CN112705264A - Catalyst for producing methyl methoxyacetate through carbonylation of formaldehyde and preparation method and application thereof - Google Patents
Catalyst for producing methyl methoxyacetate through carbonylation of formaldehyde and preparation method and application thereof Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0215—Sulfur-containing compounds
- B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
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- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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Abstract
The invention discloses a catalyst for producing methyl methoxyacetate by carbonylation of formaldehyde, a preparation method and application thereof. The catalyst takes ion exchange resin as a carrier, and organic sulfonic acid containing benzene rings is immobilized on the carrier by an isometric impregnation method. The catalyst is used for producing methyl methoxyacetate, trioxymethylene or paraformaldehyde is used as a source of a formaldehyde monomer, formaldehyde and carbon monoxide are used as raw materials, and the methyl methoxyacetate is produced intermittently at the reaction temperature of 70-120 ℃ and the reaction pressure of 2-8 MPa.
Description
Technical Field
The invention relates to the field of catalysts, and relates to a catalyst for producing methyl methoxyacetate through carbonylation of formaldehyde, and a preparation method and application thereof.
Background
Methyl methoxyacetate is a valuable intermediate, can be used for the kinetic resolution of chiral amine compounds, the synthesis of vitamin B6, sulfanilamide-5-pyrimidine and the like, can be used as a catalyst for polymerization, can also be hydrogenated and hydrolyzed to prepare ethylene glycol, and is an important ethylene glycol precursor.
The synthesis method of methyl methoxyacetate mainly comprises the following steps: carbonylation: dimethoxymethane is taken as a raw material, carbon monoxide, formic acid, methyl formate and the like are taken as carbonyl sources, and methyl methoxyacetate is prepared through carbonylation reaction; substitution method: taking sodium methoxide and chloroacetic acid as raw materials, firstly synthesizing methoxyacetic acid, and then synthesizing methoxyacetic acid methyl ester through esterification reaction with methanol; (iii) oxidation: the method comprises the steps of oxidizing ethylene glycol monomethyl ether serving as a raw material to obtain methoxy acetic acid, and esterifying to obtain methyl methoxy acetate. The substitution method and the oxidation method are generally used for small-amount synthesis in a laboratory, and the carbonylation method can be used for industrially and independently synthesizing methyl methoxyacetate and can also be used as an intermediate process for synthesizing ethylene glycol by the carbonylation method, so that the method is the route with the most development potential.
The current carbonylation technology has two main routes: homogeneous catalysis and heterogeneous catalysis. The traditional homogeneous phase method mainly adopts inorganic liquid acid as a catalyst, such as concentrated sulfuric acid, hydrofluoric acid, fluorosulfonic acid and the like. DuPont, USP2152852 and USP2285448 disclose the use of sulfuric acid as a catalyst to catalyze the carbonylation of formaldehyde and CO for the commercial production of ethylene glycol at 200 ℃ and 90MPa, with a production outage of 1968. Chevron in USP3911003 discloses the carbonylation of formaldehyde with HF as catalyst at 22-50 deg.C and 6.89-13.78 MPa. Because the inorganic acid has strong corrosivity and serious pollution, the production is stopped after the production is put into operation for a long time. Patent CN201210205619.7, EP19820305617 show that methyl methoxyacetate is produced by catalyzing carbonylation of methylal under liquid condition by using strong acid, and the problems of difficult separation of products, corrosion of a device by liquid acid and the like exist.
In order to solve the above problems, development of a solid acid which has strong acidity, low corrosiveness and is easily activated, instead of an inorganic acid, has been a new research direction, and thus solid acids such as heteropolyacids, ion exchange resins and molecular sieves have been further developed and used as catalysts for carbonylation reactions. CN103172517A of the institute of chemical and physical university of Chinese academy of sciences discloses a method for synthesizing methyl methoxyacetate by using heteropolyacid as a catalyst, wherein the yield of methyl methoxyacetate in the carbonylation reaction can reach 47%. The carbonylation of formaldehyde follows a Koch reaction mechanism, namely a Bronsted acid catalyzed reaction, and as a classical Bronsted acid catalyst, resin catalysts such as Amberlyst-15, Amberlyst-38, Nafion NR-50 and the like have excellent catalytic carbonylation performance of formaldehyde. In the heterogeneous catalysis formaldehyde carbonylation reaction, the sulfonic acid resin catalyst has the most excellent catalytic performance, however, in an aqueous system, the resin catalyst is easy to swell and run off.
Disclosure of Invention
In order to solve the problems, the development of a more stable catalyst or the optimized process conditions is a problem to be solved when the solid acid is applied to catalyzing the carbonylation reaction of formaldehyde.
