CN109092348B - Mordenite molecular sieve catalyst, preparation method thereof and application thereof in carbonylation synthesis of methyl acetate - Google Patents
Mordenite molecular sieve catalyst, preparation method thereof and application thereof in carbonylation synthesis of methyl acetate Download PDFInfo
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Abstract
The invention provides a mordenite molecular sieve catalyst, a preparation method thereof and application thereof in carbonylation synthesis of methyl acetate, which comprises the following steps: adding water into a silicon source, an aluminum source and an alkali source, stirring and aging to form sol; adding one or more of a template agent, cations and seed crystals into the sol prepared in the step 1, and stirring and aging; carrying out crystallization reaction to prepare Na-MOR molecular sieve; and obtaining the H-MOR molecular sieve after ammonia exchange. Under the condition of ensuring certain silicon-aluminum ratio, specific surface area, pore volume and the like, mordenite with different crystal grains can be rapidly and controllably prepared, the size of the crystal grains which are beneficial to preparing methyl acetate by carbonylation of dimethyl ether is selected, the diffusion resistance is reduced, and the carbon deposition of a catalyst is reduced.
Description
Technical Field
The invention relates to a catalytic technology for improving the reaction activity of synthesizing methyl acetate by carbonylation of methanol or dimethyl ether, in particular to a mordenite molecular sieve catalyst for synthesizing methyl acetate by carbonylation and a preparation method thereof.
Background
Methyl acetate (also known as methyl acetate) has the advantages of low toxicity, biodegradability and the like, and has active chemical properties and excellent solubility. The organic pollutant emission is not limited, the organic pollutant emission can reach the environmental protection standard, acetone, butanone, ethyl acetate, cyclopentane and the like are gradually replaced as solvents, and the organic pollutant emission can be applied to the fields of coatings, printing ink, resins, adhesives and the like. With the worldwide popularization of fuel ethanol, the synthesis of ethanol by methyl acetate hydrogenation is widely concerned by academia and industry in recent years, the synthesis of the catalyst and the development of key process technology are expected to open up a new path for preparing ethanol by synthesis gas, and the dependence degree of the synthesis gas on petroleum is greatly reduced, so that the application prospect of the catalyst is very wide.
The synthesis process of methyl acetate comprises an acetic acid methanol esterification method, a methanol dehydrogenation synthesis method, a methanol carbonylation method, a methyl formate homologous method, a dimethyl ether carbonylation method and the like. The dimethyl ether carbonylation synthesis of methyl acetate avoids the use of noble metals (Ru and the like) along with the introduction of a molecular sieve system catalyst, realizes the halogen-free of the catalyst, shows good activity and selectivity at low temperature, meets the requirements of green chemical industry and has great industrial value. The overall reaction of the industry is as follows:
CH3OCH3+CO→CH3COOCH3
PCT patent WO2006121778 entitled "alkylation carbonylation Process" reports the use of molecular sieve catalysts supported by H-MOR and H-FER molecular sieves or metals such as copper, nickel, iridium and the like for the carbonylation of dimethyl ether to produce methyl acetate. The reaction shows good activity under high CO partial pressure at the temperature of 150 ℃ and 180 ℃ and under the pressure of 5 MPa.
PCT patent WO2009081099 a1 entitled "carbonylation process for producing acetic acid and/or methyl acetate" reported that the use of commercially available Mordenite (MOR) molecular sieves having a crystallite size of not more than 3 microns, particularly 0.1 to 1.5 microns, had better catalytic activity. Therefore, the method can synthesize the Mordenite (MOR) catalyst with smaller crystal grains, and is greatly beneficial to improving the yield of the dimethyl ether carbonylation reaction.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides a catalyst which is used for synthesizing nano-level Mordenite (MOR) and is suitable for a reaction of synthesizing methyl acetate by carbonylation and a preparation method thereof; the activity of the catalyst in the carbonylation synthesis of methyl acetate reaction is improved by eliminating the diffusion limitation influence in the reaction process; different grain sizes, especially nano-level Mordenite (MOR) molecular sieves, can be controllably synthesized by adopting a microwave promotion and crystallization process quenching mode, and the activity and selectivity of the Mordenite (MOR) molecular sieves in the reaction of synthesizing methyl acetate by carbonylation are improved.
The purpose of the invention is realized by the following technical scheme.
