Use of silicate zeolite molecular sieve ZMQ-1 in carbonylation reaction

Abstract

The application discloses application of a silicate zeolite molecular sieve ZMQ-1 in a carbonylation reaction and belongs to the field of zeolite molecular sieves. The silicate zeolite molecular sieve ZMQ-1 has a novel topological structure, a unique pore system and high thermal and hydrothermal stability, and thus exhibits unique performance in the carbonylation reaction, especially in a reaction of preparing methyl methoxyacetate through carbonylation of methylal. The reaction activity and stability are obviously improved on the basis of maintaining high carbonylation selectivity.

Description

Technical Field

[0001] This application relates to the application of a silicate zeolite molecular sieve ZMQ-1 in carbonylation reactions, and belongs to the field of zeolite molecular sieves. Background Technology

[0002] Methanol, as an important platform compound for the efficient utilization of coal, can be catalytically converted into high-value-added chemical products. Using methanol as a raw material, dimethyl ether (DME) and dimethyl acetal (DMM) can be prepared. Further, through carbonylation processes, high-value-added chemicals such as acetic acid (EA), methyl acetate (MA), methyl methoxyacetate (MMAc), and dimethyl carbonate (DMC) can be obtained. This route involves little or no water, effectively reducing separation energy consumption and production costs, and yields products with high purity.

[0003] Currently, carbonylation reactions mainly follow two pathways: homogeneous and heterogeneous methods. Traditional homogeneous methods suffer from problems such as high cost of precious metal catalysts, precious metal loss, difficulty in separating the catalyst from the product, easy corrosion of equipment by organic solutions, and inability to achieve continuous and efficient production. Heterogeneous methods generally use solid acids such as zeolite molecular sieves as catalysts. The product and catalyst are easily separated, there is virtually no corrosion to the equipment, and pollutant emissions are reduced, providing a green and environmentally friendly pathway for carbonylation reactions. Patent CN111995521A, using HSUZ-4 molecular sieves containing small and medium pores as catalysts, achieved a stability of 48 hours for the carbonylation of dimethyl acetal (DMM) to methyl methoxyacetate (MMAc), but the DMM conversion rate was less than 30%. Bell's research group (J. Catal., 2010, 270, 185–195) utilized macroporous acidic high-silica Y molecular sieves to catalyze the gas-phase carbonylation of methyl acetal to prepare methyl methoxyacetate. Compared with conventional mesoporous MFI molecular sieves, it exhibited higher activity and product selectivity, but the catalyst stability was poor. This is because methyl acetal can be simultaneously converted into large aromatic rings on the acidic molecular sieve, leading to easy carbon deposition and deactivation of the catalyst. Patent CN109368655A prepared a hierarchical porous HY molecular sieve with high crystallinity and large pore size for the carbonylation of methyl acetal to produce high-value-added methyl methoxyacetate. At a reaction pressure of 5.0 MPa and a reaction temperature of 100 °C, the methyl acetal conversion rate was close to 100%, the methyl methoxyacetate selectivity was higher than 95%, and the catalyst stability was evaluated for 1000 h without significant deactivation. However, the DMM throughput of this process is relatively small, and there is still a gap before industrial-scale production. Summary of the Invention

[0004] According to one aspect of this application, an application of silicate zeolite molecular sieve ZMQ-1 in carbonylation reactions is provided. Due to its novel topology, unique pore system, and high thermal and hydrothermal stability, silicate zeolite molecular sieve ZMQ-1 exhibits unique performance in carbonylation reactions, especially in the carbonylation of methyl acetal to prepare methyl methoxyacetate. It can significantly improve both reaction activity and stability while maintaining high carbonylation selectivity.

[0005] Application of ZMQ-1, a silicate zeolite molecular sieve, in carbonylation reactions.

[0006] Optionally, the silicate zeolite molecular sieve ZMQ-1 is processed to obtain hydrogen-form ZMQ-1 molecular sieve, which is used as a solid acid catalyst for carbonylation reaction.

[0007] Optionally, the treatment includes ammonium exchange or acid exchange.

[0008] Optionally, the silicate zeolite molecular sieve ZMQ-1 has a silicon-to-aluminum atomic ratio of 10 to 200.

[0009] Preferably, the silicate zeolite molecular sieve ZMQ-1 has a silicon-to-aluminum atomic ratio of 10 to 100.

[0010] Optionally, the silicon-to-aluminum atomic ratio of the silicate zeolite molecular sieve ZMQ-1 is independently selected from any value or a range between 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 70, 80, 90, 100, 120, 140, 160, 180, and 200.

[0011] Optionally, the carbonylation reaction includes one of methyl acetal carbonylation, dimethyl ether carbonylation, and methanol oxidative carbonylation.

