CN110746301B - Method for synthesizing methyl glycolate by hydrogenating dimethyl oxalate - Google Patents
Method for synthesizing methyl glycolate by hydrogenating dimethyl oxalate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
Disclosed is a method for synthesizing methyl glycolate by hydrogenating dimethyl oxalate, wherein the reaction catalyst used by the method comprises a titanium silicalite molecular sieve carrier and silver and/or copper atoms supported on the carrier, and the silver and/or copper atoms account for 1-40% of the total weight of the catalyst.
Description
Technical Field
The invention relates to a method for synthesizing methyl glycolate by hydrogenating dimethyl oxalate. The method can avoid the problem of carrier loss of the existing catalyst, is beneficial to the long-term stable operation of the catalyst, simultaneously obtains a methyl glycolate product with higher purity, and reduces the cost of product purification.
Background
Glycolic acid methyl ester (HOCH) 2 COOCH 3 MG) is an important chemical product and intermediate, and is widely used in many fields such as chemical industry, medicine, pesticide, feed, dye and spice. The application mainly comprises the following steps: 1) as excellent solvents for fibers, resins and rubbers; 2) further hydrogenation reduction is carried out to prepare ethylene glycol; 3) carbonylation to prepare methyl malonate; 4) ammonolysis to prepare glycine; 5) oxidative dehydrogenation is carried out to prepare methyl glyoxylate; 6) glycolic acid by hydrolysis, and the like. Among these, the potential market for glycolic acid is of particular importance.
At present, a carbonylation route or a reaction route of formaldehyde and hydrocyanic acid which is mainly adopted for synthesizing the glycollic acid takes formaldehyde as a raw material, the requirements on corrosion resistance and high pressure resistance of equipment are high, the one-time investment is large, and the large-scale production is difficult; the process route of mixing, reacting and re-esterifying chloroacetic acid and caustic soda solution is still used for producing glycolic acid in China, acetic acid is used as a raw material for producing chloroacetic acid, sulfur is used as a catalyst, and a chlorine method is used for producing chloroacetic acid. Therefore, the development of an environmentally friendly synthetic route is urgently needed.
With the increasing shortage of petroleum resources, the development of C1 chemical industry using natural gas or coal as raw materials has more and more important practical significance. The production of dimethyl oxalate (DMO) by synthesis gas and the subsequent hydrogenation of DMO to methyl glycolate is an important route to C1 chemical industry.
The preparation of methyl glycolate by a dimethyl oxalate hydrogenation route is currently focused on the development of high performance catalysts. Compared with other routes, the route has the advantages that the hydrogenation raw material can be prepared by using the synthesis gas of the C1 route, the route for generating methyl glycolate through fixed bed gas phase hydrogenation is easy to realize continuous production, and the ethylene glycol as a byproduct of hydrogenation is also a bulk chemical with higher added value. Thus, during catalyst development, there is a need to further reduce the formation of other non-ethylene glycol by-products while increasing the selectivity to methyl glycolate.
Japanese patent JP 06135895 reports the preparation of methyl glycolate by hydrogenation of dimethyl oxalate with Cu-Ag/SiO 2 The catalyst is prepared by a cuprammonium complexing ammonia distillation method, and the yield of the methyl glycolate is lower than 70 percent; chinese patent CN101138730A also describes the study of this reaction, using modified silica impregnated supported copper silver catalyst, with catalytic performance comparable to the results reported in japanese patent.
The US patent US4409395A adopts silver or palladium loaded on silicon oxide as a catalyst for preparing glycolate through oxalate hydrogenation, the catalyst has higher hydrogenation activity, but the selectivity of glycolate is still to be improved, and the generation of by-products is reduced by further optimizing the catalyst preparation, so that the economy of future application is improved; meanwhile, compared with copper as an active component, the catalyst with silver as an active component is easier to sinter in the reaction process, so that the catalyst is easy to deactivate. For this reason, it is generally necessary to introduce other promoters to improve the stability of the silica-supported silver catalyst.
Chinese CN101816934A discloses a method for synthesizing methyl glycolate and ethylene glycol by hydrogenation of dimethyl oxalate with silver-silica catalyst prepared by sol-gel method and adding polyvinylpyrrolidone as protecting agent and structure directing agent.