The mordenite molecular sieve catalyst and the preparation method thereof are carried out according to the following steps:
in the step 1, a silicon source is silica sol, sodium silicate, silicon dioxide or ethyl orthosilicate, an aluminum source is sodium metaaluminate or aluminum oxide, an alkali source is sodium hydroxide or ammonia water, wherein the molar ratio of Si to Al in the silicon source and the aluminum source is (5-25):1, and OH in the alkali source and the aluminum source-The molar ratio of Al to Al is (2-8): 1, preferably (3-6): 1, the molar ratio of water to Si in the silicon source is (0-10):1 and does not include 0:1 and 10: 1;
in the step 1, mechanical stirring or magnetic stirring is adopted for stirring, and the stirring and aging time is 1-24 h;
in step 2, the template agent is tetraethylammonium hydroxide or tetraethylammonium bromide, and the cation is ammonium nitrate or ammonium chloride, wherein the molar ratio of the template agent to the Si in the silicon source is (0.1-0.4): 1, the molar ratio of the positive ions to the Si in the silicon source is (0.03-0.1): 1, preferably (0.05-0.09): 1, the adding amount of the seed crystal is 1-10 wt% of the mass of the silicon source;
in the step 2, mechanical stirring or magnetic stirring is adopted for stirring, and the aging time is more than zero and less than or equal to 24 hours, preferably 4-24 hours;
wherein, the reaction conditions of the microwave high-pressure reaction system are as follows: the crystallization temperature is 150-;
wherein the reaction conditions of the hydrothermal reaction system are as follows: the crystallization temperature is 150-;
wherein the drying temperature is 100-;
wherein the concentration of the ammonium nitrate solution or the ammonium chloride solution is 0.1-1mol/L, preferably 0.4-0.6mol/L, and the ammonia exchange condition is as follows: the exchange time is 5-7h, preferably 5.5-6.5h, the exchange temperature is 50-70 ℃, preferably 55-65 ℃, and the solid-to-liquid ratio of the Na-MOR molecular sieve to the ammonium nitrate solution or the ammonium chloride solution is 1: (8-12), preferably 1: (9-11);
wherein the drying temperature is 100-150 ℃, the drying time is 5-10h, the roasting temperature is 400-600 ℃, and the roasting time is 1-5 h.
And (3) loading a single-activity metal or double-activity metal component of the H-MOR molecular sieve prepared in the step (4) onto the H-MOR molecular sieve by adopting an ion exchange method, an impregnation method, an ammonia evaporation method or a solid ion exchange method, wherein the single-activity metal is any one of copper, silver, iron, cobalt or nickel, and the double-activity metal component is any two of copper, silver, iron, cobalt or nickel.
Mordenite molecular sieve catalyst and application thereof in carbonylation synthesis of methyl acetate, wherein reaction conditions are that the feeding molar ratio of raw materials is n (CH)3OCH3) N (CO) 1 (5-60), the reaction temperature is 180-220 ℃, the reaction pressure is 1-3MPa, and the gas space velocity is 1000-4000h-1。
The invention has the beneficial effects that: under the condition of ensuring certain silicon-aluminum ratio, specific surface area, pore volume and the like, mordenite with different crystal grains can be rapidly and controllably prepared, the size of the crystal grains which are beneficial to preparing methyl acetate by carbonylation of dimethyl ether is selected, the diffusion resistance is reduced, and the carbon deposition of a catalyst is reduced. The catalyst is environment-friendly and pollution-free; the microwave reaction system is used in the catalyst preparation process, so that the nucleation time of the molecular sieve is greatly shortened, the particle size of the molecular sieve is reduced, and the synthesis of the nano-grade Mordenite (MOR) molecular sieve is promoted; the reaction system is simple and quick to operate, and the catalyst preparation time is saved.
Drawings
FIG. 1 is an XRD pattern of a nano-sized mordenite molecular sieve prepared in examples 1-5 of the present invention, wherein 1 is example 1, 2 is example 2, 3 is example 3, 4 is example 4, and 5 is example 5;
FIG. 2 is an XRD pattern of the nano-sized mordenite molecular sieves prepared in comparative examples 1-5 of the present invention, wherein 1 is comparative example 1, 2 is comparative example 2, 3 is comparative example 3, 4 is comparative example 4, and 5 is comparative example 5;
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
Weighing 24g of silica sol (the mass percent of silicon dioxide is 30 wt%), 0.656g of sodium metaaluminate and 1.28g of sodium hydroxide in a plastic beaker, uniformly mixing the materials, stirring the mixture at room temperature for 1 hour, fully and uniformly mixing the materials until the mixture becomes gel, and stirring and aging the gel for 4 hours.
