Preparation method and application of carbonylation catalyst

Abstract

The present invention discloses a preparation method and application of a carbonylation catalyst. The method comprises the following steps: 1) mixing a silicon source, an aluminum source, an alkali, water and a template A in a certain mass ratio, transferring the mixture to a pre-crystallization kettle for pre-crystallization, filtering and drying to obtain a precursor; 2) forming the precursor and a binder, and then transferring the mixture to a crystallization solution containing templates B+C for crystallization, filtering, washing and drying after the crystallization, and roasting-exchanging-re-roasting to obtain a molecular sieve catalyst. The molecular sieve catalyst is used for the carbonylation reaction of dimethyl ether and carbon monoxide. The molecular sieve catalyst has a higher yield and exhibits better performance. The present invention has the advantages of simple preparation process, high raw material utilization rate, and good industrial application prospects.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemical synthesis, and particularly relates to a preparation method and application of a carbonylation catalyst. Background Art

[0002] With the growing demand for energy and the intensifying contradiction of tight oil supply, as well as the increasing global environmental pressure, fuel ethanol has attracted widespread attention from countries around the world for its cleanliness and environmental protection. As an important clean energy, ethanol is mixed with gasoline at a ratio of 10%. Fuel ethanol gasoline can reduce the emission of carbon monoxide and hydrocarbons in automobile exhaust.

[0003] Currently, fuel ethanol is mainly divided into three categories: grain ethanol, non-grain ethanol, and cellulosic ethanol. Grain ethanol uses grains such as corn and wheat as raw materials. Since the production of grain ethanol and non-grain ethanol requires more arable land, there is a problem of competing with people and livestock for food.

[0004] At present, the "dimethyl ether → methyl acetate → ethanol" technical route has been developed, and dimethyl ether and carbon monoxide undergo carbonylation reaction to produce methyl acetate, and methyl acetate and hydrogen undergo hydrogenation reaction to produce ethanol. Among them, the technology of hydrogenating methyl acetate to ethanol has long been mature and has been industrially applied.

[0005] Patent CN104338553A uses microwave acid-base treatment on ZSM-35 molecular sieves to improve the activity and stability of dimethyl ether carbonylation reactions. Patent CN101613274A uses pyridine and other organic amines to modify mordenite molecular sieve catalysts, achieving methyl acetate selectivity exceeding 99% and significantly improving catalyst lifespan to over 50 hours. Patent CN103896766A increases the single-pass lifespan of mordenite catalysts to over 1,000 hours by adding pyridine and other organic amines to the feed. This pyridine modification method effectively addresses the short lifespan of mordenite catalysts. Patent CN106311336A selectively modifies the pores of mordenite molecular sieves with methyl or acetyl organic compounds, increasing the single-pass lifespan of dimethyl ether carbonylation catalysts to over 600 hours. Industrial catalysts require a certain level of strength, and large amounts of binders are added during the molding process to enhance this strength. The binder in the catalyst is inert during the reaction, or may have some adverse effects on the reaction, and this effect becomes greater as the binder dosage increases. Furthermore, during the crystallization process of conventional molecular sieves, some silicon source dissolves in the mother liquor and cannot be used, resulting in low raw material utilization. Summary of the Invention

[0006] To address the problems of the prior art, the present invention provides a method for preparing a carbonylation catalyst. In this method, a pre-crystallized precursor is first formed and then placed in a crystallization solution for further crystallization. The resulting molecular sieve catalyst is then used in the carbonylation reaction of dimethyl ether and carbon monoxide. This method not only improves the yield of the molecular sieve, but also enhances the catalytic performance of the molecular sieve catalyst.

[0007] In order to achieve the above invention objectives, the specific technical solutions adopted by the present invention are:

[0008] A method for preparing a carbonylation catalyst, comprising the following steps:

[0009] (1) mixing a silicon source, an aluminum source, an alkali, water, and a template agent A in a certain mass ratio (i.e., a pre-crystallization solution), transferring the mixture to a pre-crystallization kettle for hydrothermal pre-crystallization, filtering, and drying to obtain a precursor;

[0010] (2) The precursor and the binder are formed, and after the formed sample is dried, it is transferred to a crystallization solution prepared from the template B+C and the pre-crystallization solution obtained by filtration in step (1) for crystallization. After filtering, washing and drying, it is calcined-exchanged-and calcined again to obtain the catalyst.