Chinese patent CN 102336666a discloses a method for preparing a supported silver catalyst for preparing methyl glycolate and ethylene glycol by hydrogenation of dimethyl oxalate with mesoporous silica as a carrier.
Chinese patent CN 102091650a discloses a microporous molecular sieve promoted oxalate copper-silicon hydrogenation catalyst for synthesizing ethylene glycol by hydrogenating oxalate and a preparation method thereof, for example, related X-type, Y-type, mordenite, ZSM series or beta series molecular sieves are all silica-alumina molecular sieves.
Li Xiangxiang et al, the theoretical research on the reaction mechanism of preparing methyl glycolate by hydrogenating dimethyl oxalate with silver and copper catalysts (chemical engineering of Natural gas-C1, volume 43 in 2018) researched the reaction mechanism of preparing methyl glycolate by hydrogenating dimethyl oxalate with dimethyl oxalate, and it is considered that the reaction process is likely that one end of dimethyl oxalate is firstly dissociated into methoxy and acyloxy, the former is easily hydrogenated into methanol, and the latter is gradually hydrogenated into methyl glycolate.
Chinese patent CN101954288A discloses a catalyst for preparing methyl glycolate by hydrogenation of dimethyl oxalate, which takes silicon dioxide as a carrier, takes Cu as a main active component, and simultaneously contains one or more of Ag, Mg, Au, Ru, Rh, Pd, Pt, Re, Ni, Co, Cr, Zn and Zr as an auxiliary agent. By adopting the catalyst, the highest conversion rate of dimethyl oxalate in the reaction can reach 87.5 percent, and the highest selectivity of methyl glycolate can reach 89.8 percent.
Although the conventional silver and/or copper catalyst supported on a silica carrier can catalyze the reaction for producing methyl glycolate by hydrogenation of dimethyl oxalate and has a high conversion rate of dimethyl oxalate and a high selectivity of methyl glycolate, there is room for improvement in the purity of methyl glycolate produced by the conventional method.
Therefore, there is still a need in the art to develop a reaction method for preparing methyl glycolate by hydrogenation of dimethyl oxalate, which can improve the purity of the product, facilitate the long-term stable operation of the catalyst, and reduce the subsequent separation and purification costs of the product, methyl glycolate.
Disclosure of Invention
It is an object of the present invention to provide a process for the hydrogenation of dimethyl oxalate to produce methyl glycolate, in which process undesirable impurities in the product methyl glycolate are avoided.
Accordingly, one aspect of the present invention is to provide a catalyst for the reaction of preparing methyl glycolate by hydrogenation of dimethyl oxalate, which comprises a titanium silicalite molecular sieve carrier and silver and/or copper atoms supported on the carrier, wherein the silver and/or copper atoms account for 1 to 40% by weight of the total weight of the catalyst.
Another aspect of the present invention relates to a method for preparing methyl glycolate by hydrogenating dimethyl oxalate, which uses a reaction catalyst comprising a titanium silicalite support and silver and/or copper atoms supported on the support, the silver and/or copper atoms comprising 1 to 40% by weight based on the total weight of the catalyst.
In still another aspect, the invention relates to a use of a catalyst in a reaction for preparing methyl glycolate by hydrogenating dimethyl oxalate, wherein the catalyst comprises a titanium silicalite molecular sieve carrier and silver and/or copper atoms carried on the carrier, and the silver and/or copper atoms account for 1-40% of the catalyst by weight.
Detailed Description
The inventor of the invention researches and discovers that the methyl glycolate prepared by the prior method contains organic silicon impurities, thereby affecting the separation and purification cost of subsequent products, because a small amount of methyl orthosilicate by-product exists in the methyl glycolate product, and the methyl orthosilicate by-product is difficult to separate and remove, thereby affecting the downstream market use of the methyl glycolate as an intermediate product.
The inventors believe that the methyl silicate impurity formed in the product of the prior art reaction for the preparation of methyl glycolate by the hydrogenation of dimethyl oxalate using a silver and/or copper catalyst supported on a silica support is likely to be formed by the reaction of methanol produced during the reaction with the silica support. If a silica-free support could be sought and a catalyst formed using the support would have substantially comparable selectivity and conversion to the silica-containing catalyst, the purity of the methyl glycolate could be advantageously increased without adversely affecting the final catalytic reaction itself. The present invention has been completed based on this finding.