[0012] Specifically, the carbonylation reaction is a methyl acetal carbonylation reaction.

[0013] According to another aspect of this application, a method for the carbonylation of methyl acetal to produce methyl methoxyacetate is provided. Using methyl acetal and carbon monoxide as raw materials, the carbonylation reaction of methyl acetal is catalyzed by a hydrogen-form ZMQ-1 molecular sieve, resulting in the efficient synthesis of methyl methoxyacetate under mild conditions of relatively low temperature and pressure.

[0014] A method for producing methyl methoxyacetate by carbonylation of methyl acetal, the method comprising: passing a feed gas containing methyl acetal and carbon monoxide into a reactor equipped with a hydrogen-form ZMQ-1 molecular sieve, reacting to obtain methyl methoxyacetate. The feed gas methyl acetal can be derived from the conversion of syngas, and the carbon monoxide can be derived from fossil fuels, renewable biomass, or the reduction conversion of carbon dioxide.

[0015] Optionally, the molar ratio of carbon monoxide to methyl acetal is 2:1 to 100:1.

[0016] Preferably, the molar ratio of carbon monoxide to methyl acetal is 5:1 to 60:1.

[0017] Optionally, the molar ratio of carbon monoxide to methyl acetal is independently selected from any value or a range between 2:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, 60:1, 70:1, 80:1, 90:1, and 100:1.

[0018] Optionally, the mass hourly space velocity (WHSV) of methylal is 0.05–50 h⁻¹. -1 .

[0019] Preferably, the mass hourly space velocity (WHSV) of methylal is 0.1–20 h⁻¹. -1 .

[0020] Optionally, the mass hourly space velocity (MSV) of the methylal is independently selected from 0.05 h⁻¹. -1 0.1h -1 0.5h -1 1.0h -1 2.5h -1 5.0h -1 7.5h -1 10.0h -1 12.5h -1 15.0h -1 17.5h -1 20h -1 25h -1 30h -1 40h -1 50h -1 Any value in the range or any value between the two.

[0021] Optionally, a dilution gas is also provided, wherein the dilution gas is selected from at least one of nitrogen, helium, and argon.

[0022] Optionally, carbon monoxide accounts for 5-100% of the volume. The volume is calculated as the sum of carbon monoxide and diluent gases.

[0023] The dilution gas added in this application does not react with the reactants, catalysts, products, or the reactor itself in the reactor.

[0024] Optionally, the reaction temperature is 40–350℃ and the reaction pressure is 0.5–10 MPa.

[0025] Preferably, the reaction temperature is 40–150°C and the reaction pressure is 1–7 MPa.

[0026] Optionally, the reaction temperature is independently selected from any value or a range between any two of 40°C, 50°C, 75°C, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, 300°C, 325°C, and 350°C.

[0027] Optionally, the reaction pressure is independently selected from any value or a range between any two of 0.5 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 2.5 MPa, 3.0 MPa, 3.5 MPa, 4.0 MPa, 4.5 MPa, 5.0 MPa, 5.5 MPa, 6.0 MPa, 6.5 MPa, 7.0 MPa, 7.5 MPa, 8.0 MPa, 8.5 MPa, 9.0 MPa, 9.5 MPa, and 10.0 MPa.

[0028] Alternatively, the reactor may be one of a fixed-bed reactor, a fluidized-bed reactor, or a moving-bed reactor.

[0029] Preferably, the reactor is a fixed-bed reactor.

[0030] Hydrogen-form ZMQ-1 molecular sieves can also be mixed with molecular sieves with FAU, BEA, and MFI topologies to be used as catalysts.

[0031] The hydrogen-form ZMQ-1 molecular sieve was activated before the reaction under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500℃ at a rate of 10℃ / min under normal pressure, maintained at the corresponding temperature for about 1 hour, and then lowered to the temperature required for the reaction.

[0032] The beneficial effects that this application can produce include:

[0033] 1) The method for producing methyl methoxyacetate provided in this application uses hydrogen-form ZMQ-1 molecular sieve as a catalyst, which can efficiently produce methyl methoxyacetate, a precursor of important chemical raw materials such as ethylene glycol, glycolic acid, and glycolate, using carbon monoxide and methyl acetal as raw materials under relatively mild reaction conditions.

[0034] 2) The existing molecular sieve catalysts for the carbonylation reaction of methyl acetal provided in this application are limited to molecular sieves with 12-membered or 10-membered ring channels such as MFI, BEA, and FAU. The catalyst used in this application is ZMQ-1 molecular sieve with 28-membered ring, which can significantly improve the reaction activity and stability while maintaining high carbonylation selectivity.