[0011] As a better choice in this application, the pre-crystallization solution in step (1) is a substance prepared by mixing H2O, NaOH, template A, silicon source and aluminum source in a mass ratio of 100: (0.01-10.0): (0.01-2.0): (0.01-10.0): (0.01-10.0).

[0012] The template agent A is any one of cyclohexylamine, aniline, monomethylamine, dimethylamine and the like.

[0013] The pre-crystallization temperature is 100-150°C for 5-24 hours, and the drying temperature after filtration is 20-70°C for 1-10 hours.

[0014] As a better selection method in this application, the silicon source is any one of silica sol, silica powder or white carbon black; the aluminum source is any one of aluminum chloride, aluminum sulfate, aluminum nitrate and sodium aluminate.

[0015] As a preferred method in this application, the precursor and binder are formed in step (2), including ball forming and extrusion forming. The ball size is 1-5mm, the extrusion diameter is 1-5mm, and the length is 3-5mm. The binder is one or a combination of silica sol or SB powder. The mass ratio of the precursor to the binder is 1: (0.1-1.0). The drying temperature after forming is 20-70°C and the drying time is 1-10 hours. The drying temperature after crystallization is 100-130°C and the drying time is 1-10 hours.

[0016] As a better choice in this application, template B+C is any two combinations of hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride, tetrapropylammonium chloride, etc. The molded sample, pre-crystallization liquid, and template B+C are crystallized in a ratio of 1kg: (4-20)L: (10-50)g, and the mass ratio of template B / C is (3-10): 1. The crystallization temperature is 130-200℃, and the time is 5-96h. After filtration and drying, the roasting temperature is 450-600℃, and the roasting time is 2-10h. The exchange reagent is one of ammonium salts such as ammonium chloride, ammonium nitrate or ammonium sulfate. The re-roasting temperature is 450-550℃, and the roasting time is 2-10h.

[0017] The catalyst type obtained by adopting any one of the above methods or a combination of the methods is one of MOR, ZSM-35 or FER molecular sieves, and its Si / Al (molar) ratio is 5-50.

[0018] Another invention objective of the present application is to use the catalyst prepared by the above scheme for the carbonylation reaction of dimethyl ether and carbon monoxide.

[0019] As a better choice in this application, the catalyst is used in the carbonylation reaction of dimethyl ether and carbon monoxide to obtain methyl acetate product, the reaction temperature is 150-210 ° C, the reaction pressure is 1.0-10.0 MPa, and the raw gas space velocity is 1000-10000 h -1 The ratio of carbon monoxide to dimethyl ether in the raw gas is 5:1 to 20:1. Before the reaction, the catalyst is pre-adsorbed with pyridine or methyl iodide at a temperature of 250-350°C and a pyridine or methyl iodide concentration of 0.1-10.0% by volume. The inert diluent gas is N2 or He gas.

[0020] Due to the adoption of the above solution, the beneficial effects of the present invention are:

[0021] (1) After the carbonylation catalyst is formed, the binder does not have any catalytic activity. Instead, it may change the acid strength of the catalyst, resulting in a decrease in the selectivity of the reaction product. At the same time, in the general molecular sieve crystallization process, the crystallization mother liquor contains a large amount of raw materials such as silicon and aluminum, resulting in material waste. The present invention forms the pre-crystallized precursor and then uses a secondary crystallization method. On the one hand, it can improve the utilization rate of the silicon source, aluminum source, etc., and on the other hand, it can reduce the binder content and increase the content of the molecular sieve, thereby improving the catalytic performance of the molecular sieve catalyst and reducing production costs.

[0022] (2) The process of the present invention is simple to operate, repeatable, and has good industrial application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 is the XRD pattern of 5# catalyst;

[0024] Figure 2 This is the XRD pattern of catalyst #2. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical solutions and advantages of the present invention more clear, the following examples further describe the present invention in detail. All features disclosed in this specification, or steps in all methods or processes disclosed, except for mutually exclusive features and / or steps, can be combined in any way.