Therefore, the titanium silicalite molecular sieve is used as a carrier for the reaction catalyst for preparing the methyl glycolate by hydrogenating the dimethyl oxalate. Titanium silicalite supports are known per se from the prior art. For example, master's paper entitled "preparation of titanium silicalite molecular sieves and study of catalytic oxidation performance" by wujing (university of eastern china), which is incorporated herein by reference as part of the present invention, describes several methods for the preparation of titanium silicalite molecular sieves and their use in catalyzing the liquid phase ammoxidation of cyclohexanone in a fixed bed reactor. Titanium silicalite supports suitable for use in the process of the present invention are also commercially available, for example, from Shanghai Zeolite, Inc.
The catalyst of the present invention comprises silver and/or copper atoms supported on the carrier, said silver and/or copper atoms being present in an amount of 1 to 40%, preferably 5 to 35%, more preferably 10 to 30%, preferably 15 to 25%, based on the total weight of the catalyst.
In one embodiment of the present invention, the catalyst comprises silver as a major active ingredient and copper as a minor active ingredient, wherein the silver is present in an amount of 1 to 30%, preferably 4 to 25%, and more preferably 10 to 20% by weight based on the total weight of the catalyst; the copper is present in an amount of 0-10%, preferably 1-8%, more preferably 3-5%.
The method for supporting silver and/or copper on the carrier is not particularly limited, and may be any conventional method in the art. In one embodiment of the present invention, the method for supporting silver and/or copper on a carrier comprises dissolving a soluble silver salt and/or a soluble copper salt and optionally a soluble auxiliary agent in a solvent to prepare an impregnation solution, then soaking the titanium silicalite molecular sieve carrier in the impregnation solution, separating out the soaked solid after sufficient absorption, and then drying and roasting the solid to obtain the catalyst.
In one embodiment of the present invention, the method for carrying silver and/or copper onto the carrier comprises dissolving a soluble silver salt and/or a soluble copper salt and optionally a soluble assistant in water or ammonia water to prepare an impregnation solution, then soaking the titanium-silicon molecular sieve carrier in the impregnation solution for 1-10 hours, preferably 2-8 hours, more preferably 3-7 hours, after sufficient absorption, separating out the soaked solid, then drying the solid at 80-140 ℃, preferably 90-130 ℃, more preferably 100-120 ℃, and calcining the solid in a muffle furnace at 300-800 ℃, preferably 400-600 ℃, more preferably 450-550 ℃, for 1-24 hours, preferably 2-20 hours, more preferably 3-18 hours to obtain the catalyst.
In one embodiment of the invention, the catalyst is prepared by an isovolumetric impregnation method and a precipitation method, wherein sodium hydroxide or sodium carbonate is used as a precipitator.
In one embodiment of the present invention, the catalyst is prepared by using a synthetic microporous titanium silicalite molecular sieve as a carrier and adopting an impregnation method or a deposition precipitation method.
In one example of the present invention, the impregnation method comprises: taking a salt solution of a main active component Ag as a primary impregnation liquid, and taking a salt solution of an auxiliary component as a secondary impregnation liquid to impregnate the carrier; or simultaneously taking a mixed salt solution of the main active component and the auxiliary agent as an impregnation solution to impregnate the carrier; the impregnated support is then dried, calcined and reduced to give the desired catalyst. When the catalyst is prepared by adopting an impregnation method, active components Ag and the auxiliary agents can be supported by adopting different impregnation sequences, the auxiliary agents are firstly impregnated on the carrier, the catalyst is dried and roasted, then the salt solution of Ag is impregnated, and the required catalyst is obtained by further drying and roasting.
In one example of the present invention, the precipitation method comprises: dispersing a carrier in a certain aqueous solution, stirring, preparing a metal salt solution and an alkali solution with a certain concentration, adding the metal salt solution and the alkali solution into the carrier aqueous solution according to a certain sequence, stirring, controlling a certain pH value, and then aging, stirring, washing, filtering, drying, roasting and reducing to obtain the required catalyst.