[0035] 3) In the production method of methyl methoxyacetate provided in this application, only the side reaction of methyl acetal disproportionation can be observed during the production process. The disproportionation products, methyl formate and dimethyl ether, also have great application value.

[0036] 4) The method for producing methyl methoxyacetate provided in this application, using hydrogen-form ZMQ-1 molecular sieve as a catalyst, provides a reliable route for the production and large-scale application of mesoporous molecular sieve materials in important chemical raw materials. Attached Figure Description

[0037] Figure 1 Powder X-ray diffraction patterns of ZMQ-1 molecular sieves with different silicon-aluminum atomic ratios provided in Example 1 of the present invention.

[0038] Figure 2 The Fourier transform infrared spectrum of ZMQ-1 molecular sieve with a silicon-aluminum atomic ratio of 16 provided in Example 1 of this invention was collected after vacuum adsorption of pyridine at room temperature and vacuum desorption at 150°C to a steady state.

[0039] Figure 3 The Fourier transform infrared spectrum is obtained by adsorbing and purging di-tert-butylpyridine onto the ZMQ-1 molecular sieve with a silicon-to-aluminum ratio of 16 provided in Example 1 of the present invention.

[0040] Figure 4 The adsorption curves of the reactant methyl acetal and the carbonylation product methyl methoxyacetate in the ZMQ-1 molecular sieve with a silicon-to-aluminum ratio of 16 provided in Example 1 are shown. The adsorption curves are shown in the figure. Detailed Implementation

[0041] The present application is described in detail below with reference to the embodiments, but the present application is not limited to these embodiments.

[0042] Unless otherwise specified, the raw materials and catalysts used in the embodiments of this application were all purchased commercially.

[0043] Unless otherwise specified, all test methods are standard and all instrument settings are those recommended by the manufacturer.

[0044] Powder X-ray diffraction data analysis of the samples was performed using a Rigaku LabVIEW X-ray diffractometer (Japan), with a CuKα X-ray source and a wavelength of [wavelength missing].

[0045] The Fourier transform infrared characterization of pyridine adsorption / desorption and di-tert-butylpyridine adsorption / desorption was performed using a Thermo Scientific Nicolet iS50 infrared spectrometer equipped with a deuterated triglycine sulfate (DTGS) detector connected to a dynamic vacuum system. The single-dose vacuum cell volume was 2.617 cm³. 3All spectral acquisitions had a resolution of 4 cm⁻¹. -1 The number of spectral scans per spectral sample was 128, and the spectral data were normalized based on the mass of a 20mg self-supporting tablet.

[0046] The diffusion rate curves of the reactant methyl acetal and the carbonylation product methyl methoxyacetate in ZMQ-1 molecular sieve were measured using an IGA-100 intelligent gravimetric analyzer. During the test, 20-30 mg of the molecular sieve sample was weighed and placed in the instrument. The temperature was first raised to 350℃ and maintained for 2 hours to allow small molecules to desorb from the molecular sieve until the system mass remained constant. Then, the temperature was lowered to the test temperature of 20℃, and methyl acetal or methyl methoxyacetate was introduced at a pressure of 3 mbar. The change in system mass was recorded until stability was achieved.

[0047] The conversion rate and selectivity are calculated in the following ways in this application:

[0048] Methylal conversion rate = [(moles of methylal at reactor inlet) - (moles of methylal at reactor outlet)] ÷ (moles of methylal at reactor inlet) × (100%).

[0049] Selectivity of methyl methoxyacetate = [3 × (moles of methyl methoxyacetate at reactor outlet)] / [2 × (moles of dimethyl ether at reactor outlet) + 2 × (moles of methyl formate at reactor outlet) + (moles of methanol at reactor outlet) + 3 × (moles of methyl methoxyacetate at reactor outlet)].

[0050] In this application, the silicate zeolite molecular sieve ZMQ-1 adopts the method in the prior art CN118515294A.

[0051] The silicate zeolite molecular sieve ZMQ-1 has an anhydrous chemical composition of SiO2·1 / xXO. 1.5 ·mMO 0.5 Where X is a trivalent element in the framework, the molar ratio of Si / X is x≥5, and M is a balanced cation in the framework, the molar ratio of M / Si is 0≤m≤1.

[0052] The framework trivalent element X is selected from at least one of boron, aluminum, gallium, indium, iron, and chromium; the framework balanced cation M is selected from at least one of hydrogen ion, ammonium ion, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, magnesium ion, calcium ion, strontium ion, and barium ion; the molecular sieve contains a non-silicon tetravalent framework element (Y) with a mass greater than 0 and less than or equal to 10 wt%, wherein Y is selected from at least one of germanium, tin, titanium, zirconium, and hafnium; silicon in the molecular sieve can be partially replaced by at least one of germanium, tin, titanium, zirconium, and hafnium; other framework divalent elements (Z) can be introduced into the molecular sieve, wherein Z is selected from at least one of zinc, beryllium, copper, cobalt, iron, manganese, chromium, molybdenum, and tungsten, and the molar ratio of the divalent element to silicon is greater than 0 and less than or equal to 0.1.