The first aspect of the invention provides a catalyst for producing methyl methoxyacetate by carbonylation of formaldehyde, which comprises a carrier and organic sulfonic acid containing benzene rings, wherein the organic sulfonic acid is fixedly supported on the carrier.
According to the catalyst, the organic sulfonic acid containing benzene rings as an active component is immobilized on the carrier, so that the action interfacial area of active acid sites can be increased, the loss of the active component is avoided, and the organic sulfonic acid can be recovered through simple operations such as filtration and the like after the reaction is finished.
According to some embodiments of the invention, the support is an ion exchange resin.
According to some embodiments of the invention, the support is selected from at least one of Amberlyst-15, Amberlyst-25, Amberlyst-35, Amberlyst-36, Amberlite IR 120, Purolite CT 251, Purolite CT 275, Purolite CT 482.
According to some embodiments of the invention, the organic sulfonic acid containing a benzene ring is selected from one or more of p-toluenesulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid.
According to some embodiments of the invention, the organic sulfonic acid containing benzene rings is supported at a ratio of 10% to 60% by weight of the catalyst.
According to some embodiments of the invention, the organic sulfonic acid containing benzene rings is supported at a ratio of 20% to 50% by weight of the catalyst.
According to some embodiments of the invention, the organic sulfonic acid containing benzene rings is supported at a weight ratio of 25% to 40% of the catalyst.
A second aspect of the present invention provides a method for preparing the catalyst of the first aspect, comprising the steps of:
s1, mixing the carrier with an impregnation liquid to obtain the carrier impregnated with the organic sulfonic acid containing benzene rings, wherein the impregnation liquid is a solution containing the organic sulfonic acid containing benzene rings and alcohol;
s2, drying and heat treating the carrier impregnated with organic sulfonic acid containing benzene ring obtained in the step S1 to obtain the catalyst.
The preparation method of the invention effectively reduces the dosage of the organic sulfonic acid containing benzene rings, and the dispersion is more uniform.
According to some embodiments of the invention, the volume of the impregnation fluid is equal to the pore volume of the support.
According to some embodiments of the invention, the support is mixed with the impregnation solution and allowed to stand at 20-100 ℃ for 2-24 hours.
According to some embodiments of the invention, the benzene ring-containing organic sulfonic acid concentration in the alcohol solution of benzene ring-containing organic sulfonic acid is 30% to 60%.
According to some embodiments of the invention, the drying is performed at 100-120 ℃.
According to some embodiments of the invention, the heat treatment is calcination.
According to some embodiments of the present invention, the calcination is performed at 200-400 ℃ for 2-5 h.
According to some embodiments of the invention, the alcohol solution is one or more selected from the group consisting of methanol, ethanol, n-propanol, and isopropanol.
According to some embodiments of the present invention, the S1 step and the S2 step are repeated one or more times.
A third aspect of the present invention provides a process for producing methyl methoxyacetate, comprising contact-reacting a formaldehyde monomer source, carbon monoxide and a mixed solvent with the catalyst of the first aspect or the catalyst prepared by the process of the second aspect; after the reaction, methanol was added to conduct esterification.
According to some embodiments of the invention, the formaldehyde monomer source material is trioxane or paraformaldehyde.
According to some embodiments of the invention, the mixed solvent is a mixture of an organic solvent and an organic acid.
According to some embodiments of the invention, the organic solvent is selected from at least one of sulfolane, toluene, dioxolane, 1, 4-dioxane.
According to some embodiments of the invention, the organic acid comprises at least one of acetic acid and propionic acid.
According to some embodiments of the invention, the molar ratio of the organic acid to the organic solvent is from 1:01 to 10: 1.
According to some embodiments of the invention, the temperature of the reaction is 70-120 ℃.
According to some embodiments of the invention, the pressure of the reaction is 2 to 8 MPa.
A fourth aspect of the invention provides the use of a catalyst according to the first aspect or prepared by the process of the second aspect in the production of methyl methoxyacetate.
The calculation method of the methyl methoxyacetate comprises the following steps:
yield (%) of methyl methoxyacetate, (% by mole) of methyl methoxyacetate/mole of formaldehyde as a raw material × 100%.
The invention has the beneficial effects that:
the catalyst is used for synthesizing methyl methoxyacetate, and the yield of methyl methoxyacetate is obviously improved and approaches to 85%. The catalyst of the invention has the characteristics of high product yield, no corrosion to reaction equipment, easy separation and recovery of the catalyst and the like.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.