[0026] In the examples, the pyridine-treated molecular sieve catalyst was prepared according to the method disclosed in CN103896766A, and the iodomethane-treated molecular sieve catalyst was prepared according to the method disclosed in CN106311336A.

[0027] Example 1

[0028] This embodiment provides a method for preparing a carbonylation catalyst of the present invention, and the specific steps are as follows:

[0029] Step (1): A pre-crystallization solution is prepared by mixing H2O, NaOH, cyclohexylamine, silica sol, and aluminum nitrate in a mass ratio of 100:0.3:0.02:4.0:1.0, and then the pre-crystallization solution is transferred to a pre-crystallization kettle for hydrothermal pre-crystallization, and filtered and dried to obtain a precursor; the pre-crystallization temperature is 110°C, and the pre-crystallization time is 6 hours. After filtration, the drying temperature is 30°C, and the drying time is 5 hours.

[0030] Step (2): The precursor and SB powder were rolled into balls with a diameter of 3.0 mm and a mass ratio of 1:0.3. The molded sample was dried at 40°C for 5 h.

[0031] Crystallization was performed using a molded sample, pre-crystallization solution, and templates B and C in a ratio of 1 kg:10 L:20 g. Templates B and C were hexadecyltrimethylammonium chloride and dodecyltrimethylammonium chloride, respectively, with a B / C mass ratio of 4:1. Crystallization was performed at 165°C for 72 hours. The catalyst was then filtered, washed, and dried, followed by calcination, exchange, and recalcination. The drying temperature was 110°C for 8 hours, and the calcination temperature was 550°C for 4 hours.

[0032] The calcined product is placed in an exchange reagent for exchange, wherein the exchange reagent is ammonium nitrate.

[0033] The exchanged product was calcined again at a temperature of 550° C. for 6 h to obtain a carbonylation catalyst. The catalyst was a MOR molecular sieve with a Si / Al molar ratio of 15.2, numbered 1#. The calculated Si utilization is shown in Table 1.

[0034] Weigh 20g of catalyst #1 for performance testing of the production of methyl acetate from dimethyl ether and carbon monoxide. Catalyst #1 was placed in a 43mm inner diameter stainless steel reaction tube. The reaction pressure was then slowly increased to 2.0MPa with N2 gas, and the reaction temperature was controlled at 165°C. The nitrogen flow was stopped and the feed gas (by volume ratio, carbon monoxide: dimethyl ether = 7:1) was introduced, with the feed gas volumetric space velocity controlled at 2000h / min. -1 , start recording the reaction time. When the reaction time reaches 100 hours, the reaction product is analyzed online by gas chromatography. The activity test results are shown in Table 2.

[0035] Example 2

[0036] This embodiment provides a method for preparing a carbonylation catalyst of the present invention, and the specific steps are as follows:

[0037] Step (1): A pre-crystallization solution is prepared by mixing H2O, NaOH, monomethylamine, silica sol, and aluminum nitrate in a mass ratio of 100:0.6:0.1:5.0:3.0, and then the pre-crystallization solution is transferred to a pre-crystallization kettle for hydrothermal pre-crystallization, and filtered and dried to obtain a precursor; the pre-crystallization temperature is 130°C, and the pre-crystallization time is 6 hours. After filtration, the drying temperature is 35°C, and the drying time is 5 hours.

[0038] Step (2): The precursor and aluminum sol were formed into balls with a diameter of 3.5 mm and a mass ratio of the precursor to the aluminum sol of 1:0.4. The formed sample was dried at a drying temperature of 45° C. for 5 h.

[0039] Crystallize the molded sample, pre-crystallization solution, and templates B and C at a ratio of 1 kg:15 L:30 g. Templates B and C are tetradecyltrimethylammonium chloride and octadecyltrimethylammonium chloride, respectively, with a B / C mass ratio of 4.9:1. Crystallization temperature is 155°C, and crystallization time is 80 hours. The catalyst is then filtered, washed, and dried, followed by calcination, exchange, and recalcination. Drying temperature is 110°C, drying time is 8 hours, and calcination temperature is 550°C, and calcination time is 4 hours.