[0053] The silicate zeolite molecular sieve ZMQ-1 contains a three-dimensional channel system composed of 28×10×10-membered rings, wherein the size of the 28-membered rings is... The dimensions of the 10-member ring are as follows: and

[0054] Alternatively, non-carbonylating non-framework aluminum can be removed from silicate zeolite molecular sieve ZMQ-1 by ammonium exchange or weak acid washing.

[0055] Optionally, the silicate zeolite molecular sieve ZMQ-1 can be synthesized directly or its silica-alumina ratio can be adjusted through post-treatment methods such as acid washing and hydrothermal treatment.

[0056] The silicate zeolite molecular sieve ZMQ-1 was obtained using the method described in patent CN118515294 A. Specifically, ZMQ-1 molecular sieves with silicon-to-aluminum atomic ratios of 16, 35, or 68 were obtained.

[0057] From CN118515294 A Figure 1 and Figure 2 As can be seen, ZMQ-1 zeolite molecular sieves possess high thermal and hydrothermal stability. Figure 5 in CN118515294 A shows that ZMQ-1 zeolite molecular sieves feature intrinsically mesoporous and microporous channels connected by crystallography and arranged in a regular pattern, along with tunable acidic sites. The thermal and hydrothermal stability temperature of ZMQ-1 zeolite molecular sieves can reach 1000℃, making it well-suited for carbonylation reactions.

[0058] In this application, the organic structure directing agent is synthesized according to Example 1 in CN118515294 A.

[0059] Example 1: Preparation of Hydrogen-Form Silicate-Aluminum ZMQ-1 Molecular Sieve Catalyst

[0060] Preparation method of ZMQ-1 molecular sieve with a silicon-to-aluminum atomic ratio of 16: A synthetic gel was prepared according to the molar ratio of SiO2:0.02Al2O3:0.25Q(OH)2:10H2O, where Q is octamethylene-1,8-bis(tricyclohexyl)phosphine cation. 6 mmol of organic structure-directing agent solution was weighed, and 0.21 g of aluminum isopropoxide was added. The mixture was magnetically stirred for 1 hour, followed by the addition of 5.21 g of tetraethyl orthosilicate. The resulting mixture was stirred at room temperature for 12 hours. The resulting transparent gel was placed in a vacuum oven and heated at 100 °C for 3 hours to remove the solvent and excess water. The final synthetic gel was transferred to a 25 mL stainless steel synthesis vessel with a polytetrafluoroethylene liner and crystallized at 190 °C for 10 days. The product was washed by filtration with 200 mL of water, 200 mL of ethanol, and 100 mL of acetone, and dried overnight to obtain a fresh synthetic zeolite molecular sieve precursor. The product was then calcined in a muffle furnace at 600°C for 6 hours under a flowing air atmosphere to remove the organic structure-directing agent. Powder X-ray diffraction confirmed the phase as ZMQ-1, and ICP-OES elemental analysis showed a silicon-to-aluminum atomic ratio of 16.

[0061] Preparation method of ZMQ-1 molecular sieve with a silicon-to-aluminum atomic ratio of 35: A synthetic gel was prepared according to the molar ratio of SiO2:0.01Al2O3:0.25Q(OH)2:10H2O, where Q is octamethylene-1,8-bis(tricyclohexyl)phosphine cation. 6 mmol of organic structure-directing agent solution was weighed, and 0.21 g of aluminum isopropoxide was added. The mixture was magnetically stirred for 1 hour, followed by the addition of 5.21 g of tetraethyl orthosilicate. The resulting mixture was stirred at room temperature for 12 hours. The resulting transparent gel was placed in a vacuum oven and heated at 100 °C for 3 hours to remove the solvent and excess water. The final synthetic gel was transferred to a 25 mL stainless steel synthesis vessel with a polytetrafluoroethylene liner and crystallized at 190 °C for 10 days. The product was washed by filtration with 200 mL of water, 200 mL of ethanol, and 100 mL of acetone, and dried overnight to obtain a fresh synthetic zeolite molecular sieve precursor. The product was then calcined in a muffle furnace at 600°C for 6 hours under a flowing air atmosphere to remove the organic structure-directing agent. Powder X-ray diffraction confirmed the phase as ZMQ-1, and ICP-OES elemental analysis showed a silicon-to-aluminum atomic ratio of 35.

