular sieve pores more unobstructed and the accessibility of reaction active sites better by using the mother liquor concentrate and introducing boron into the synthesis system, and through subsequent hydrothermal and / or acid treatment. When used as a catalyst for the synthesis of methyl acetate by dimethyl ether carbonylation, the conversion reaction temperature of dimethyl ether is significantly reduced and the conversion rate is increased, indicating that its accessibility of active sites is better, and its low-temperature activity is significantly better than that of the mordenite molecular sieve synthesized by the one-step method under the same conditions.

[0011] According to the first aspect of the present application, there is provided a method for synthesizing a high-silica mordenite molecular sieve with better accessibility of reaction active sites.

[0012] A method for synthesizing a high-silica mordenite zeolite molecular sieve with better accessibility of reactive sites, comprising the following steps:

[0013] S1. Obtaining a silicon-boron precursor made from a mother liquor concentrate and a boron source;

[0014] S2. Obtaining an aluminum-containing alkaline solution;

[0015] S3. Hydrothermally crystallizing a mixture containing the silicon-boron precursor and the alkaline solution to obtain a product;

[0016] S4. Heat-treating and / or acid-treating the above product under water vapor to obtain the high-silica mordenite zeolite molecular sieve.

[0017] The atmosphere for heat treatment includes air and nitrogen.

[0018] Optionally, the preparation of the silicon-boron precursor is as follows:

[0019] Mixing materials containing a silicon source, a boron source, a template agent A, water, and a mother liquor concentrate, and stirring and aging to prepare the silicon-boron precursor.

[0020] Optionally, the preparation of the alkaline solution is as follows:

[0021] Mixing materials containing an aluminum source, an alkali source, a template agent B, and water, and stirring and aging to prepare the alkaline solution.

[0022] Optionally, in step S3, separating and distilling the mother liquor containing the product to obtain the mother liquor concentrate.

[0023] The preparation method of the mother liquor concentrate is as follows:

[0024] 1) Filtering and separating the molecular sieve solid product synthesized for the first time, and then recovering the mother liquor;

[0025] 2) Analyzing the contents of each component in the recovered mother liquor;

[0026] 3) Loading the mother liquor into a sealed container, heating and distilling out a certain amount of water to obtain a concentrated solution;

[0027] 4) Analyzing the contents of each component in the mother liquor concentrate.

[0028] Optionally, in step S3, the hydrothermal crystallization conditions are as follows:

[0029] The temperature is 120 - 200;

[0030] The time is 12 - 120 h.

[0031] Optionally, the conditions for the hydrothermal crystallization include: the crystallization temperature is 60-150, and the crystallization time is 2-15 h.

[0032] Optionally, in step S4, the conditions for the heat treatment are as follows:

[0033] The temperature is 80-200;

[0034] The time is 0.5-2.0 h.

[0035] Optionally, the acid treatment includes placing the product in an acid solution with a certain concentration.

[0036] Optionally, the mass ratio of the product to the acid is 3-10:1.

[0037] Optionally, the acid is selected from at least one of sulfuric acid, nitric acid, hydrochloric acid, citric acid, acetic acid, etc.

[0038] Optionally, the conditions for the acid treatment are as follows:

[0039] The temperature is 55-85;

[0040] The time is 0.5-2.5 h.

[0041] Optionally, the silicon source is selected from at least one of sol, sodium silicate, silica white, and diatomite.

[0042] Optionally, the boron source is selected from boric acid.

[0043] Optionally, the template agent A is selected from at least one of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrapropylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, cetyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, cyclohexylamine, caprolactam, hexamethyleneimine, heptamethyleneimine, cycloheptanamine, and cyclopentanamine.

[0044] Optionally, the molar ratio of the raw materials in the material is:

[0045] M2O:SiO2:B2O3:template agent A:H2O = (0.06-0.50):1:(0.01-0.15):

[0046] (0.01-0.12):(10-150).

[0047] Optionally, the aluminum source is selected from at least one of sodium aluminate, aluminum isopropoxide, aluminum hydroxide, and aluminum sulfate.