The catalyst of the invention needs to be reduced before use, the reducing gas is hydrogen or a mixed gas of nitrogen and hydrogen, and the airspeed of the catalyst is 500-10000 h -1 The activation temperature is 100-400 ℃, and the activation time is 0.5-8 hours.
The activity evaluation of the catalyst of the invention is carried out in a fixed bed stainless steel pressurized reactor, and the reaction tube has an inner diameter of 15mm and a length of 600 mm. The reaction pressure is controlled by front and back pressure-stabilizing valves and back pressure valve, and the fluctuation range of the reaction temperature is +/-0.5 ℃. The reactor is filled with 2g of 20-30 mesh catalyst, and inert quartz sand is filled up and down in the bed layer to prevent gas channeling in the tube. The catalyst was subjected to on-line reductive activation with hydrogen at a temperature of 300 ℃ for 5 hours. After the activation is finished, adjusting the feeding of dimethyl oxalate melting material or methanol solution for reaction. Dimethyl oxalate or a methanol solution thereof is pumped into a gasifier by a metering pump for vaporization, hydrogen from a steel cylinder is decompressed by a pressure stabilizing valve, the flow rate of the hydrogen is controlled and measured by a high-pressure mass flow meter, and the hydrogen enters the gasifier to be fully mixed with the dimethyl oxalate from the high-pressure metering pump and then flows into a reactor for hydrogenation reaction. The product was collected after cooling and analyzed.
The hydrogenation catalyst has the advantages of simple preparation process, good repeatability, high reaction activity and selectivity in the reaction of synthesizing methyl glycolate and ethylene glycol by hydrogenating dimethyl oxalate, stable reaction performance and long service life.
The technical solution of the present invention is further described in detail with reference to the following specific examples, but the present invention is not limited to the examples.
Examples
1. Test method
Analysis was performed using an Agilent gas chromatograph model GC-7890. Chromatographic conditions are as follows: chromatographic column DB-624, 30m × 0.25mm × 0.25 μm, FID detector, vaporizing chamber temperature 250 deg.C, detection chamber temperature 250 deg.C. Adopting temperature programming: the initial temperature was maintained at 80 ℃ for 1.5min, then ramped up to 250 ℃ at 40 ℃/min for 3 min. Conversion and selectivity were calculated by normalized area normalization.
Fi, F is the molar correction factor of product i and DMO,
ai, A is the chromatographic peak area of the product i and DMO,
mi and M are the molar masses of the product and DMO,
ni is the number of carbon atoms per molecule of product i relative to DMO.
Example 1
Taking 23.6g of silver nitrate to dissolve in 100mL of water, soaking the formed 100g of MFI type titanium silicon microporous molecular sieve (purchased from Shanghai Zhuoyue molecular sieve Co., Ltd.) in the prepared solution for 2 hours, separating out solid after full absorption, drying at 80 ℃ for 4 hours, and roasting at 400 ℃ for 5 hours to obtain the catalyst.
Sieving the catalyst, taking 20-30 mesh particles, filling the particles into a fixed bed reactor, introducing hydrogen, reducing for 4 hours at 300 ℃, and then reacting at 200 ℃, 2.5Mpa, 50 hydrogen ester molar ratio and 0.7 hour hourly space velocity of feeding liquid -1 The hydrogenation reaction is carried out under the conditions of (1).
The test was carried out by the above method, and the results were: the conversion of dimethyl oxalate was 98%, the selectivity for methyl glycolate was 94%, and the selectivity for ethylene glycol was 4%, and no methyl silicate component was detected in the product by chromatography and mass spectrometry.
Example 2
Dissolving 23.6g of silver nitrate in 90mL of water, soaking the formed 100g of MFI type titanium-silicon microporous molecular sieve (purchased from Shanghai Zhuyue molecular sieve Co., Ltd.) in the prepared solution for 2 hours, completely absorbing, drying the solid at 80 ℃ for 4 hours, and roasting at 300 ℃ for 4 hours. The obtained catalyst was immersed in a solution containing 0.5g of indium nitrate in an equal volume, dried under the above conditions, and then calcined at 420 ℃ for 4 hours.