[ example 1 ]
1. Catalyst preparation
Preparing a p-toluenesulfonic acid-ethanol solution as an impregnation solution, taking ion exchange resin Amberlyst-36 (Dow) as a carrier, controlling the volume of the impregnation solution to be the same as the pore volume of the carrier, controlling the concentration of the impregnation solution to enable the final solid catalyst to contain active component p-toluenesulfonic acid with the mass fraction of 40%, mixing the carrier and the impregnation solution, standing for 12 hours after uniform mixing to obtain the carrier impregnated with the organic sulfonic acid as a sample, drying the sample at 100 ℃, and roasting for 3 hours at 210 ℃ to obtain the catalyst for producing methyl methoxyacetate.
The catalyst formulation is shown in table 1.
2. Synthesis of methyl methoxyacetate
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of the catalyst, putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
Comparative example 1
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of p-toluenesulfonic acid, filling the p-toluenesulfonic acid into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
Comparative example 2
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of ion exchange resin Amberlyst-36 (Dow) and putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3h at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
Comparative example 3
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of ion exchange resin Amberlite IR 120(Rohm & Haas company), putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting at 90 ℃ for 3 h. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
[ example 2 ]
1. Catalyst preparation
Preparing a p-toluenesulfonic acid-ethanol solution as an impregnation solution, taking ion exchange resin Amberlyst-36 (Dow) as a carrier, controlling the volume of the impregnation solution to be the same as the pore volume of the carrier, controlling the concentration of the impregnation solution to enable the final solid catalyst to contain 25% by mass of active component p-toluenesulfonic acid, mixing the carrier and the impregnation solution, uniformly mixing, standing for 12h to obtain a carrier impregnated with the organic sulfonic acid as a sample, drying the sample at 100 ℃, and roasting at 210 ℃ for 3h to obtain the catalyst for producing methyl methoxyacetate.
The catalyst formulation is shown in table 1.
2. Synthesis of methyl methoxyacetate
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of the catalyst, putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
[ example 3 ]
1. Catalyst preparation
Preparing a p-toluenesulfonic acid-ethanol solution as an impregnation solution, taking ion exchange resin Amberlyst-36 (Dow) as a carrier, controlling the volume of the impregnation solution to be the same as the pore volume of the carrier, controlling the concentration of the impregnation solution to enable the final solid catalyst to contain active component p-toluenesulfonic acid with the mass fraction of 40%, mixing the carrier and the impregnation solution, standing for 12 hours after uniform mixing to obtain the carrier impregnated with the organic sulfonic acid as a sample, drying the sample at 100 ℃, and roasting for 3 hours at 210 ℃ to obtain the catalyst for producing methyl methoxyacetate.
The catalyst formulation is shown in table 1.
2. Synthesis of methyl methoxyacetate
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, toluene: 20mL of a 1:1 mixed solvent. Weighing 2g of the catalyst, putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
[ example 4 ]
1. Catalyst preparation
Preparing a p-toluenesulfonic acid-ethanol solution as an impregnation solution, taking ion exchange resin Amberlyst-36 (Dow) as a carrier, controlling the volume of the impregnation solution to be the same as the pore volume of the carrier, controlling the concentration of the impregnation solution to enable the final solid catalyst to contain active component p-toluenesulfonic acid with the mass fraction of 40%, mixing the carrier and the impregnation solution, standing for 12 hours after uniform mixing to obtain the carrier impregnated with the organic sulfonic acid as a sample, drying the sample at 100 ℃, and roasting for 3 hours at 210 ℃ to obtain the catalyst for producing methyl methoxyacetate.
The catalyst formulation is shown in table 1.
2. Synthesis of methyl methoxyacetate
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 2:1 propionic acid mixed solvent. Weighing 2g of the catalyst, putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
[ example 5 ]
1. Catalyst preparation
Preparing a p-toluenesulfonic acid-ethanol solution as an impregnation solution, taking ion exchange resin Purolite CT 251(Purolite company) as a carrier, controlling the concentration of the impregnation solution to ensure that the final solid catalyst contains 40% by mass of active component p-toluenesulfonic acid, mixing the carrier and the impregnation solution, uniformly mixing, standing for 12h to obtain a carrier impregnated with the organic sulfonic acid as a sample, drying the sample at 100 ℃, and roasting at 210 ℃ for 3h to obtain the catalyst for producing methyl methoxyacetate.
The catalyst formulation is shown in table 1.