[0048] Optionally, the alkali source is selected from at least one of alkali metal hydroxides and oxides.

[0049] Optionally, the alkali source is selected from at least one of potassium hydroxide and sodium hydroxide.

[0050] Optionally, the template agent B is selected from at least one of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrapropylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, cetyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, cyclohexylamine, caprolactam, hexamethyleneimine, heptamethyleneimine, cycloheptanamine, cyclopentanamine.

[0051] Optionally, after adding the materials, the gel molar ratio is:

[0052] SiO2:Al2O3:B2O3:M2O:H2O:T = 1:(0.01 - 0.1):(0.02 - 0.45):

[0053] (0.05 - 0.3):(10 - 50):(0.01 - 0.30).

[0054] Optionally, the aging conditions are as follows:

[0055] The temperature is 40 - 120;

[0056] The time is 4 - 12 h.

[0057] According to an embodiment of the present application, a method for synthesizing a high-silica mordenite zeolite molecular sieve with better accessibility of reaction active sites, the method at least comprises the following steps:

[0058] (1) Preparation of silicon-boron precursor: The silicon source, boron source, template agent A, water and mother liquor concentrate are stirred and aged at a certain ratio and temperature to prepare a silicon-boron precursor; Preparation of alkaline solution: The aluminum source, alkali source, template agent B and water are stirred and aged at a certain ratio and temperature to prepare an alkaline solution;

[0059] (2) The alkaline solution is added to the silicon-boron precursor in a certain proportion, and a hydrothermal crystallization reaction is carried out in a stainless steel autoclave. The product is washed, dried, and then subjected to acid hydrothermal treatment to obtain a high-silica mordenite zeolite molecular sieve with better reaction accessibility; The mother liquor after product separation is distilled to obtain a mother liquor concentrate, which can be used for the preparation of the above-mentioned silicon-boron precursor after component analysis.

[0060] In step (1) of the mordenite synthesized by the said method, the preparation conditions of the silicon-boron precursor and the alkaline solution are: the temperature is 40-120, and the time is 4-12 h;

[0061] In step (2), the hydrothermal and acid treatment means that under the condition of containing water vapor, the molecular sieve powder is heat-treated and then acid-treated.

[0062] According to the second aspect of the present application, a high-silica mordenite molecular sieve is provided.

[0063] For the high-silica mordenite molecular sieve obtained by the above-mentioned synthesis method, the silica-alumina ratio of the high-silica mordenite molecular sieve is 15-85.

[0064] Optionally, the total acid amount of the high-silica mordenite molecular sieve is 550-700 μmol / g.

[0065] Optionally, the specific surface area of the high-silica mordenite molecular sieve is 350-450 m 2 / g.

[0066] According to the third aspect of the present application, an application of a high-silica mordenite molecular sieve is provided.

[0067] The high-silica mordenite molecular sieve obtained by the above-mentioned synthesis method and / or the above-mentioned high-silica mordenite molecular sieve are used as catalysts in the carbonylation of dimethyl ether.

[0068] The beneficial effects that the present application can produce include:

[0069] 1) The synthesis method of a high-silica mordenite molecular sieve with better accessibility of reaction active sites provided by the present application makes the low-temperature activity of the reaction better while increasing the acid strength and the proportion of 8-membered ring acid; the solid waste in molecular sieve synthesis is greatly reduced; the sewage treatment cost in molecular sieve scale-up production is reduced; the initial reaction temperature is significantly lower than the current one under the same conditions; the single-pass life of the catalyst can be greatly improved.

[0070] 2) For the application of a high-silica mordenite molecular sieve provided by the present application, when it is used as a catalyst for the carbonylation of dimethyl ether to synthesize methyl acetate, the conversion reaction temperature of dimethyl ether is significantly reduced and the conversion rate is increased, indicating that the accessibility of its active sites is better, and its low-temperature activity is significantly better than that of the mordenite molecular sieve synthesized by the one-step method under the same conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0071] Figure 1 XRD of Examples 2, 4, 6 and Comparative Example 1 of the present application. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0072] The present application will be described in detail below with reference to the examples, but the present application is not limited to these examples.