[0062] Preparation method of ZMQ-1 molecular sieve with a silicon-to-aluminum atomic ratio of 68: A synthetic gel was prepared according to the molar ratio of SiO2:0.005Al2O3:0.25Q(OH)2:10H2O, where Q is octamethylene-1,8-bis(tricyclohexyl)phosphine cation. 6 mmol of organic structure-directing agent solution was weighed, and 0.21 g of aluminum isopropoxide was added. The mixture was magnetically stirred for 1 hour, followed by the addition of 5.21 g of tetraethyl orthosilicate. The resulting mixture was stirred at room temperature for 12 hours. The resulting transparent gel was placed in a vacuum oven and heated at 100 °C for 3 hours to remove the solvent and excess water. The final synthetic gel was transferred to a 25 mL stainless steel synthesis vessel with a polytetrafluoroethylene liner and crystallized at 190 °C for 10 days. The product was washed by filtration with 200 mL of water, 200 mL of ethanol, and 100 mL of acetone, and dried overnight to obtain a fresh synthetic zeolite molecular sieve precursor. The product was then calcined in a muffle furnace at 600°C for 6 hours under a flowing air atmosphere to remove the organic structure-directing agent. Powder X-ray diffraction confirmed the phase as ZMQ-1, and ICP-OES elemental analysis showed a silicon-to-aluminum atomic ratio of 68.

[0063] The calcined molecular sieve was placed in a 1M NH4Cl solution and magnetically stirred overnight at 70°C to remove residual phosphorus species. Then, it was washed three times by centrifugation with deionized water, dried at 100°C, and calcined at 600°C for 3 hours to finally obtain the hydrogen form ZMQ-1 molecular sieve, which was used in the carbonylation reaction.

[0064] The ZMQ-1 molecular sieve described above was characterized, and the specific analysis is as follows:

[0065] The powder X-ray diffraction pattern of ZMQ-1 zeolite molecular sieve is shown below. Figure 1 It has clear and unique characteristic diffraction peaks and a high degree of crystallinity.

[0066] ZMQ-1 zeolite molecular sieve contains a three-dimensional channel system composed of 28×10×10-membered rings, wherein the size of the 28-membered rings is... The dimensions of the 10-member ring are as follows: and The mesoporous channels of the 28-membered ring facilitate the diffusion of reactants and products, reduce carbon deposition, and improve stability. The 10-membered ring "window" is located on the pore wall of the straight channels of the 28-membered ring, with framework aluminum all situated within it, providing active acid sites. The number of acid sites can be modulated during the synthesis process, which is beneficial for the introduction of other metal active species and the controllable adjustment of the number and location of active sites, thereby further benefiting the directional adsorption of reactants and products and the progress of the reaction. Taking the ZMQ-1 molecular sieve with a silicon-to-aluminum ratio of 16 provided in Example 1 as a typical example, pyridine ( Figure 2 ) and di-tert-butylpyridine (DTBPY) Figure 3The adsorption-desorption Fourier transform infrared characterization results showed that the active sites within these "windows" could be adsorbed by both small and large pyridine molecules, indicating that these acidic sites can be fully contacted by guest molecules, thus providing high reactivity. The adsorption results of methyl acetal and its carbonylation product methyl methoxyacetate in ZMQ-1 showed... Figure 4 Its pore structure facilitates the adsorption and diffusion of reactants and products, thereby improving catalytic activity and product selectivity.

[0067] Comparative Example 1

[0068] JZO molecular sieve (Si / Al = 15) was synthesized according to the method in the literature (Science, 2021, 374, 1605–1608). After calcination, NH4Cl exchange, drying and calcination, hydrogen-form JZO molecular sieve was obtained and used in carbonylation reaction.

[0069] Comparative Example 2

[0070] Commercially available hydrogen-form FAU molecular sieves (Si / Al = 15) were used in the carbonylation reaction.

[0071] Comparative Example 3

[0072] Commercially available hydrogen-form Beta molecular sieves (Si / Al = 15) were used in the carbonylation reaction.