[0040] The calcined product is placed in an exchange reagent for exchange, wherein the exchange reagent is ammonium nitrate.

[0041] The exchanged product was calcined again at a temperature of 550° C. for 6 h to obtain a carbonylation catalyst. The catalyst was a MOR molecular sieve with a Si / Al molar ratio of 15.9, numbered 2#. The calculated Si utilization is shown in Table 1.

[0042] Weigh 20g of catalyst #2 for performance testing of the production of methyl acetate from dimethyl ether and carbon monoxide. Catalyst #2 was placed in a 43mm inner diameter stainless steel reaction tube. The reaction pressure was then slowly increased to 3.0MPa with N2 gas, and the reaction temperature was controlled at 175°C. The nitrogen flow was stopped and the feed gas (by volume ratio, carbon monoxide: dimethyl ether = 6:1) was introduced, with the feed gas volumetric space velocity controlled at 3000h / min. -1 , start recording the reaction time. When the reaction time reaches 100 hours, the reaction product is analyzed online by gas chromatography. The activity test results are shown in Table 2.

[0043] Example 3

[0044] This embodiment provides a method for preparing a carbonylation catalyst of the present invention, and the specific steps are as follows:

[0045] Step (1): A pre-crystallization solution is prepared by mixing H2O, NaOH, aniline, silica sol, and aluminum nitrate in a mass ratio of 100:1.0:0.2:7.0:6.0, and then the pre-crystallization solution is transferred to a pre-crystallization kettle for hydrothermal pre-crystallization, and filtered and dried to obtain a precursor; the pre-crystallization temperature is 140°C, and the pre-crystallization time is 6 hours. After filtration, the drying temperature is 40°C, and the drying time is 5 hours.

[0046] Step (2): The precursor and aluminum sol were extruded into strips with a diameter of 2.7 mm and a length of 4.0 mm. The mass ratio of the precursor to the aluminum sol was 1:0.5. The molded sample was dried at 50°C for 5 hours.

[0047] Crystallization was performed using a molded sample, pre-crystallization solution, and templates B and C in a ratio of 1 kg:16 L:35 g. Templates B and C were tetramethylammonium chloride and tetrapropylammonium chloride, respectively, with a B / C mass ratio of 5.7:1. The crystallization temperature was 175°C for 96 hours. The catalyst was then filtered, washed, and dried, followed by calcination, exchange, and recalcination. The drying temperature was 110°C for 8 hours, and the calcination temperature was 550°C for 4 hours.

[0048] The calcined product is placed in an exchange reagent for exchange, wherein the exchange reagent is ammonium chloride.

[0049] The exchanged product was calcined again at a temperature of 550° C. for 4 h to obtain a carbonylation catalyst. The catalyst was a MOR molecular sieve with a Si / Al molar ratio of 16.3, numbered 3#. The calculated Si utilization is shown in Table 1.

[0050] Weigh 20g of catalyst #3 for performance testing of the production of methyl acetate from dimethyl ether and carbon monoxide. Catalyst #3 was placed in a 43mm inner diameter stainless steel reaction tube. The reaction pressure was then slowly increased to 2.0MPa with N2 gas, and the reaction temperature was controlled at 190°C. The nitrogen flow was stopped and the feed gas (by volume ratio, carbon monoxide: dimethyl ether = 8:1) was introduced, with the feed gas volumetric space velocity controlled at 3500h / min. -1 , start recording the reaction time. When the reaction time reaches 100 hours, the reaction product is analyzed online by gas chromatography. The activity test results are shown in Table 2.

[0051] Comparative Example 1

[0052] This embodiment provides a preparation method and application of a catalyst of the present invention, and the specific steps are as follows:

[0053] This embodiment provides a method for preparing a carbonylation catalyst of the present invention, and the specific steps are as follows:

[0054] Step (1): A crystallization solution is prepared by mixing H2O, NaOH, cyclohexylamine, silica sol, and aluminum nitrate in a mass ratio of 100:0.3:0.02:4.0:1.0, and then transferring the crystallization solution to a crystallization kettle for hydrothermal crystallization, filtering, washing, and drying to obtain a precursor; the crystallization temperature is 165°C, and the crystallization time is 72 hours. After filtration, the drying temperature is 110°C, and the drying time is 8 hours.