[0073] Unless otherwise specified, the raw materials in the embodiments of this application are all purchased through commercial channels.

[0074] The dimethyl ether adsorption experiment was carried out on a Mettler Toledo thermogravimetric analyzer (TGA / DSC 3+). The sample (about 30 mg) was dehydrated under high vacuum conditions at 350 for 6 hours before testing. Then, the sample was transferred to the thermogravimetric analyzer and stabilized at 50, and then dimethyl ether (5.0 v% DME balanced in Ar) was introduced into the system for adsorption.

[0075] Fourier transform infrared spectroscopy

[0076] Infrared fitting, the infrared spectrum was measured using a Bruke Tensor II spectrometer equipped with a vacuum in-situ cell. First, 5 mg of the powdered sample was pressed into a self-supporting wafer, which was then placed in the in-situ infrared cell. Then, it was pretreated at 400 (heating rate of 5 / min) under vacuum conditions for 1 h to remove water in the sample. After pretreatment, it was cooled to room temperature, and infrared spectrum scanning was performed. The scanning range was 4000 - 600 cm -1 , the number of scans was 32, and the resolution was 4 cm -1 .

[0077] Nitrogen physical adsorption and desorption

[0078] The nitrogen physical adsorption experiment was carried out on a Quantachrome Autosorb-iQ instrument. First, 0.05 g of the molecular sieve sample (20 mesh - 40 mesh) was weighed into the physical adsorption tube. Before testing, the sample was pretreated at 350 under vacuum conditions for 6 h to remove adsorbed water and other surface substances. Then, nitrogen physical adsorption and desorption tests were carried out at the liquid nitrogen temperature of 77 K. The specific surface area of the sample was calculated using the BET equation, the total pore volume of the molecular sieve was calculated based on the nitrogen adsorption amount at the highest relative pressure point; the micropore specific surface area and micropore volume of the sample were calculated using the t-plot method; the pore size distribution of the sample was calculated using the BJH method; the pore width and total pore distribution were calculated using the DFT method.

[0079] X-ray diffractometer (XRD)

[0080] A SmartLab SE type X-ray diffractometer from Rigaku Corporation of Japan. The sample test conditions were: Cu target, Kα ray (λ = 0.1542 nm), tube voltage 40 kV, tube current 30 mA, scanning rate of 20° / min, and the range was 3° - 55°.

[0081] X-ray fluorescence spectroscopy (XRF)

[0082] The elemental composition and content of the samples were analyzed using a ZSX PrimusⅢ+ fluorescence spectrometer from Rigaku Corporation. Before testing, the molecular sieve samples were fully ground into fine powder, pressed into tablets at 30 MPa, and then placed in a test cell for analysis.

[0083] Ammonia Temperature Programmed Desorption (NH3-TPD)

[0084] Chemical adsorption analysis was performed using the AMI300 chemical adsorption instrument from AMI, USA. 0.1 g of molecular sieve sample was placed in a U-shaped quartz tube. It was first pretreated in a He atmosphere at 600°C for 1 hour, then cooled to 150°C and introduced with a NH3 / He mixed gas for adsorption for 0.5 hour. Then, the physically adsorbed NH3 was removed by purging in a He atmosphere for 0.5 hour. After the baseline was stabilized, the temperature was raised to 700°C at a rate of 10° / min, and the desorbed NH3 was recorded using a thermal conductivity detector (TCD).

[0085] Reaction performance evaluation:

[0086] Catalyst evaluation was performed on a high-pressure fixed bed reactor. The reaction tube was 316L stainless steel with an inner diameter of 9 mm, a catalyst loading of 1.0 g, and a size of 20-40 mesh. The raw gas (DME: CO: H2 = 5:35:60), the reaction pressure was 2.0 MPa, and the hourly space velocity was 1800 mL / g cat / h. The reaction temperature was 180°C, and the gas products after the reaction were analyzed online on a Pano A60 or 1949 gas chromatograph, with an HP-PLOT / Q capillary column and a FID detector.