[0073] Example 2: Carbonylation of DMM to produce methyl methoxyacetate (MMAc)

[0074] 1.0 g of the hydrogen-form ZMQ-1 molecular sieve catalyst (Si / Al = 16, 20-40 mesh) synthesized in Example 1, or the molecular sieve catalysts obtained in the comparative examples above, were respectively loaded into fixed-bed reactors. The catalyst beds were filled with quartz sand at both the top and bottom. The reactors had carbon monoxide and methyl acetal inlets at the top and a reaction product outlet at the bottom. A thermocouple was installed in the middle of each catalyst layer to monitor the reaction temperature. Before the reaction began, the catalyst was activated under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500°C at a rate of 10°C / min under normal pressure, maintained at that temperature for approximately 1 hour, and then lowered to the required reaction temperature. The reaction conditions were: reaction temperature 90°C, reaction pressure 5 MPa, and methyl acetal mass hourly space velocity (HSV) of 0.5 h⁻¹. -1 The ratio of the total molar amount of carbon monoxide to the total molar amount of methyl acetal in the reactor per unit time was 40:1. The products were separated by a PLOT-Q capillary column, detected by an FID detector, and analyzed by an Agilent 7890A gas chromatograph. The reaction results are shown in Table 1. ZMQ-1 molecular sieves exhibit higher DMM conversion and selectivity than other commercially available molecular sieves.

[0075] Table 1. Reaction results of Example 2, Comparative Examples 1, 2 and 3

[0076]

[0077] Example 3

[0078] 1.0 g of the ZMQ-1 molecular sieve catalyst (Si / Al = 16, 20-40 mesh) from Example 1 was loaded into a fixed-bed reactor. The catalyst bed was filled with quartz sand both above and below. The reactor had a carbon monoxide inlet and a methyl acetal inlet at the top, and a reaction product outlet at the bottom. Before the reaction, the catalyst was activated under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500°C at a rate of 10°C / min under normal pressure, maintained at that temperature for approximately 1 hour, and then lowered to the required reaction temperature. The reaction conditions were: reaction temperature 40-100°C, reaction pressure 5 MPa, and methyl acetal mass hourly space velocity (HSV) of 0.5 h⁻¹. -1 The ratio of the total molar amount of carbon monoxide to the total molar amount of methyl acetal in the reactor per unit time was 40:1. The products were separated by a PLOT-Q capillary column, detected by an FID detector, and analyzed by an Agilent 7890A gas chromatograph. The reaction results are shown in Table 2. ZMQ-1 molecular sieve exhibited high reactivity and product selectivity at a mild reaction temperature.

[0079] Table 2 Reaction results of Example 3

[0080]

[0081] Example 4

[0082] 1.0 g of the ZMQ-1 molecular sieve catalyst (Si / Al = 16, 20-40 mesh) from Example 1 was loaded into a fixed-bed reactor. The catalyst bed was filled with quartz sand both above and below. The reactor had a carbon monoxide inlet and a methyl acetal inlet at the top, and a reaction product outlet at the bottom. Before the reaction, the catalyst was activated under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500°C at a rate of 10°C / min under normal pressure, maintained at that temperature for approximately 1 hour, and then lowered to the required reaction temperature. The reaction conditions were: reaction temperature 90°C, reaction pressure 5 MPa, and methyl acetal mass hourly space velocity (HSV) of 0.1-20 h⁻¹. -1 The ratio of the total molar amount of carbon monoxide to the total molar amount of methyl acetal in the reactor per unit time was 40:1. The products were separated by a PLOT-Q capillary column, detected by an FID detector, and analyzed by an Agilent 7890A gas chromatograph. The reaction results are shown in Table 3. ZMQ-1 maintains high reactivity and high product selectivity even at high DMM volume hourly space velocities, making it suitable for industrial-scale production.

[0083] Table 3 Reaction results of Example 4

[0084]

[0085] Example 5

[0086] 1.0 g of the ZMQ-1 molecular sieve catalyst (Si / Al = 16, 20-40 mesh) from Example 1 was loaded into a fixed-bed reactor. The catalyst bed was filled with quartz sand both above and below. The reactor had a carbon monoxide inlet and a methyl acetal inlet at the top, and a reaction product outlet at the bottom. Before the reaction, the catalyst was activated under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500°C at a rate of 10°C / min under normal pressure, maintained at that temperature for approximately 1 hour, and then lowered to the required reaction temperature. The reaction conditions were: reaction temperature 90°C, reaction pressure 5 MPa, and methyl acetal mass hourly space velocity (HSV) of 0.5 h⁻¹. -1 The ratio of the total molar amount of carbon monoxide to the total molar amount of methyl acetal in the reactor per unit time was 40:1. The products were separated by a PLOT-Q capillary column, detected by an FID detector, and analyzed by an Agilent 7890A gas chromatograph. The reaction results are shown in Table 4. After 30 days of continuous online reaction with ZMQ-1 molecular sieve, the conversion and selectivity remained largely unchanged, indicating its high stability.

