WO2024221266A1 - Synthesis method for and use of high-silicon mordenite molecular sieve having better reactive site accessibility - Google Patents

Abstract

The present application relates to the field of molecular sieves, and discloses a synthesis method for and use of a high-silicon mordenite molecular sieve having better reactive site accessibility. The synthesis method for a high-silicon mordenite molecular sieve having better reactive site accessibility comprises the following steps: S1, obtaining a silicon-boron precursor prepared from a mother liquor concentrated solution and a boron source; S2, obtaining an aluminum-containing alkaline solution; S3, carrying out hydrothermal crystallization on a mixture of the silicon-boron precursor and the alkaline solution to obtain a product; and S4, carrying out heat treatment and/or acid treatment on the product in the presence of water vapor, to obtain the high-silicon mordenite molecular sieve. According to the method, the reaction low-temperature activity is better while improving the acid strength and the 8-membered cyclic acid proportion, the solid waste of molecular sieve synthesis is greatly reduced, the cost of wastewater treatment for molecular sieve scale-up production is reduced, under the same condition, the initial reaction temperature is significantly reduced compared with the current initial reaction temperature, and the one-way service life of a catalyst can be greatly prolonged.

Description

A synthesis method and application of high-silicon mordenite molecular sieve with better accessibility of reactive active sites Technical Field

The present application relates to a synthesis method of a high-silicon mordenite molecular sieve with better accessibility of reactive active sites and its application, belonging to the field of molecular sieves.

Background Art

Mordenite is a crystalline microporous aluminosilicate with a twelve-membered ring and an eight-membered ring pore structure, suitable acidity and good hydrothermal stability. It has become an important catalytic material in the fields of petrochemicals and coal chemical industry, especially in the recent application of dimethyl ether carbonylation to methyl acetate.

Methyl acetate is an important chemical product and a good environmentally friendly organic solvent, widely used in the production of resins and leather. Its downstream products, acetic acid, acetate, acetic anhydride and ethanol, are all important chemical raw materials. Methyl acetate can be hydrogenated to produce 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 my country's long-term high dependence on foreign crude oil.

The technical route of preparing methyl acetate by carbonylation of dimethyl ether and further hydrogenation to prepare ethanol has opened up an efficient route from non-petroleum-based carbon-containing resources to the preparation of clean energy ethanol. Therefore, it is of great significance to study the catalytic reaction of carbonylation of dimethyl ether to prepare methyl acetate.

In 2006, the Iglesia group first reported the DME carbonylation reaction catalyzed by acidic molecular sieves under halogen-free and precious metal-free conditions (Angewandte Chemie, Int. Ed. 2006, 45 (10), 1617-1620). They used infrared spectroscopy to characterize the acid distribution of the molecular sieves and used probe molecules with different kinetic diameters to determine the distribution of the acid in the octahedral ring channels. The amount of acid was correlated with the carbonyl activity and it was found that the carbonylation activity was related to the number of It is directly proportional to the number of acid centers (Acc. Chem. Res. 2008, 41, 4, 559-567).

The carbonylation catalytic reaction is a highly exothermic reaction, and the catalyst needs to have high activity and stability during long-term use. Therefore, the aluminum is controlled to fall within the eight-membered ring and form a strong Acidic sites will be an effective means to improve the reactivity and stability of mordenite as a dimethyl ether carbonylation catalyst. CN 201611135717.2 discloses a method for synthesizing a mordenite (MOR) molecular sieve with adjustable B acid center location and distribution. The B acid center of the prepared MOR zeolite is preferentially located in the "side pocket" of the 8-membered ring connected to the 12-membered ring channel. The catalyst product obtained by this method exhibits excellent performance in adsorption and catalysis.

CN202011582829.9 discloses a preparation method and application of high silicon-aluminum ratio mordenite. Through pre-crystallization, a high silicon-aluminum ratio precursor is obtained and the effect of structure-guided sol is used to obtain mordenite with a silicon-aluminum ratio of 15 to 50. The mordenite has excellent performance in preparing methyl acetate by carbonylation of dimethyl ether.