[0087] In the examples of this application, the conversion rate and selectivity are calculated as follows:

[0088] Dimethyl ether conversion rate = [(molar number of dimethyl ether carbon in the feed gas) - (molar number of dimethyl ether carbon in the product)] ÷ (molar number of dimethyl ether carbon in the feed gas) × (100%);

[0089] Methyl acetate selectivity = (2 / 3) × (the number of moles of carbon of methyl acetate in the product) ÷ [(the number of moles of carbon of dimethyl ether in the feed gas) - (the number of moles of carbon of dimethyl ether in the product)] × (100%).

[0090] Example 1

[0091] Preparation of silicon-boron precursor:

[0092] Using NaOH as the alkali source, boric acid as the boron source, sodium silicate as the silicon source, aluminum isopropoxide as the aluminum source, and cetyltrimethylammonium chloride as template agent A, a certain amount of the mother liquor concentrate was taken, mixed, and transferred to a reaction kettle. After aging at 100 °C for 8 h, a silicon-boron precursor was prepared, and its molar composition was SiO2:B2O3:Na2O:H2O:A = 1:0.028:0.08:40:0.02;

[0093] Preparation of the alkaline solution:

[0094] Aluminum isopropoxide, tetraethylammonium hydroxide, and water were stirred evenly according to the molar composition of Al2O3:Na2O:H2O:B = 1:9.64:535:3.2. After aging at 60 °C for 2 h and then cooling to room temperature, an alkaline solution was prepared;

[0095] Synthesis of high-silica mordenite zeolite molecular sieve with better accessibility of reaction active sites:

[0096] A certain amount of the silicon-boron precursor and the alkaline solution were mixed, stirred for a period of time after addition, heated to 170 °C and maintained for 72 h to obtain a product. The mother liquor after separation of the product was distilled to obtain a mother liquor concentrate. After component analysis, it could be used for the preparation of the above-mentioned silicon-boron precursor, and then acid treatment was carried out to obtain the high-silica mordenite zeolite molecular sieve.

[0097] Comparative Example 1

[0098] The experimental procedure was the same as that in Example 1, except that the boron source was not added during the preparation of the silicon-boron precursor.

[0099] Examples 2-6

[0100] The preparation processes of Examples 2-6 were the same as that in Example 1. The raw material types and ratios, pre-crystallization temperature and time, crystallization temperature and time in the silicon-boron precursor and the alkaline solution of the prepared samples are shown in Table 1. The subsequent treatment materials and methods are specifically shown in Table 2.

[0101] Table 1

[0102]

[0103] Table 2

[0104]

[0105] Analysis Example 1

[0106] For Examples 1-6 and Comparative Example 1, the silicon-aluminum ratio, total acid amount of TPD, and physical adsorption of the obtained molecular sieve catalysts were measured, and the results are shown in Table 3.

[0107] Table 3

[0108]

[0109] For Examples 1-6 and the molecular sieve catalyst obtained in Comparative Example 1, a dimethyl ether gravimetric adsorption experiment was carried out, and the results are shown in Table 4.

[0110] Table 4

[0111]

[0112]

[0113] It can be seen from the above characterization results that after the synthesis and treatment method of the present application, the total acid amount of the catalyst TPD increases, and the adsorption time equilibrium time of the catalyst for dimethyl ether becomes shorter, making the reaction accessibility of the catalyst better. For the carbonylation reaction, at the same reaction temperature, the conversion rate of dimethyl ether increases.

[0114] The above are only several embodiments of the present application, and do not impose any form of limitation on the present application. Although the present application is disclosed above with preferred embodiments, it is not intended to limit the present application. Any person skilled in the art, without departing from the scope of the technical solution of the present application, makes some changes or modifications using the technical content disclosed above, which are equivalent to equivalent embodiments and all fall within the scope of the technical solution.