[0087] Table 4 Reaction results of Example 5

[0088]

[0089] Example 6

[0090] 1.0 g of the ZMQ-1 molecular sieve catalyst (Si / Al = 16, 20-40 mesh) from Example 1 was loaded into a fixed-bed reactor. The catalyst bed was filled with quartz sand both above and below. The reactor had a carbon monoxide inlet and a methyl acetal inlet at the top, and a reaction product outlet at the bottom. Before the reaction, the catalyst was activated under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500°C at a rate of 10°C / min under normal pressure, maintained at that temperature for approximately 1 hour, and then lowered to the required reaction temperature. The reaction conditions were: reaction temperature 90°C, reaction pressure 1-5 MPa, and methyl acetal volume hourly space velocity (HSV) of 0.5 h⁻¹. -1 The ratio of the total molar amount of carbon monoxide to the total molar amount of methyl acetal in the reactor per unit time was 40:1. The products were separated by a PLOT-Q capillary column, detected by an FID detector, and analyzed by an Agilent 7890A gas chromatograph. The reaction results are shown in Table 5. ZMQ-1 molecular sieves can still achieve high activity and product selectivity under relatively low pressure, which is beneficial for reducing production energy consumption.

[0091] Table 5 Reaction results of Example 6

[0092]

[0093] Example 7

[0094] 1.0 g of the ZMQ-1 molecular sieve catalyst (Si / Al = 16, 20-40 mesh) from Example 1 was loaded into a fixed-bed reactor. The catalyst bed was filled with quartz sand both above and below. The reactor had a carbon monoxide inlet and a methyl acetal inlet at the top, and a reaction product outlet at the bottom. Before the reaction, the catalyst was activated under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500°C at a rate of 10°C / min under normal pressure, maintained at that temperature for approximately 1 hour, and then lowered to the required reaction temperature. The reaction conditions were: reaction temperature 90°C, reaction pressure 5 MPa, and methyl acetal mass hourly space velocity (HSV) of 0.5 h⁻¹. -1 The ratio of the total molar amount of carbon monoxide to the total molar amount of methyl acetal in the reactor per unit time was 10:1 to 60:1. The products were separated by a PLOT-Q capillary column, detected by an FID detector, and analyzed by an Agilent 7890A gas chromatograph. The reaction results are shown in Table 6. At a relatively low molar ratio of carbon monoxide to methyl acetal, the ZMQ-1 molecular sieve achieved high conversion and selectivity, indicating that this molecular sieve has a high product adsorption and conversion capacity, which is beneficial for reducing raw material costs.

[0095] Table 6 Reaction results of Example 7

[0096]

[0097] Furthermore, following the descriptions in Examples 3 to 7 above, the catalyst was replaced with the FAU molecular sieve catalyst of Comparative Example 2 (Si / Al = 15, 20-40 mesh), and corresponding tests were performed, as follows:

[0098] 1.0 g of FAU molecular sieve catalyst (Si / Al = 15, 20–40 mesh) from Comparative Example 2 was packed into a fixed-bed reactor. The catalyst bed was filled with quartz sand both above and below. The reactor had a carbon monoxide inlet and a methyl acetal inlet at the top, and a reaction product outlet at the bottom. Before the reaction, the catalyst was activated under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500 °C at a rate of 10 °C / min under normal pressure, maintained at that temperature for approximately 1 h, and then lowered to the required reaction temperature. The reaction conditions were: reaction temperature 40–100 °C, reaction pressure 5 MPa, and methyl acetal mass hourly space velocity (HSV) of 0.5 h⁻¹. -1The ratio of the total molar amount of carbon monoxide to the total molar amount of methyl acetal in the reactor per unit time was 40:1. The products were separated by a PLOT-Q capillary column, detected by an FID detector, and analyzed by an Agilent 7890A gas chromatograph. The reaction results are shown in Table 7. With increasing reaction temperature, both the activity and selectivity of FAU in the DMM carbonylation reaction increased. Compared with ZMQ-1 under the same conditions and with a similar silica-alumina ratio, FAU molecular sieves showed inferior activity and selectivity compared to ZMQ-1, demonstrating the extremely high catalytic activity and selectivity of ZMQ-1 for the DMM carbonylation reaction.

[0099] Table 7 shows the reaction results of the FAU molecular sieve catalyst in Comparative Example 2.