2. Synthesis of methyl methoxyacetate
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of the catalyst, putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
[ example 6 ]
1. Catalyst preparation
Preparing a p-toluenesulfonic acid-ethanol solution as an impregnation solution, taking ion exchange resin Amberlite IR 120(Rohm & Hass company) as a carrier, controlling the concentration of the impregnation solution to enable the final solid catalyst to contain 40% of active component p-toluenesulfonic acid by mass fraction, mixing the carrier with the impregnation solution, uniformly mixing, standing for 12h to obtain a carrier impregnated with the organic sulfonic acid as a sample, drying the sample at 100 ℃, and roasting at 210 ℃ for 3h to obtain the catalyst for producing methyl methoxyacetate.
The catalyst formulation is shown in table 1.
2. Synthesis of methyl methoxyacetate
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of the catalyst, putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
[ example 7 ]
1. Catalyst preparation
Preparing a dodecylbenzene sulfonic acid-ethanol solution as an impregnation solution, taking ion exchange resin Amberlyst-15 (Dow) as a carrier, controlling the volume of the impregnation solution to be the same as the pore volume of the carrier, controlling the concentration of the impregnation solution to ensure that the final solid catalyst contains 30 mass percent of dodecylbenzene sulfonic acid as an active component, mixing the carrier and the impregnation solution, standing for 12 hours after uniform mixing to obtain the carrier impregnated with the organic sulfonic acid as a sample, drying the sample at 100 ℃, and roasting for 3 hours at 210 ℃ to obtain the catalyst for producing methyl methoxyacetate.
The catalyst formulation is shown in table 1.
2. Synthesis of methyl methoxyacetate
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of the catalyst, putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
[ example 8 ]
1. Catalyst preparation
Preparing a dodecylbenzene sulfonic acid-ethanol solution as an impregnation solution, taking ion exchange resin Amberlyst-36 (Dow) as a carrier, controlling the volume of the impregnation solution to be the same as the pore volume of the carrier, controlling the concentration of the impregnation solution to ensure that the final solid catalyst contains 30 mass percent of dodecylbenzene sulfonic acid as an active component, mixing the carrier and the impregnation solution, standing for 12 hours after uniform mixing to obtain the carrier impregnated with the organic sulfonic acid as a sample, drying the sample at 100 ℃, and roasting for 3 hours at 210 ℃ to obtain the catalyst for producing methyl methoxyacetate.
The catalyst formulation is shown in table 1.
2. Synthesis of methyl methoxyacetate
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of the catalyst, putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
[ example 9 ]
1. Catalyst preparation
Preparing a benzenesulfonic acid-ethanol solution as an impregnation solution, taking an ion exchange resin Amberlite IR 120(Rohm & Hass company) as a carrier, controlling the concentration of the impregnation solution to ensure that the final solid catalyst contains 40% by mass of benzenesulfonic acid, mixing the carrier and the impregnation solution, uniformly mixing, standing for 12h to obtain a carrier impregnated with the organic sulfonic acid as a sample, drying the sample at 100 ℃, and roasting at 210 ℃ for 3h to obtain the catalyst for producing methyl methoxyacetate.
The catalyst formulation is shown in table 1.
2. Synthesis of methyl methoxyacetate
In a stainless steel autoclave having a volume of 100mL, 1.4g of paraformaldehyde, sulfolane: 20mL of a 1:1 mixed solvent. Weighing 2g of the catalyst, putting into a kettle, sealing the reaction kettle, replacing air in the kettle with CO for 2 times, introducing high-pressure CO to 6MPa, and reacting for 3 hours at 90 ℃. After the reaction is finished, cooling the reaction kettle to room temperature, adding 50mL of methanol, sealing the reaction kettle, reacting at 80 ℃ for 2h, cooling the reaction kettle to room temperature after the reaction is finished, taking out the feed liquid in the reaction kettle, and analyzing by high performance liquid chromatography to obtain the yield of the methyl methoxyacetate shown in Table 1.
TABLE 1 catalyst formulation and product yield
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst for preparing methyl methoxyacetate by carbonylating formaldehyde comprises a carrier and organic sulfonic acid containing benzene rings, wherein the organic sulfonic acid is immobilized on the carrier.
2. The catalyst of claim 1, wherein the support is an ion exchange resin; preferably, at least one selected from Amberlyst-15, Amberlyst-25, Amberlyst-35, Amberlyst-36, Amberlite IR 120, Purolite CT 251, Purolite CT 275, Purolite CT 482.
3. The catalyst according to claim 1 or 2, wherein the organic sulfonic acid containing benzene ring is selected from one or more of p-methyl benzene sulfonic acid, dodecyl benzene sulfonic acid and benzene sulfonic acid.
