CN114163333A - Method for synthesizing methyl ethyl carbonate by one step - Google Patents
Method for synthesizing methyl ethyl carbonate by one step Download PDFInfo
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- CN114163333A CN114163333A CN202210014857.3A CN202210014857A CN114163333A CN 114163333 A CN114163333 A CN 114163333A CN 202210014857 A CN202210014857 A CN 202210014857A CN 114163333 A CN114163333 A CN 114163333A
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Abstract
The invention discloses a method for synthesizing methyl ethyl carbonate by one step, which comprises the following steps of 1) reacting methanol, ethanol, carbon monoxide and oxygen under the condition of a high-temperature high-pressure catalyst to generate methyl ethyl carbonate; 2) and rectifying and separating the reaction product containing the methyl ethyl carbonate to obtain the methyl ethyl carbonate. The method not only can synthesize the methyl ethyl carbonate in one step, but also can obtain a high-purity product of the methyl ethyl carbonate after rectification treatment.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing methyl ethyl carbonate by one step.
Background
Methyl Ethyl Carbonate (MEC) is a colorless transparent liquid, is an excellent solvent, has the characteristics of dimethyl Carbonate and diethyl Carbonate due to the fact that the molecular structure of the MEC has Methyl and Ethyl simultaneously, can react with alcohol, ester, phenol, amine and the like, and is suitable for various organic reactions. And because the methyl ethyl carbonate has small viscosity, high dielectric constant and strong solubility to lithium salt, the methyl ethyl carbonate is an excellent lithium ion battery electrolyte solvent, can improve the energy density and discharge capacity of the battery, and can further improve the safety performance and service life of the battery. In addition, the good low-temperature service performance is also the advantage of the electrolyte.
The prior art for preparing methyl ethyl carbonate has many technical routes, mainly comprises three methods, namely a light vapor generation method, an oxidation carbonylation method and an ester exchange method, wherein the methyl ethyl carbonate is synthesized by the ester exchange method at present, and the synthesis of the methyl ethyl carbonate by the ester exchange method is divided into the following methods: the ester exchange of diethyl carbonate and methanol, the ester exchange of dimethyl carbonate and ethanol, and the ester exchange of dimethyl carbonate and diethyl carbonate.
At present, the transesterification method is mainly used as a main stream synthesis route in all methyl ethyl carbonate synthesis methods, but dimethyl carbonate serving as a raw material of the transesterification method needs to be synthesized by exchanging methyl ester with ethylene carbonate or propylene carbonate, ethylene carbonate needs to be prepared by reacting ethylene oxide and carbon dioxide, the reaction route needs to be performed in sections, the conversion rate of reactants and the selectivity of products in each stage are low, and meanwhile, the complicated rectification and separation operation needs to be performed on each product in each stage, so the energy consumption of the industrial production process is large, and the operation cost is increased.
Through comparative analysis and actual production experience, the following problems are found to exist at present:
1. the synthesis route from methanol, ethanol and other raw materials to the methyl ethyl carbonate product is longer, and the conversion rate of reactants and the selectivity of the product are low;
2. the products in each stage need to be subjected to complicated rectification separation, and the energy consumption is high.
Disclosure of Invention
The invention aims to provide a method for synthesizing methyl ethyl carbonate by one step, which can continuously produce high-purity methyl ethyl carbonate.
The invention relates to a method for synthesizing methyl ethyl carbonate by one step, which has the following reaction formula:
CH3OH+C2H5OH+CO+1/2O2→CH3OCOOC2H5+ H2O (main reaction)
CO+1/2O2→CO2(side reaction)
CH3OH+CO2→CH3OCOOCH3+H2O (side reaction)
CH3OCOOCH3+C2H5OH→CH3OCOOC2H5+CH3OH (side reaction)
CH3OCOOCH3+C2H5OCOOC2H5→CH3OCOOC2H5(side reaction)
In one embodiment, the method for synthesizing methyl ethyl carbonate by one step comprises the following steps,
1) reacting methanol, ethanol, carbon monoxide and oxygen under the condition of a high-temperature high-pressure catalyst to generate methyl ethyl carbonate, wherein the catalyst is a mixed catalyst which takes active carbon as a carrier and consists of zinc oxide, cuprous chloride and nitrogen-containing Schiff base organic matters;
2) and rectifying and separating the reaction product containing the methyl ethyl carbonate to obtain the methyl ethyl carbonate.
The above-mentioned process of the present invention, 1), wherein methanol: ethanol: the molar ratio of carbon monoxide to oxygen is 2: 1-1.5: 1-1.2: 0.5, the temperature is 110-130 ℃, the pressure is 2.0-3.0 Mpa, and the weight ratio of the zinc oxide, the cuprous chloride and the nitrogen-containing Schiff base to the mixed catalyst is 1: 5-20: 5-10, wherein the nitrogen-containing Schiff base is N-ethyl carbazole Schiff base.