Patent CN108160100A uses pyridine and nitrate to modify the twelve-membered ring and eight-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 placement, in which the proportion of aluminum placement in the eight-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.

Liu et al. obtained a mordenite with 32% of eight-membered ring acid sites through selective ion exchange, with a catalyst DME conversion rate of 50% and a service life of more than 210 hours (Catal. Sci. Technol., 2020, 10, 4663-4672). Liu et al. (Catalysis Communications, 2020, 147, 106161) introduced 1,3-dimethylimidazolium ions into MOR zeolite to selectively remove acid sites in the twelve-membered ring (12MR) channel, thereby significantly improving stability and activity, but the production cost of the catalyst increased significantly.

Summary of the invention

The present invention provides a method for synthesizing a high-silicon mordenite molecular sieve with better accessibility to reactive active sites. The mordenite molecular sieve utilizes mother liquor concentrate and introduces boron into the synthesis system, and undergoes subsequent hydrothermal and/or acid treatment to make the zeolite molecular sieve pores more unobstructed and the reactive active sites more accessible. When it is used as a catalyst for carbonylation of dimethyl ether to synthesize methyl acetate, the conversion reaction temperature of dimethyl ether is significantly reduced and the conversion rate is improved, indicating that its active site accessibility is better and its low-temperature activity is significantly better than that of the mordenite molecular sieve synthesized by a one-step method under the same conditions. Zeolite molecular sieve.

According to a first aspect of the present application, a method for synthesizing a high-silicon mordenite molecular sieve having better accessibility to reactive active sites is provided.

A method for synthesizing a high-silicon mordenite molecular sieve with better accessibility of reactive active sites comprises the following steps:

S1, obtaining a silicon-boron precursor made from a mother liquor concentrate and a boron source;

S2, obtaining an alkaline solution containing aluminum;

S3, hydrothermally crystallizing a mixture containing the silicon-boron precursor and the alkaline solution to obtain a product;

S4, subjecting the above product to heat treatment and/or acid treatment under water vapor to obtain the high-silicon mordenite molecular sieve.

The atmosphere for the heat treatment includes air and nitrogen.

Optionally, the silicon-boron precursor is prepared as follows:

The material I containing silicon source, boron source, template A, water and mother liquor concentrate is stirred and aged to prepare the silicon-boron precursor.

Optionally, the alkaline solution is prepared as follows:

The material II containing an aluminum source, an alkali source, a template agent B and water is stirred and aged to prepare the alkaline solution.

Optionally, in step S3, the mother liquor containing the product is separated and distilled to obtain the mother liquor concentrate.

The mother liquor concentrate is prepared as follows:

1) filtering and separating the molecular sieve solid product synthesized for the first time, and then recovering the mother liquor;

2) Analyze the content of each component in the recovered mother liquor;

3) The mother liquid is filled into a sealed container, heated and distilled to remove a certain amount of water to obtain a concentrated solution;

4) Analyze the content of each component in the mother liquor concentrate.

Optionally, in step S3, the conditions for hydrothermal crystallization are as follows:

The temperature is 120-200°C;

The time is 12 to 120 hours.

Optionally, the hydrothermal crystallization conditions include: a crystallization temperature of 60 to 150° C., and a crystallization time of 2 to 15 hours.

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

The temperature is 80-200°C;

The time is 0.5 to 2.0 hours.

Optionally, the acid treatment comprises placing the product in an acid solution of a certain concentration.

Optionally, the mass ratio of the product to the volume of the acid is 3 to 10:1.

Optionally, the acid is selected from at least one of sulfuric acid, nitric acid, hydrochloric acid, citric acid, acetic acid and the like.

Optionally, the conditions for the acid treatment are as follows:

Temperature is 55-85℃;

The time is 0.5 to 2.5 hours.

Optionally, the silicon source is selected from at least one of sol, water glass, white carbon black and diatomaceous earth.

Optionally, the boron source is selected from boric acid.