[0100]

[0101] 1.0 g of FAU molecular sieve catalyst (Si / Al = 15, 20–40 mesh) from Comparative Example 2 was loaded into a fixed-bed reactor. The catalyst bed was filled with quartz sand both above and below. The reactor had a carbon monoxide inlet and a methyl acetal inlet at the top, and a reaction product outlet at the bottom. Before the reaction, the catalyst was activated under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500 °C at a rate of 10 °C / min under normal pressure, maintained at that temperature for approximately 1 h, and then lowered to the required reaction temperature. The reaction conditions were: reaction temperature 90 °C, reaction pressure 1–5 MPa, and methyl acetal mass hourly space velocity (HSV) of 0.5 h⁻¹. -1 The ratio of the total molar amount of carbon monoxide to the total molar amount of methyl acetal in the reactor per unit time was 40:1. The products were separated by a PLOT-Q capillary column, detected by an FID detector, and analyzed by an Agilent 7890A gas chromatograph. The reaction results are shown in Table 8. With increasing total system pressure, both the activity and selectivity of FAU in catalyzing DMM carbonylation increased. Compared with ZMQ-1 under the same conditions and with a similar silica-alumina ratio, the carbonylation activity and selectivity of FAU molecular sieve were inferior to ZMQ-1, especially at low pressure where ZMQ-1 showed higher carbonylation selectivity.

[0102] Table 8. Reaction results of the FAU molecular sieve catalyst in Comparative Example 2

[0103]

[0104] 1.0 g of FAU molecular sieve catalyst (Si / Al = 15, 20–40 mesh) from Comparative Example 2 was packed into a fixed-bed reactor. The catalyst bed was filled with quartz sand both above and below. The reactor had a carbon monoxide inlet and a methyl acetal inlet at the top, and a reaction product outlet at the bottom. Before the reaction, the catalyst was activated under the following conditions: nitrogen flow rate of 50 mL / min, temperature increased to 500 °C at a rate of 10 °C / min under normal pressure, maintained at that temperature for approximately 1 h, and then lowered to the required reaction temperature. The reaction conditions were: reaction temperature 90 °C, reaction pressure 5 MPa, and methyl acetal mass hourly space velocity (HSV) of 0.1–20 h⁻¹. -1 The ratio of the total molar amount of carbon monoxide to the total molar amount of methyl acetal in the reactor per unit time was 40:1. The products were separated by a PLOT-Q capillary column, detected by an FID detector, and analyzed by an Agilent 7890A gas chromatograph. The reaction results are shown in Table 9. Compared with ZMQ-1 under the same conditions and with a similar silica-alumina ratio, the carbonylation activity and selectivity of FAU molecular sieves were inferior to those of ZMQ-1.

[0105] Table 9 shows the reaction results of the FAU molecular sieve catalyst in Comparative Example 2.

[0106]

[0107] The descriptions in this section are merely a few embodiments of this application and are not intended to limit this application in any way. Although the appended embodiments are preferred embodiments, they are not intended to limit this application. Any minor changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application are equivalent to equivalent implementation cases and are all within the scope of the technical solution.

Claims

1. Application of ZMQ-1, a silicate zeolite molecular sieve, in carbonylation reactions.

2. The application according to claim 1, characterized in that, The silicate zeolite molecular sieve ZMQ-1 was processed to obtain the hydrogen form ZMQ-1 molecular sieve, which was used as a solid acid catalyst for the carbonylation reaction.

3. The application according to claim 1, characterized in that, The treatment includes ammonium exchange or acid exchange.

4. The application according to claim 1, characterized in that, The silicate zeolite molecular sieve ZMQ-1 has a silicon-to-aluminum atomic ratio of 10 to 200. Preferably, the silicate zeolite molecular sieve ZMQ-1 has a silicon-to-aluminum atomic ratio of 10 to 100.

5. The application according to claim 1, characterized in that, The carbonylation reaction includes one of the following: methyl acetal carbonylation, dimethyl ether carbonylation, and methanol oxidative carbonylation.

6. A method for preparing methyl methoxyacetate by carbonylation of methyl acetal, characterized in that, The method includes: passing a raw gas containing methyl acetal and carbon monoxide into a reactor containing hydrogen-type ZMQ-1 molecular sieve, reacting to obtain methyl methoxyacetate.

7. The method according to claim 6, characterized in that, The molar ratio of carbon monoxide to methyl acetal is 2:1 to 100:1; Preferably, the molar ratio of carbon monoxide to methyl acetal is 5:1 to 60:1; Preferably, the mass hourly space velocity (WHSV) of methylal is 0.05–50 h⁻¹. -1 ; Preferably, the mass hourly space velocity (WHSV) of methylal is 0.1–20 h⁻¹. -1 .

8. The method according to claim 6, characterized in that, A dilution gas is also provided, wherein the dilution gas is selected from at least one of nitrogen, helium, and argon.

9. The method according to claim 6, characterized in that, The reaction temperature is 40–350℃, and the reaction pressure is 0.5–10 MPa; Preferably, the reaction temperature is 40–150°C and the reaction pressure is 1–7 MPa.

10. The method according to claim 6, characterized in that, The reactor is one of the following: a fixed-bed reactor, a fluidized-bed reactor, or a moving-bed reactor.

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