Weighing 16g of tetraethylammonium hydroxide (the mass percent of the tetraethylammonium hydroxide is 25 wt%), 0.07g of seed crystal, adding the mixture into the gel, stirring and aging for 4 hours, then putting the gel into a microwave high-pressure reaction kettle, putting the gel into a microwave high-pressure reaction system, and carrying out microwave crystallization reaction under the conditions that the pressure is 6MPa and the reaction temperature is 170 ℃ for 5 hours.
After the first crystallization is carried out for 0.5h, the reaction kettle is taken out and rapidly cooled to room temperature (20-25 ℃), then the reaction kettle is placed into a microwave reaction system for second crystallization, the second crystallization time is 4.5h, the product is washed by deionized water until the PH is 6.5-7.5, then the product is dried for 8h under the condition of 120 ℃, and then the product is placed into a muffle furnace for roasting for 4h, the roasting temperature is 550 ℃, so as to remove the template agent in Na-MOR, and the Na-MOR molecular sieve is obtained.
And then placing the Na-MOR molecular sieve in a beaker, adding 0.5mol/L ammonium nitrate solution into the beaker, performing ammonia ion exchange for 6 hours at the temperature of 60 ℃, wherein the solid-to-liquid ratio of the Na-MOR molecular sieve to the ammonium nitrate solution is 1:10, repeating the ammonia ion exchange twice, drying for 8 hours at the temperature of 120 ℃, and then placing the dried product in a muffle furnace at the temperature of 500 ℃ for roasting for 3 hours to prepare the H-MOR molecular sieve.
Tabletting and sieving the prepared H-MOR molecular sieve, weighing 2mL of 40-60 mesh H-MOR, and putting the H-MOR into a fixed bed reactor, wherein N is firstly used2Carrying out in-situ pretreatment for 4h at 450 ℃ for reaction, wherein the feed gas ratio is DME/Ar/CO-1/2/47, and the gas space velocity is 3000h-1The activity was evaluated at a reaction temperature of 200 ℃ and a reaction pressure of 1.5 MPa.
Examples 2 to 5
Under the same conditions as those of example 1, the first crystallization time is changed to 1H (example 2), 1.5H (example 3), 2H (example 4) and 2.5H (example 5), the reaction kettle is taken out and rapidly cooled to room temperature (20-25 ℃) to perform second crystallization, and after the crystallization is finished, the template agent is removed, ammonia ion exchange is performed, drying and roasting are performed, so that the H-MOR molecular sieve is obtained.
TABLE 1 results of the reaction of microwave crystallization with different quenching times for the carbonylation of dimethyl ether with H-MOR to produce methyl acetate
The results show that, in the case of constant total crystallization time, quenching at different times makes it possible to obtain H-MOR having different crystal grain sizes, and that the smaller the crystal grain size, the more advantageous the catalyst activity is.
Examples 6 to 10
Under the same conditions as in example 5, the silica sol was changed to sodium silicate, water (example 6) and fumed silica were added (example 7), tetraethylammonium hydroxide was changed to tetraethylammonium bromide, water was added (example 8), sodium hydroxide was changed to potassium hydroxide (example 9), and the amount of seed crystal added was changed to 0.2g (example 10).
Examples 11 to 12
Under otherwise identical conditions as in example 10, 0.5g of ammonium nitrate (example 11) was added after the addition of the templating agent tetraethylammonium hydroxide, and the amount of sodium metaaluminate added was changed to 0.492g (example 12).
TABLE 2 influence of microwave crystallization source material on the reaction of H-MOR catalyzed carbonylation of dimethyl ether to produce methyl acetate
The results show that the optimum raw materials are sodium hydroxide, silica sol, sodium metaaluminate and tetraethyl ammonium hydroxide, the addition of seed crystals can reduce the grain size, improve the catalyst activity, and increase the silica-alumina ratio can reduce the grain size, but reduce the activity.
Examples 13 to 16
Under the same conditions as those of example 10, the total crystallization time was changed to 4 hours (example 13), the crystallization temperature was changed to 150 ℃ (example 14), the crystallization pressure was changed to 5MPa (example 15), and the aging time was changed to 24 hours (example 16).
TABLE 3 influence of microwave crystallization conditions on the reaction of H-MOR catalyzed carbonylation of dimethyl ether to produce methyl acetate
The results show that the optimal crystallization conditions are that the crystallization time is 5 hours, the crystallization temperature is 170 ℃, the crystallization pressure is 6MPa, and the crystal grain size can be reduced and the catalyst activity can be improved by prolonging the aging time.