[0055] Step (2): The precursor and SB powder are rolled into balls with a diameter of 3.0 mm. The mass ratio of the precursor to the SB powder is 1:0.3. The molded sample is dried at a drying temperature of 110°C and a drying time of 8 hours. The catalyst is then obtained by calcination-exchange-recalcination. The calcination temperature is 550°C, the calcination time is 4 hours, and the exchange reagent is ammonium nitrate. The re-calcination temperature is 550°C, and the re-calcination time is 6 hours to obtain a carbonylation catalyst. The catalyst is a MOR molecular sieve with a Si / Al molar ratio of 6.4, numbered 4#. The calculated Si utilization rate is shown in Table 1.

[0056] Weigh 20g of catalyst #4 for performance testing of the production of methyl acetate from dimethyl ether and carbon monoxide. Catalyst #4 was placed in a 43mm inner diameter stainless steel reaction tube. The reaction pressure was then slowly increased to 2.0MPa with N2 gas, and the reaction temperature was controlled at 165°C. The nitrogen flow was stopped and the feed gas (by volume ratio, carbon monoxide: dimethyl ether = 7:1) was introduced, with the feed gas volumetric space velocity controlled at 2000h / min. -1 , start recording the reaction time. When the reaction time reaches 100 hours, the reaction product is analyzed online by gas chromatography. The activity test results are shown in Table 2.

[0057] Comparative Example 2

[0058] This embodiment provides a preparation method and application of a catalyst of the present invention, and the specific steps are as follows:

[0059] This embodiment provides a method for preparing a carbonylation catalyst of the present invention, and the specific steps are as follows:

[0060] Step (1): A crystallization solution is prepared by mixing H2O, NaOH, monomethylamine, tetradecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, silica sol, and aluminum nitrate in a mass ratio of 100:0.6:0.1:0.06:0.08:5.0:3.0, and then transferring the crystallization solution to a crystallization kettle for hydrothermal crystallization, filtering, washing, and drying to obtain a precursor; the crystallization temperature is 155°C, the crystallization time is 80 hours, and the drying temperature is 110°C, and the drying time is 8 hours.

[0061] Step (2): The precursor and aluminum sol are rolled into balls with a diameter of 3.5 mm. The mass ratio of the precursor to the aluminum sol is 1:0.4. The molded sample is dried at a drying temperature of 110°C and a drying time of 8 hours. The catalyst is then obtained by calcination-exchange-recalcination. The calcination temperature is 550°C, the calcination time is 6 hours, the exchange reagent is ammonium nitrate, the recalcination temperature is 550°C, and the recalcination time is 6 hours. A carbonylation catalyst is obtained, which is a MOR molecular sieve with a Si / Al molar ratio of 4.8, numbered 5#, and the calculated Si utilization rate is shown in Table 1.

[0062] Weigh 20g of catalyst #5 for performance testing of the production of methyl acetate from dimethyl ether and carbon monoxide. Catalyst #5 was placed in a 43mm inner diameter stainless steel reaction tube. The reaction pressure was then slowly increased to 3.5MPa with N2 gas, and the reaction temperature was controlled at 185°C. The nitrogen flow was stopped and the feed gas (by volume ratio, carbon monoxide: dimethyl ether = 6:1) was introduced, with the feed gas volumetric space velocity controlled at 3000h / min. -1 , start recording the reaction time. When the reaction time reaches 100 hours, the reaction product is analyzed online by gas chromatography. The activity test results are shown in Table 2.

[0063] Comparative Example 3

[0064] This embodiment provides a preparation method and application of a catalyst of the present invention, and the specific steps are as follows:

[0065] This embodiment provides a method for preparing a carbonylation catalyst of the present invention, and the specific steps are as follows:

[0066] Step (1): A pre-crystallization solution is prepared by mixing H2O, NaOH, aniline, silica sol, and aluminum nitrate in a mass ratio of 100:1.0:0.2:7.0:6.0. The pre-crystallization solution is then transferred to a pre-crystallization kettle for hydrothermal pre-crystallization at a pre-crystallization temperature of 175°C for 96 hours. After filtration, the solution is dried at a temperature of 70°C for 10 hours to obtain a precursor.