Sieving to obtain 20-30 mesh granules, loading into fixed bed reactor, introducing hydrogen gas, reducing at 300 deg.C for 4 hr, reacting at 200 deg.C and 2.5Mpa under hydrogen ester molar ratio of 50, and feeding liquidSpace velocity of 0.7h -1 The hydrogenation reaction is carried out under the conditions of (1).
The test was carried out by the above method, and the results were: the conversion rate of dimethyl oxalate was 97%, the selectivity for methyl glycolate was 92%, and the selectivity for ethylene glycol was 6%, and no methyl silicate component was detected in the product by chromatography and mass spectrometry.
Example 3
Dissolving 23.6g of silver nitrate in 100mL of water, soaking 100g of MWW type titanium-silicon microporous molecular sieve (purchased from Shanghai Zhuoyue molecular sieve Co., Ltd.) in the prepared solution for 2 hours, separating out solids after full absorption, drying at 80 ℃ for 4 hours, and roasting at 400 ℃ for 5 hours to obtain the catalyst.
Sieving the catalyst, taking 20-30 mesh particles, filling the particles into a fixed bed reactor, introducing hydrogen, reducing for 4 hours at 300 ℃, and then reducing at the reaction temperature of 200 ℃, the pressure of 2.5Mpa, the hydrogen ester molar ratio of 50 and the hourly space velocity of feeding liquid of 0.7 hour -1 The hydrogenation reaction is carried out under the conditions of (1).
The test was carried out by the above method, and the results were: the conversion rate of dimethyl oxalate was 99%, the selectivity for methyl glycolate was 93%, and the selectivity for ethylene glycol was 5%, and no methyl silicate component was detected in the product by chromatography and mass spectrometry.
Comparative example 1
Dissolving 23.6g of silver nitrate in 100mL of water, adding ammonia water to prepare a silver-ammonia solution, soaking 100g of silicon dioxide (purchased from Shanghai Zhuyue molecular sieves Co., Ltd.) in the prepared solution, fully absorbing, separating out a solid, drying at 80 ℃ for 4 hours, and roasting at 400 ℃ for 5 hours to prepare a catalyst precursor.
Sieving the catalyst, taking 20-30 mesh particles, filling the particles into a fixed bed reactor, introducing hydrogen, reducing for 4 hours at 300 ℃, and then reacting at 200 ℃, 2.5Mpa, 50 hydrogen ester molar ratio and 0.7 hour hourly space velocity of feeding liquid -1 The hydrogenation reaction is carried out under the conditions of (1).
The test was carried out by the above method, and the results were: the conversion rate of dimethyl oxalate is 96%, the selectivity of methyl glycolate is 91%, the selectivity of ethylene glycol is 7%, carrier components are detected in products through chromatographic analysis and mass spectrometric analysis, and qualitative analysis mainly refers to methyl orthosilicate formed by reaction of carrier silicon loss.
Example 4
20g of an MFI type titanium silicalite molecular sieve (available from Shanghai Zhuyue molecular sieves Co., Ltd.) was added to deionized water and stirred for 2 hours to obtain a suspension. After 5g of silver nitrate had completely dissolved, it was added to the suspension and stirred for 2 hours. Dropwise adding 0.1mol/L sodium hydroxide solution into the solution, fully stirring for 8 hours at room temperature, filtering, washing, drying for 6 hours at 80 ℃, and roasting for 4 hours at 400 ℃ to obtain the catalyst.
Sieving the catalyst, taking 20-30 mesh particles, filling the particles into a fixed bed reactor, activating for 4 hours at 240 ℃, and then at the reaction temperature of 200 ℃, the pressure of 3Mpa, the hydrogen ester molar ratio of 25 and the feed liquid hourly space velocity of 1h -1 The hydrogenation reaction is carried out under the conditions of (1).
The test was carried out using the method described above, and the results: the conversion of dimethyl oxalate was 93%, the selectivity for methyl glycolate was 95%, and the selectivity for ethylene glycol was 4%, and no methyl silicate component was detected in the product by chromatography and mass spectrometry.
Example 5
Dissolving 5g of silver nitrate and 1g of copper nitrate in 20mL of water, soaking the formed 20g of MWW type titanium silicalite molecular sieve (purchased from Shanghai Zhuoyue molecular sieve Co., Ltd.) in the prepared solution for 4 hours, separating out solids after full absorption, drying the solids at 100 ℃ for 3 hours, and roasting the solids at 430 ℃ for 2 hours to obtain the catalyst.