Comparative example 1
Under the same conditions as those in example 16, the crystallization was carried out in a hydrothermal process instead of the microwave process, and the total crystallization time was 5 days.
Comparative examples 2 to 5
Under the same conditions as those of example 16, during the hydrothermal synthesis, the first crystallization time is 3H (comparative example 2), 6H (comparative example 3), 12H (comparative example 4) and 24H (comparative example 5), the reaction kettle is taken out and rapidly cooled to room temperature (20-25 ℃), the second crystallization is carried out, and after the crystallization is finished, the template agent is removed, ammonia ion exchange is carried out, drying and roasting are carried out, so that the H-MOR molecular sieve is obtained.
TABLE 4 reaction results of H-MOR catalyzed dimethyl ether carbonylation to produce methyl acetate by hydrothermal synthesis at different quenching times
The result shows that compared with microwave crystallization, the H-MOR crystal grain obtained by hydrothermal synthesis is larger, and the catalyst performance is poorer.
Example 17
Under the same conditions as those of the example 16, the H-MOR molecular sieve prepared in the example 16 is used for preparing a copper modified catalyst for dimethyl ether carbonylation by an exchange method. The preparation method of the copper modified catalyst comprises the following steps: weigh 0.76gCu (NO)3)2·3H2O is prepared into 100mL aqueous solution, 10g of the prepared H-MOR molecular sieve is added into the aqueous solution, the exchange is carried out for 2H at 80 ℃, after suction filtration, the drying is carried out for 24H at 110 ℃, and then the aqueous solution is roasted for 4H at 500 ℃ in a muffle furnace.
Example 18
Under the conditions which are otherwise identical to those of the example 16, the H-MOR molecular sieve prepared in the example 16 is used for preparing a copper modified catalyst by an impregnation method, and is used for dimethyl ether carbonylation reaction. The preparation method of the copper modified catalyst comprises the following steps: weigh 0.76gCu (NO)3)2·3H2O is prepared into 100mL ethanol solution, 10g of the prepared H-MOR molecular sieve is added into the solution, the solution is soaked for 4 hours at the temperature of 40 ℃, after suction filtration, the solution is dried for 24 hours at the temperature of 110 ℃, and then the solution is roasted for 4 hours in a muffle furnace at the temperature of 500 ℃.
Example 19
Under the same conditions as those of the example 16, the H-MOR molecular sieve prepared in the example 16 is used for preparing a copper modified catalyst by a cuprammonia method, and is used for dimethyl ether carbonylation reaction. The preparation method of the copper modified catalyst comprises the following steps: weigh 0.76gCu (NO)3)2·3H2O is prepared into 100mL of copper ammonia solution, the pH value of the copper ammonia solution is adjusted to be 11, 10g of the prepared H-MOR molecular sieve is added into the solution, then a small amount of ammonia water is added into the solution, the pH value of the liquid is adjusted to be 11, the solution is kept at 40 ℃ for 2 hours, after suction filtration, the solution is dried at 110 ℃ for 24 hours, and then the solution is placed in a 500 ℃ muffle furnace for roasting for 4 hours.
Example 20
Under the same conditions as those of the example 16, the H-MOR molecular sieve prepared in the example 16 is used for preparing a copper modified catalyst for dimethyl ether carbonylation by adopting an ammonia evaporation method. The preparation method of the copper modified catalyst comprises the following steps: taking Cu (NO)3)2·3H2O0.76 g of copper ammonia solution 100mL is prepared, pH is adjusted to about 11, and thenAdding 10g of the prepared H-MOR molecular sieve, adding a small amount of ammonia water, adjusting the pH of the liquid to 11, keeping the liquid at 40 ℃ for 3H, heating to 80 ℃ for ammonia evaporation for 2H, performing suction filtration, drying at 110 ℃ for 24H, and then roasting in a muffle furnace at 500 ℃ for 4H.
TABLE 5 results of the H-MOR catalyzed carbonylation of dimethyl ether to methyl acetate by different copper-supported processes
| Catalyst sample | DME conversion (%) | MA selectivity (%) | MA space time yield (mg/L.h) |
| Example 17 | 80 | 99 | 276 |
| Example 18 | 79 | 99 | 273 |
| Example 19 | 88 | 99 | 304 |
| Example 20 | 83 | 99 | 287 |
The results show that the copper-loaded H-MOR increases the active sites of the dimethyl ether carbonylation reaction and improves the catalyst activity. Meanwhile, the Cu/H-MOR activity obtained by the cuprammonium method is optimal.