Optionally, the template A is selected from at least one of hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrapropylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, hexadecyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, cyclohexylamine, caprolactam, hexamethyleneimine, heptamethyleneimine, cycloheptylamine, and cyclopentylamine.

Optionally, the molar ratio of the raw materials in the material I is:

_M2O : _SiO2 : _{B2O3 :} template A: _H2O =(0.06-0.50):1:(0.01-0.15):(0.01-0.12):(10-150).

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

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

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

Optionally, the template B is selected from at least one of hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrapropylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, hexadecyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, cyclohexylamine, caprolactam, hexamethyleneimine, heptamethyleneimine, cycloheptaneamine, and cyclopentaneamine.

Optionally, after adding material II, the gel molar ratio is:

SiO ₂ : Al ₂ O ₃ : B ₂ O ₃ : M ₂ O: H ₂ O: T＝1: (0.01～0.1): (0.02～0.45): (0.05～0.3): (10～50): ( 0.01～0.30).

Optionally, the aging conditions are as follows:

The temperature is 40-120°C;

The time is 4 to 12 hours.

According to one embodiment of the present application, a method for synthesizing a high-silicon mordenite molecular sieve with better accessibility to reactive active sites comprises at least the following steps:

(1) Preparation of silicon-boron precursor: a silicon source, a boron source, a template agent A, water and a concentrated mother liquor are stirred and aged in a certain proportion under a certain temperature to prepare a silicon-boron precursor; preparation of alkaline solution: an aluminum source, an alkali source, a template agent B and water are stirred and aged in a certain proportion under a certain temperature to prepare an alkaline solution;

(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 and dried, and then subjected to acid hydrothermal treatment to obtain a high-silicon mordenite molecular sieve with better reaction accessibility; the mother liquor after the product is separated 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;

The preparation conditions of the silicon-boron precursor and the alkaline solution in step (1) of synthesizing the mordenite according to the method are: temperature of 40 to 120° C. and time of 4 to 12 hours;

In step (2), the hydrothermal and acid treatment refers to heat-treating the molecular sieve powder in the presence of water vapor and then performing an acid treatment.

According to a second aspect of the present application, a high-silicon mordenite molecular sieve is provided.

The high-silicon mordenite molecular sieve obtained by the synthesis method described above has a silicon-aluminum ratio of 15-85.

Optionally, the total acid content of the high-silica mordenite molecular sieve is 550-700 μmol/g.

Optionally, the high-silica mordenite molecular sieve has a specific surface area of 350 to 450 m ² /g.

According to a third aspect of the present application, an application of a high-silicon mordenite molecular sieve is provided.

The high-silicon mordenite molecular sieve obtained by the above-mentioned synthesis method and/or the application of the high-silicon mordenite molecular sieve as a catalyst in the carbonylation of dimethyl ether.

The beneficial effects of this application include:

1) The present application provides a method for synthesizing a high-silica mordenite molecular sieve with better accessibility to reactive active sites, which improves the acid strength and the ratio of 8-membered cyclic acids while making the reaction activity at low temperatures better; the solid waste from molecular sieve synthesis is greatly reduced; the cost of wastewater treatment for molecular sieve scale-up production is reduced; the initial reaction temperature is significantly lower than the current one under the same conditions; and the catalyst single-pass life can be greatly increased.

2) The application of a high-silica mordenite molecular sieve provided in the present application, which is used as a catalyst for the carbonylation of dimethyl ether to synthesize methyl acetate, significantly reduces the conversion reaction temperature of dimethyl ether and improves the conversion rate, indicating that its active site accessibility is better, and its low-temperature activity is significantly better than that of the mordenite molecular sieve synthesized in one step under the same conditions.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is the XRD of Examples 2, 4, 6 and Comparative Example 1 of the present application.

DETAILED DESCRIPTION

The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.

Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.