Sieving the catalyst, taking 20-30 mesh particles, filling the particles into a fixed bed reactor, activating for 2 hours at 250 ℃, and then at the reaction temperature of 200 ℃, the pressure of 3Mpa, the hydrogen ester molar ratio of 50 and the hourly space velocity of the feeding liquid of 1h -1 The hydrogenation reaction is carried out under the conditions of (1).
The test was carried out using the method described above, and the results: the conversion rate of dimethyl oxalate is 99%, the selectivity of methyl glycolate is 85%, the selectivity of ethylene glycol is 12%, and a methyl silicate component is not detected in the product through chromatographic analysis and mass spectrum analysis.
Example 6
Dissolving 5g of silver nitrate in 20mL of water, soaking 20g of a molded MFI type titanium silicalite molecular sieve (purchased from Shanghai Zhuyue molecular sieve Co., Ltd.) in the prepared solution for 4 hours, separating out solids after full absorption, drying for 3 hours at 100 ℃, and pre-roasting for 1 hour at 300 ℃ in an air atmosphere; then 1g of calcium nitrate and 0.5g of copper nitrate were dissolved in 20ml of water, and the previously calcined solid was immersed in the prepared solution. Soaking for 4 hours, separating out solid after full absorption, and roasting for 2 hours at 450 ℃ to obtain the catalyst. Sieving the catalyst, taking 20-30 mesh particles, filling the particles into a fixed bed reactor, activating for 2 hours at 250 ℃, and then carrying out reaction at 200 ℃, under the pressure of 3Mpa, at the hydrogen ester molar ratio of 50 and at the feed liquid hourly space velocity of 1 hour -1 The hydrogenation reaction is carried out under the conditions of (1).
The test was carried out by the above method, and the results were: the conversion rate of dimethyl oxalate is 95%, the selectivity of methyl glycolate is 88%, the selectivity of ethylene glycol is 10%, and no carrier component can be detected in the product through chromatographic analysis and mass spectrometric analysis.
Example 7
Dissolving 6g of silver nitrate in 20mL of water, soaking 20g of a molded MFI type titanium silicalite molecular sieve (purchased from Shanghai Zhuyue molecular sieve Co., Ltd.) in the prepared solution for 4 hours, separating out solids after sufficient absorption, drying the solids for 3 hours at 100 ℃, and then pre-roasting the solids for 1 hour at 320 ℃; then 0.1g of a solution of ruthenium acetate was diluted in 20ml of water and the pre-calcined solid was immersed in the prepared solution. Soaking for 4 hours, separating out solid after full absorption, and roasting for 2 hours at 450 ℃ to obtain the catalyst.
Sieving the catalyst, loading 20-30 mesh particles into a fixed bed reactor, activating at 250 deg.C for 2 hr, reacting at 200 deg.C and 3Mpa under hydrogen ester molar ratio of 50 and hourly space velocity of feeding liquid of 1 hr -1 The hydrogenation reaction is carried out under the conditions of (1).
The test was carried out by the above method, and the results were: the conversion rate of dimethyl oxalate was 92%, the selectivity for methyl glycolate was 87%, and the selectivity for ethylene glycol was 10%, and no methyl silicate component was detected in the product by chromatography and mass spectrometry.
Claims (2)
1. The application of a catalyst in the reaction of preparing methyl glycolate by hydrogenating dimethyl oxalate, wherein the catalyst comprises a microporous titanium silicalite molecular sieve carrier and silver loaded on the carrier, and the silver accounts for 1-40% of the total weight of the catalyst;
the microporous titanium silicalite molecular sieve carrier is selected from MFI type or MWW type.
2. The use according to claim 1, wherein the catalyst comprises a microporous titanium silicalite support and supported thereon silver and one or more auxiliary elements selected from the group consisting of Cu, Ca, Au, Ru, Rh, Pd, Pt, Ir, Ni, In, the silver comprising from 1 to 30% and the auxiliary elements comprising from 0.01 to 10% by weight of the total catalyst.
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