Example 21
Under the same conditions as those in example 17, the metal precursor copper nitrate was changed to silver nitrate and used for the carbonylation of dimethyl ether. The preparation method comprises the following steps: weighing 1.40g AgNO3Preparing 100mL of aqueous solution, adding 10g of the prepared H-MOR molecular sieve into the aqueous solution under a dark environment, exchanging for 2H at room temperature, filtering, drying for 24H at 110 ℃, and then roasting for 4H in a muffle furnace at 500 ℃.
Example 22
17 under the same condition, the metal precursor copper nitrate is changed into cobalt nitrate for dimethyl ether carbonylation reaction. The preparation method comprises the following steps: weighing 1.18Co (NO)3)2·6H2O is prepared into 100mL aqueous solution, 10g of the prepared H-MOR molecular sieve is added into the solution for exchange for 2H at room temperature, after suction filtration, the solution is dried for 24H at 110 ℃, and then the solution is roasted for 4H in a muffle furnace at 500 ℃.
| Catalyst sample | DME conversion (%) | MA selectivity (%) | MA space-time yield (mg/L. h) |
| Example 21 | 80 | 99 | 275 |
| Example 22 | 81 | 99 | 279 |
The mass content of all metal components is 0.5-10%, preferably 2-5%.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The preparation method of the mordenite molecular sieve catalyst is characterized by comprising the following steps: the method comprises the following steps:
step 1, adding water into a silicon source, an aluminum source and an alkali source, stirring and aging to form sol;
wherein the silicon source is silica sol, sodium silicate, silicon dioxide or ethyl orthosilicate, the aluminum source is sodium metaaluminate or aluminum oxide, the molar ratio of Si to Al in the silicon source and the aluminum source is (5-25):1, the alkali source is sodium hydroxide or ammonia water, and OH in the alkali source and the aluminum source-The molar ratio of Al to Al is (2-8): 1, the molar ratio of water to Si in the silicon source is (0-10):1 and does not include 0:1 and 10: 1;
mechanical stirring or magnetic stirring is adopted for stirring, and the stirring and aging time is 1-24 h;
step 2, adding a template agent, cations and seed crystals into the sol prepared in the step 1, and stirring and aging;
wherein the template agent is tetraethylammonium hydroxide or tetraethylammonium bromide, and the molar ratio of the template agent to Si in the silicon source is (0.1-0.4): 1, the cation is ammonium nitrate or ammonium chloride, and the mole ratio of the cation to Si in the silicon source is (0.03-0.1): 1, the adding amount of the seed crystal is 1-10 wt% of the mass of the silicon source;
in the step 2, mechanical stirring or magnetic stirring is adopted for stirring, and the aging time is more than zero and less than or equal to 24 hours, preferably 4-24 hours;
step 3, adding the sample prepared in the step 2 into a high-pressure reaction kettle, sealing and then placing the sample into a microwave high-pressure reaction system for primary crystallization, taking out the high-pressure reaction kettle after 0.1-3h of primary crystallization, quickly cooling the high-pressure reaction kettle to room temperature of 20-25 ℃, then placing the high-pressure reaction kettle into the microwave high-pressure reaction system again for secondary crystallization, so that the total crystallization time is 1-9h, taking out the product in the high-pressure reaction kettle after the secondary crystallization is finished, washing the product with water until the pH value is 6.5-7.5, and drying and roasting the product to obtain the Na-MOR molecular sieve;
wherein the drying temperature is 100-;
step 4, uniformly dispersing the Na-MOR molecular sieve prepared in the step 3 in ammonium nitrate or ammonium chloride liquid for ammonia exchange, and drying and roasting after 2-3 times of ammonia exchange to obtain the H-MOR molecular sieve;
wherein the concentration of the ammonium nitrate solution or the ammonium chloride solution is 0.1-1mol/L, and the ammonia exchange conditions are as follows: the exchange time is 5-7h, the exchange temperature is 50-70 ℃, and the solid-to-liquid ratio of the Na-MOR molecular sieve to the ammonium nitrate solution or the ammonium chloride solution is 1: (8-12);
wherein the drying temperature is 100-150 ℃, the drying time is 5-10h, the roasting temperature is 400-600 ℃, and the roasting time is 1-5 h.