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

Fourier transform infrared spectroscopy

IR fitting,IR spectra were performed using a Bruke Tensor II spectrometer equipped with a vacuum in-situ cell. First, 5 mg of powdered sample was pressed into The self-supporting disc was placed in an in-situ infrared cell and then pretreated at 400℃ (heating rate of 5℃/min) under vacuum for 1h to remove water from the sample. After pretreatment, the sample was cooled to room temperature and infrared spectroscopy was performed with a scanning range of 4000-600cm ^-1 , 32 scans, and a resolution of 4cm ^-1 .

Nitrogen physical adsorption and desorption

The nitrogen physical adsorption experiment was carried out on the Autosorb-iQ instrument of Quantachrome. First, 0.05g of molecular sieve sample (20 mesh-40 mesh) was weighed into the physical adsorption tube. Before the test, the sample was pretreated at 350℃ and vacuum conditions for 6h to remove adsorbed water and other surface substances. After that, nitrogen physical adsorption and desorption tests were carried out at liquid nitrogen temperature of 77K. The specific surface area of the sample was calculated using the BET equation, and the total pore volume of the molecular sieve was calculated using 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.

X-ray diffractometer (XRD)

SmartLab SE X-ray diffractometer of Rigaku Corporation of Japan, sample test conditions: Cu target, Kα ray (λ=0.1542nm), tube voltage 40kV, tube current 30mA, scanning rate 20°/min, range 3°～55°.

X-ray fluorescence spectroscopy (XRF)

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 the test cell for analysis.

Ammonia Temperature Programmed Desorption (NH ₃ -TPD)

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 at 600°C in a He atmosphere for 1 hour, then cooled to 150°C and introduced with a NH ₃ /He mixed gas for adsorption for 0.5 hour. Then, the physically adsorbed NH ₃ was purged for 0.5 hour in a He atmosphere. After the baseline was stable, the temperature was raised to 700°C at a rate of 10°/min, and the desorbed NH ₃ was recorded by a thermal conductivity detector (TCD).

Reaction performance evaluation:

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: H ₂ = 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 product after the reaction was analyzed online on a Pano A60 or 1949 gas chromatograph, with an HP-PLOT/Q capillary column and a FID detector.

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

Conversion rate of dimethyl ether = [(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%);

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%).

Example 1

Preparation of silicon-boron precursor:

With NaOH as the alkali source, boric acid as the boron source, sodium silicate as the silicon source, aluminum isopropoxide as the aluminum source, and hexadecyltrimethylammonium chloride as the template A, a certain amount of the mother liquor concentrate was taken, mixed, and transferred to a reactor, and aged at 100°C for 8 hours to prepare a silicon-boron precursor with a molar composition of is SiO ₂ : B ₂ O ₃ : Na ₂ O: H ₂ O: A = 1: 0.028: 0.08: 40: 0.02;

Preparation of alkaline solution:

Aluminum isopropoxide, tetraethylammonium hydroxide and water have a molar composition of Al ₂ O ₃ :Na ₂ O:H ₂ O:B=1:9.64:535:3.2, are stirred evenly, aged at 60°C for 2 hours and then cooled to room temperature to prepare an alkaline solution;

Synthesis of high-silica mordenite molecular sieve with better accessibility of reactive sites:

A certain amount of silicon boron precursor and alkaline solution are mixed, stirred for a period of time after addition, heated to 170°C and maintained for 72 hours to obtain a product. 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, and then acid-treated to obtain the high-silicon mordenite molecular sieve.

Comparative Example 1

The experimental steps are the same as those in Example 1, except that no boron source is added when preparing the silicon-boron precursor.

Embodiment 2-6

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

Table 1

Table 2

Analysis Example 1

The molecular sieve catalysts obtained in Examples 1-6 and Comparative Example 1 were subjected to measurements of silicon-aluminum ratio, TPD total acid content, and physical adsorption. The results are shown in Table 3.

Table 3

The molecular sieve catalysts obtained in Examples 1-6 and Comparative Example 1 were subjected to a dimethyl ether gravimetric adsorption experiment. The results are shown in Table 4.