Claims

1. A method for synthesizing a high-silica mordenite zeolite molecular sieve with better accessibility of reactive sites, characterized in that It includes the following steps: S1. Obtain a silicon-boron precursor made from a mother liquor concentrate and a boron source; The preparation of the silicon-boron precursor is as follows: Prepare the silicon-boron precursor by stirring and aging a material I containing a silicon source, a boron source, a template agent A, water, and a mother liquor concentrate; S2. Obtain an aluminum-containing alkaline solution; The preparation of the alkaline solution is as follows: Prepare the alkaline solution by stirring and aging a material II containing an aluminum source, an alkali source, a template agent B, and water; S3. Hydrothermally crystallize a mixture containing the silicon-boron precursor and the alkaline solution to obtain a product; S4. Heat-treat and / or acid-treat the above product under steam to obtain the high-silica mordenite zeolite molecular sieve.

2. The synthesis method according to claim 1, wherein In step S3, separate and distill the mother liquor containing the product to obtain the mother liquor concentrate.

3. The synthesis method according to claim 1, wherein, In step S3, the conditions for hydrothermal crystallization are as follows: The temperature is 120 - 200 °C; The time is 12 - 120 h.

4. The synthesis method according to claim 1, characterized in that, In step S4, the conditions for heat treatment are as follows: The temperature is 80 - 200 °C; The time is 0.5 - 2.0 h.

5. The synthesis method according to claim 1, characterized in that, In step S4, the acid treatment includes placing the product in an acid.

6. The synthesis method according to claim 5, characterized in that, The mass ratio of the product to the volume of the acid is 3 - 10:

1.

7. The synthesis method according to claim 5, wherein, The acid is selected from at least one of sulfuric acid, nitric acid, hydrochloric acid, citric acid, and acetic acid.

8. The synthesis method according to claim 5, characterized in that, The conditions for acid treatment are as follows: The temperature is 55 - 85 °C; The time is 0.5 - 2.5 h.

9. The synthesis method according to claim 1, characterized in that, The silicon source is selected from at least one of silica sol, sodium silicate, precipitated silica, and diatomaceous earth; The boron source is selected from boric acid; The template agent A is selected from at least one of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrapropylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, cetyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, cyclohexylamine, caprolactam, hexamethyleneimine, heptamethyleneimine, cycloheptanamine, and cyclopentanamine.

10. The synthesis method according to claim 1, characterized in that, The molar ratio of raw materials in the material I is as follows: M2O:SiO2:B2O3:template agent A:H2O = (0.06 - 0.50):1:(0.01 - 0.15):(0.01 - 0.12):(10 - 150).

11. According to the synthesis method described in claim 1, characterized in that, The aluminum source is selected from at least one of sodium aluminate, aluminum isopropoxide, aluminum hydroxide, and aluminum sulfate; The alkali source is selected from at least one of alkali metal hydroxides and oxides; The template agent B is selected from at least one of cetyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrapropylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, cetyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, cyclohexylamine, caprolactam, hexamethyleneimine, heptamethyleneimine, cycloheptanamine, cyclopentanamine.

12. The synthesis method according to claim 1, wherein, After adding Material II, the molar ratio of the gel is: SiO2:Al2O3:B2O3:M2O:H2O:T = 1:(0.01~0.1):(0.02~0.45):(0.05~0.3):(10~50):(0.01~0.30).

13. The synthesis method according to claim 1, wherein The conditions for aging are as follows: The temperature is 40~120 °C; The time is 4~12 h.

14. The high-silica mordenite molecular sieve obtained by the synthesis method according to any one of claims 1 to 13, characterized in that, The silica-alumina ratio of the high-silica mordenite molecular sieve is 15~85.

15. The high-silica mordenite molecular sieve according to claim 14, wherein The total acid amount of the high-silica mordenite molecular sieve is 550~700 μmol / g.

16. The high-silica mordenite molecular sieve according to claim 14, wherein The specific surface area of the high-silica mordenite zeolite molecular sieve is 400-450 m 2 / g.

17. Application of the high-silica mordenite molecular sieve obtained by the synthesis method according to any one of claims 1 to 13 and / or the high-silica mordenite molecular sieve according to any one of claims 14 to 16 as a catalyst in the carbonylation of dimethyl ether.

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