2. A process for the preparation of a mordenite molecular sieve catalyst as claimed in claim 1, characterized in that: in the step 1, OH in the alkali source and the aluminum source-The molar ratio of Al to Al is (3-6): 1.
3. a process for the preparation of a mordenite molecular sieve catalyst as claimed in claim 1, characterized in that: in the step 2, the molar ratio of the cation to Si in the silicon source is (0.05-0.09): 1.
4. a process for the preparation of a mordenite molecular sieve catalyst as claimed in claim 1, characterized in that: in the step 3, the reaction conditions of the microwave high-pressure reaction system are as follows: the crystallization temperature is 150-.
5. A process for the preparation of a mordenite molecular sieve catalyst as claimed in claim 1, characterized in that: in the step 3, the reaction conditions of the microwave high-pressure reaction system are as follows: the crystallization temperature is 150-.
6. A process for the preparation of a mordenite molecular sieve catalyst as claimed in claim 1, characterized in that: in the step 4, the concentration of the ammonium nitrate solution or the ammonium chloride solution is 0.4-0.6mol/L, and in the step 4, the ammonia exchange conditions are as follows: the exchange time is 5.5-6.5h, the exchange temperature is 55-65 ℃, and the solid-to-liquid ratio of the Na-MOR molecular sieve to the ammonium nitrate solution or the ammonium chloride solution is 1: (9-11).
7. A process for the preparation of a mordenite molecular sieve catalyst as claimed in claim 1, characterized in that: and (3) loading a single-activity metal or double-activity metal component of the H-MOR molecular sieve prepared in the step (4) onto the H-MOR molecular sieve by adopting an ion exchange method, an impregnation method, an ammonia evaporation method or a solid ion exchange method, wherein the single-activity metal is any one of copper, silver, iron, cobalt or nickel, and the double-activity metal component is any two of copper, silver, iron, cobalt or nickel.
8. A mordenite molecular sieve catalyst prepared by a method of preparing a mordenite molecular sieve catalyst as claimed in any of claims 1 to 7.
9. Use of a mordenite molecular sieve catalyst as claimed in claim 8 in the carbonylation of methyl acetate.
10. The use of a mordenite molecular sieve catalyst as claimed in claim 9 in the carbonylation synthesis of methyl acetate, wherein: reaction conditions are as follows: the feeding molar ratio of the raw materials is n (CH)3OCH3) N (CO) =1 (5-60), the reaction temperature is 180--1。
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| CN111792994B (en) * | 2019-04-09 | 2021-09-28 | 中国科学院大连化学物理研究所 | Method for producing methyl acetate by dimethyl ether carbonylation |
| CN111977665A (en) * | 2019-05-22 | 2020-11-24 | 中国科学院大连化学物理研究所 | Preparation method of mordenite molecular sieve |
| CN112645349B (en) * | 2020-12-28 | 2023-10-20 | 延长中科（大连）能源科技股份有限公司 | Preparation method and application of mordenite molecular sieve |
| CN112844452B (en) * | 2021-02-23 | 2023-03-14 | 北京弗莱明科技有限公司 | Modified molecular sieve, preparation method thereof, catalyst for preparing methyl acetate by carbonylation of dimethyl ether and method |
| CN113694960B (en) * | 2021-08-20 | 2023-05-30 | 常州工学院 | ZrCu-MOR zeolite for synthesizing 5-ethoxymethyl furfural and preparation method thereof |
| CN113731474B (en) * | 2021-09-02 | 2022-11-18 | 湖北大学 | Preparation method and catalytic application of multifunctional hybrid zeolite molecular sieve |
| CN115536040B (en) * | 2022-09-27 | 2023-08-15 | 厦门大学 | Nano lotus leaf-shaped aluminum-rich mordenite molecular sieve, and synthetic method and application thereof |
| CN115463685B (en) * | 2022-10-27 | 2023-01-31 | 淄博恒亿化工科技有限公司 | Preparation method and application of composite molecular sieve catalyst for synthesizing nitroaromatic compound |
| CN116477638A (en) * | 2023-03-23 | 2023-07-25 | 延长中科（大连）能源科技股份有限公司 | Preparation method and application of high-stability mordenite molecular sieve |
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| EP2251082A1 (en) * | 2009-05-14 | 2010-11-17 | BP Chemicals Limited | Carbonylation catalyst and process |
| CN103170360B (en) * | 2011-12-23 | 2015-03-25 | 中国科学院大连化学物理研究所 | Dimethyl ether carbonylation catalyst, and preparation method and application thereof |
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