Table 4

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

The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims (10)

A method for synthesizing a high-silicon mordenite molecular sieve with better accessibility of reactive active sites, characterized in that it comprises the following steps: S1, obtaining a silicon-boron precursor made from a mother liquor concentrate and a boron source; S2, obtaining an alkaline solution containing aluminum; S3, hydrothermally crystallizing a mixture containing the silicon-boron precursor and the alkaline solution to obtain a product; S4, subjecting the above product to heat treatment and/or acid treatment under water vapor to obtain the high-silicon mordenite molecular sieve. The synthesis method according to claim 1 is characterized in that the preparation of the silicon-boron precursor is as follows: The material I containing silicon source, boron source, template A, water and mother liquor concentrate is stirred and aged to prepare the silicon-boron precursor. The synthesis method according to claim 1, characterized in that the alkaline solution is prepared as follows: The material II containing an aluminum source, an alkali source, a template agent B and water is stirred and aged to prepare the alkaline solution. The synthesis method according to claim 1, characterized in that, in step S3, the mother liquor containing the product is separated and distilled to obtain the mother liquor concentrate; In step S3, the conditions for hydrothermal crystallization are as follows: The temperature is 120-200°C; The time is 12 to 120 hours. 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; Time is 0.5～2.0h; The acid treatment comprises placing the product in an acid: The mass ratio of the product to the volume of the acid is 3 to 10:1; The acid is selected from at least one of sulfuric acid, nitric acid, hydrochloric acid, citric acid, acetic acid, etc.; The conditions for the acid treatment are as follows: Temperature is 55-85℃; The time is 0.5 to 2.5 hours. The synthesis method according to claim 2, characterized in that the silicon source is selected from at least one of silica sol, water glass, white carbon black, and diatomaceous earth; The boron source is selected from boric acid; The template agent A is selected from at least one of hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrapropylammonium chloride, tetraethylammonium chloride, tetramethylammonium chloride, hexadecyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, cyclohexylamine, caprolactam, hexamethyleneimine, heptamethyleneimine, cycloheptylamine, and cyclopentylamine; The molar ratio of the raw materials in the material I is: _M2O : _SiO2 : _{B2O3 :} template A: _H2O =(0.06-0.50):1:(0.01-0.15):(0.01-0.12):(10-150). The synthesis method according to claim 3, characterized in that the aluminum source is selected from at least one of sodium aluminate, aluminum isopropoxide, aluminum hydroxide, aluminum sulfate, etc.; The alkali source is selected from at least one of alkali metal hydroxides and oxides; The template agent B is selected from hexadecyltrimethylammonium bromide, dodecyltrimethylammonium bromide, tetrapropylammonium bromide, tetraethylammonium bromide, tetramethylammonium bromide, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetrapropylammonium chloride, tetraethylammonium chloride, At least one of tetramethylammonium chloride, hexadecyltrimethylammonium hydroxide, dodecyltrimethylammonium hydroxide, tetrapropylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, triethylamine, isopropylamine, diisopropylamine, triisopropylamine, n-butylamine, cyclohexylamine, caprolactam, hexamethyleneimine, heptamethyleneimine, cycloheptylamine, and cyclopentylamine; After adding material II, the gel molar ratio is: SiO ₂ : Al ₂ O ₃ : B ₂ O ₃ : M ₂ O: H ₂ O: T＝1: (0.01～0.1): (0.02～0.45): (0.05～0.3): (10～50): ( 0.01～0.30). The synthesis method according to claim 2 or 3, characterized in that the aging conditions are as follows: The temperature is 40-120°C; The time is 4 to 12 hours. The high-silicon mordenite molecular sieve obtained by the synthesis method according to any one of claims 1 to 8 is characterized in that the silicon-aluminum ratio of the high-silicon mordenite molecular sieve is 15 to 85; The total acid content of the high-silica mordenite molecular sieve is 550-700 μmol/g; The specific surface area of the high-silicon mordenite molecular sieve is 400-450 m ² /g. The high-silicon mordenite molecular sieve obtained by the synthesis method according to any one of claims 1 to 8 or the high-silicon mordenite molecular sieve according to claim 9 is used as a catalyst in the carbonylation of dimethyl ether.