4. A catalyst according to any one of claims 1 to 3, characterized in that the organic sulfonic acid containing benzene rings is supported in an amount of 10% to 60%, preferably 20% to 50%, and more preferably 25% to 40% by weight of the catalyst.
5. A process for preparing a catalyst according to any one of claims 1 to 4, comprising the steps of:
s1, mixing the carrier with an impregnation liquid to obtain the carrier impregnated with the organic sulfonic acid containing benzene rings, wherein the impregnation liquid is a solution containing the organic sulfonic acid containing benzene rings and alcohol;
s2, drying and heat treating the carrier which is impregnated with the organic sulfonic acid containing the benzene ring and is obtained in the step S1 to obtain the catalyst;
preferably, the volume of the impregnation fluid is equal to the pore volume of the support;
preferably, the carrier and the impregnation liquid are mixed and then are kept stand for 2 to 24 hours at the temperature of between 20 and 100 ℃;
preferably, the concentration of the organic sulfonic acid containing benzene rings in the solution containing the organic sulfonic acid containing benzene rings and alcohol is 30-60% by weight/volume ratio;
preferably, the drying is carried out at 100-;
preferably, the heat treatment is roasting, and the roasting condition is preferably roasting at 200-400 ℃ for 2-5 h.
6. The method according to claim 5, wherein the alcohol solution is one or more selected from the group consisting of methanol, ethanol, n-propanol and isopropanol.
7. A process for producing methyl methoxyacetate, comprising contacting a formaldehyde monomer source, carbon monoxide and a mixed solvent with the catalyst according to any one of claims 1 to 4 or the catalyst prepared by the process according to claim 5 or 6; after the reaction, methanol was added to conduct esterification.
8. The method according to claim 7, wherein the formaldehyde monomer source material is trioxymethylene or paraformaldehyde, and/or the mixed solvent is a mixture of an organic solvent and an organic acid;
further preferably, the organic solvent is selected from at least one of sulfolane, toluene, dioxolane, 1, 4-dioxane, and/or the organic acid comprises at least one of acetic acid and propionic acid; and/or the molar ratio of the organic acid to the organic solvent is 1:10-10: 1.
9. The process according to claim 7 or 8, characterized in that the temperature of the reaction is 70-120 ℃ and/or the pressure of the reaction is 2-8 MPa.
10. Use of a catalyst according to any one of claims 1 to 4 or prepared according to the process of claim 5 or 6 in the production of methyl methoxyacetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911024554.4A CN112705264A (en) | 2019-10-25 | 2019-10-25 | Catalyst for producing methyl methoxyacetate through carbonylation of formaldehyde and preparation method and application thereof |
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Citations (7)
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| US4501917A (en) * | 1981-08-07 | 1985-02-26 | Hoechst Aktiengesellschaft | Process for carbonylating formaldehyde acetals |
| CN102690199A (en) * | 2012-05-29 | 2012-09-26 | 中国科学院新疆理化技术研究所 | Preparation method for methyl methoxyacetate |
| CN103506171A (en) * | 2012-06-15 | 2014-01-15 | 华东理工大学 | Modified acidic cation exchange resin and applications thereof |
| CN103896775A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for direct production of methyl methoxyacetate via gas-phase carbonylation of methyl aldehyde with methyl alcohol |
| CN103894228A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Catalyst used for producing methyl methoxyacetate, and preparation method thereof |
| CN106582833A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Methyl methoxyacetate catalyst |
| CN107501091A (en) * | 2017-07-20 | 2017-12-22 | 沈阳化工大学 | A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate |
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2019
- 2019-10-25 CN CN201911024554.4A patent/CN112705264A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4501917A (en) * | 1981-08-07 | 1985-02-26 | Hoechst Aktiengesellschaft | Process for carbonylating formaldehyde acetals |
| CN102690199A (en) * | 2012-05-29 | 2012-09-26 | 中国科学院新疆理化技术研究所 | Preparation method for methyl methoxyacetate |
| CN103506171A (en) * | 2012-06-15 | 2014-01-15 | 华东理工大学 | Modified acidic cation exchange resin and applications thereof |
| CN103896775A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Method used for direct production of methyl methoxyacetate via gas-phase carbonylation of methyl aldehyde with methyl alcohol |
| CN103894228A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Catalyst used for producing methyl methoxyacetate, and preparation method thereof |
| CN106582833A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Methyl methoxyacetate catalyst |
| CN107501091A (en) * | 2017-07-20 | 2017-12-22 | 沈阳化工大学 | A kind of method of catalyst preparation methyl glycollate and by-product methoxy menthyl acetate |
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