[0067] Step (2): The precursor and aluminum sol were extruded into strips with a diameter of 2.7 mm and a length of 4.0 mm. The mass ratio of the precursor to the aluminum sol was 1:0.5. The molded sample was dried at 50°C for 5 hours.

[0068] Crystallization was performed using a molded sample, pre-crystallization solution, and templates B and C in a ratio of 1 kg:16 L:35 g. Templates B and C were tetramethylammonium chloride and tetrapropylammonium chloride, respectively, with a B / C mass ratio of 5.7:1. Crystallization was performed at 175°C for 96 hours. The catalyst was then filtered, washed, and dried, followed by calcination, exchange, and recalcination. The drying temperature was 110°C for 8 hours, and the calcination temperature was 550°C for 4 hours.

[0069] The calcined product is placed in an exchange reagent for exchange, wherein the exchange reagent is ammonium chloride.

[0070] The exchanged product was calcined again at a temperature of 550° C. for 4 h to obtain a carbonylation catalyst. The catalyst was a MOR molecular sieve with a Si / Al molar ratio of 4.9, numbered 6#. The calculated Si utilization is shown in Table 1.

[0071] Weigh 20g of catalyst #6 for performance testing of the production of methyl acetate from dimethyl ether and carbon monoxide. Catalyst #6 was placed in a 43mm inner diameter stainless steel reaction tube. The reaction pressure was then slowly increased to 2.0MPa with N2 gas, and the reaction temperature was controlled at 190°C. The nitrogen flow was stopped and the feed gas (by volume ratio, carbon monoxide: dimethyl ether = 8:1) was introduced, with the feed gas volumetric space velocity controlled at 3500h / min. -1 , start recording the reaction time. When the reaction time reaches 100 hours, the reaction product is analyzed online by gas chromatography. The activity test results are shown in Table 2.

[0072] Table 1 Analysis results of Si utilization of different catalysts

[0073] Serial number Si utilization Example 1 94.2％ Example 2 95.0％ Example 3 95.5％ Comparative Example 1 74.2％ Comparative Example 2 73.1％ Comparative Example 3 82.3％

[0074] Table 2 Activity test results of different catalysts

[0075] Serial number Dimethyl ether conversion rate (100h) Methyl acetate selectivity (at 100h) Example 1 47.2％ 99.5％ Example 2 48.0％ 99.1％ Example 3 47.4％ 98.8％ Comparative Example 1 37.3％ 94.7％ Comparative Example 2 39.0％ 95.6％ Comparative Example 3 42.4％ 96.4％

[0076] Table 3 Crystallinity and micropore volume of different catalysts

[0077]

[0078]

[0079] From the comparison of Si utilization in Table 1, we can see that the Si utilization of the catalysts in Examples 1, 2, and 3 is 94.2%, 95.0%, and 95.5%, respectively. The Si utilization of the catalysts in Comparative Examples 1 and 2, which were formed after ordinary crystallization, was only 74.2% and 73.1%, respectively. The Si utilization of the catalyst in Comparative Example 3, which was formed and recrystallized after crystallization, was increased to 82.3%, but it was still significantly lower than that in Examples 1, 2, and 3. As can be seen from the XRD patterns of catalysts 2# and 5#, the molecular sieve crystallinity of catalyst 2# is higher. The micropore volume of catalysts 1-3# is significantly higher than that of catalysts 4-6#, indicating that part of the binder has been converted into molecular sieve crystals.

[0080] As shown in the activity test results in Table 2, in the dimethyl ether and carbon monoxide to methyl acetate reaction, the molecular sieve catalysts in Comparative Examples 1 and 2, due to the presence of a binder, exhibited dimethyl ether conversions of 37.3% and 39.0%, respectively, and methyl acetate selectivities of 94.7% and 95.6%, respectively, in the dimethyl ether carbonylation reaction. Compared to Examples 1, 2, and 3, both dimethyl ether conversion and methyl acetate selectivity decreased significantly. The performance of the catalyst in Comparative Example 3, which was formed and recrystallized after crystallization, improved, but was still significantly lower than that of Examples 1, 2, and 3.

[0081] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a carbonylation catalyst, characterized in that The following steps are involved: (1) The silicon source, aluminum source, sodium hydroxide, water and template A are mixed in proportion to obtain a pre-crystallization solution, which is then transferred to a pre-crystallization kettle for hydrothermal pre-crystallization, filtered and dried to obtain a precursor; Template A is any one of cyclohexylamine, aniline, monomethylamine, and dimethylamine; the mass ratio of H2O, NaOH, template A, silicon source, and aluminum source is 100: 0.01-10.0: 0.01-2.0: 0.01-10.0: 0.01-10.0; the pre-crystallization temperature is 100-150°C, and the pre-crystallization time is 5-10 hours; (2) forming the precursor and the binder, and after the formed sample is dried, transferring it to a crystallization kettle containing a crystallization solution for crystallization for a certain period of time, filtering, washing and drying, and then calcining-exchanging-recalcining to obtain a catalyst; the crystallization solution contains the template B+C and the pre-crystallization solution filtered in step (1); The template B+C is a combination of any two of hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, tetramethylammonium chloride, tetrabutylammonium chloride or tetrapropylammonium chloride; in step (2), the ratio of the molded sample, the pre-crystallization liquid and the template B+C is 1 kg:4-20 L:10-50 g, and the mass ratio of the template B / C is 3-10:1, the crystallization temperature is 130-200 ° C, and the time is 5-96 h; the crystallization temperature is greater than the pre-crystallization temperature, and the crystallization / pre-crystallization time ratio is greater than 5.

2. The method for preparing a carbonylation catalyst according to claim 1, wherein: The silicon source described in step (1) is any one of silica sol, silica powder or white carbon black; the aluminum source is any one of aluminum chloride, aluminum sulfate, aluminum nitrate or sodium aluminate; the drying temperature is 20-70°C, and the drying time is 1-10h.

3. The method for preparing a carbonylation catalyst according to claim 1, wherein: The binder described in step (2) is any one of silica sol or SB powder or a mixture of the two; the mass ratio of the precursor to the binder is 1:0.1-1.

0.

4. The method for preparing a carbonylation catalyst according to claim 1, wherein: The molding methods include ball molding and extrusion molding; the ball size is 1-5mm, the extrusion diameter is 1-5mm, and the length is 3-5mm.

5. The method for preparing a carbonylation catalyst according to claim 1, wherein: In step (2), the drying temperature of the molded sample is 20-70°C, and the drying time is 1-10 hours; the drying temperature after crystallization is 100-200°C, and the drying time is 1-10 hours.

6. The method for preparing a carbonylation catalyst according to claim 1, wherein: In step (2), the calcination temperature is 450-600° C., and the calcination time is 2-10 h. The exchange reagent is any one of ammonium chloride, ammonium nitrate, or ammonium sulfate. The re-calcination temperature is 450-550° C., and the calcination time is 2-10 h.

7. A carbonylation catalyst prepared according to the method according to any one of claims 1 to 6, characterized in that: The obtained catalyst type is one of MOR, ZSM-35 or FER molecular sieve, and its Si / Al ratio is 5-50.

8. The use of the carbonylation catalyst according to claim 7, characterized in that: The catalyst is used in the carbonylation reaction of dimethyl ether and carbon monoxide to obtain methyl acetate product. The reaction temperature is 120-210°C, the reaction pressure is 1.0-10.0 MPa, and the feed gas volume space velocity is 1000-10000 h -1 The volume ratio of carbon monoxide and dimethyl ether in the raw gas is 5:1~20:

1.

9. The use of the carbonylation catalyst according to claim 8, characterized in that: Before the reaction, the catalyst is pre-adsorbed with pyridine or methyl iodide at a temperature of 250-350° C. The concentration of pyridine or methyl iodide is 0.1-10.0 v.%, and the inert diluent gas is N2 or He gas.

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