The method for synthesizing the methyl ethyl carbonate by one step comprises the following steps:
a) sending ethanol, methanol, carbon monoxide and oxygen dissolved with sodium ethoxide into a fixed bed reactor R1 for reaction to obtain a reaction product, condensing ethyl methyl carbonate EMC, dimethyl carbonate DMC, water and unreacted methanol and ethanol from the bottom of the fixed bed reactor R1 through a condenser E2, then entering an intermediate tank V2, and discharging non-condensable gas from the top of the intermediate tank V2;
b) condensing the reaction product in the step a), sending the condensate to a first rectifying tower for rectification, and sending the liquid phase part of the first rectifying tower to a third rectifying tower for rectification;
c) after condensing the gas phase at the top of the first rectifying tower, returning one part of the gas phase to the first rectifying tower for refluxing, sending the other part of the gas phase to the second rectifying tower for rectifying, condensing the gas phase at the top of the second rectifying tower, returning one part of condensate to the second rectifying tower for refluxing, sending one part of mixture containing methanol and ethanol to the fixed bed reactor for reacting, and discharging residual liquid at the bottom of the tower;
d) and after the gas phase at the top of the third rectifying tower is condensed, returning a part of condensate to the third rectifying tower for reflux, taking the other part of condensate as a product of ethyl methyl carbonate for extraction, and discharging heavy components from the bottom of the tower.
The method further comprises the steps of extracting carbon monoxide, oxygen and part of liquid carried by the carbon monoxide, the oxygen and the oxygen which are not reacted in the step a) from the top of the fixed bed reactor, cooling, returning the condensate to the fixed bed reactor to continuously participate in the reaction, and discharging non-condensable gas.
According to the method, the reaction product in the step a) contains methyl ethyl carbonate, dimethyl carbonate, methanol, ethanol and water, the operation pressure of the first rectifying tower in the step b) is normal pressure, the tower top temperature is 70-75 ℃, and the reflux ratio is 1-3: 1, the operating pressure of the second rectifying tower in the step c) is normal pressure, the temperature of the top of the tower is 65-70 ℃, and the reflux ratio is 1-3: 1, the operating pressure of the third rectifying tower in the step d) is normal pressure, the temperature of the top of the tower is 105-110 ℃, and the reflux ratio is 1-3: 1.
in a preferred embodiment, the method for synthesizing methyl ethyl carbonate by one step comprises the following steps,
1) reacting methanol, ethanol, carbon monoxide and oxygen under the condition of a high-temperature high-pressure catalyst to generate methyl ethyl carbonate, wherein the catalyst is a mixed catalyst which takes active carbon as a carrier and consists of zinc oxide, cuprous chloride and nitrogen-containing Schiff base, and the weight ratio of the zinc oxide to the cuprous chloride to the nitrogen-containing Schiff base is 1: 5-20: 5-10;
2) rectifying and separating the reaction product containing the methyl ethyl carbonate to obtain electronic grade methyl ethyl carbonate with the content of more than or equal to 99.99 percent,
wherein, in the step 1), the mol ratio of methanol, ethanol, carbon monoxide and oxygen is 2: 1-1.5: 1-1.2: 0.5, the nitrogen-containing Schiff base is N-ethyl carbazole Schiff base, and the high temperature and the high pressure are 110-130 ℃ and 2.0-3.0 MPa.
In a specific embodiment, the method for synthesizing methyl ethyl carbonate by one step comprises the following process steps:
1) methanol, ethanol, carbon monoxide, oxygen (molar ratio of 2: 1-1.5: 1-1.2: 0.5) and sodium ethoxide solution dissolved in ethanol are fed into a fixed bed reactor R1 for reaction, and zinc oxide, cuprous chloride and nitrogen-containing Schiff base (the weight ratio is 1: 5-20: 5-10) to obtain a reaction product, wherein unreacted carbon monoxide and oxygen carry partial liquid to enter a flash tank V1 after being condensed by a condenser E1 from the top of the fixed bed reactor, non-condensable gas is discharged from the top of V1, condensate (containing methanol and ethanol) is sent to the fixed bed reactor R1 through a reflux pump P1 to participate in reaction, the reaction product (containing methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), methanol, ethanol and water) flows out from the bottom of the fixed bed reactor R1 and is condensed by a condenser E2, then the condensate enters an intermediate tank V2, and the non-condensable gas is discharged from the top of the intermediate tank V2;
2) feeding the condensate of the intermediate tank V2 in the step 1) to a first rectifying tower (T1) through a material pump P2 for rectification, condensing the gas phase at the top of the T1 through a condenser E3, feeding the condensate into a reflux tank V3, feeding part of the condensate to the rectifying tower T1 through a pump P3 for reflux, and feeding part of the condensate to a second rectifying tower (T2). The liquid phase in the bottom of the first rectifying tower T1 is sent to a third rectifying tower T3 for rectification through a material pump P4;
3) after the feed sent to the second rectifying tower T2 in the step 2) transfers heat and mass in the tower, the gas phase at the top of the tower is condensed by a condenser E5, then the condensate enters a reflux tank V4, part of the condensate is sent to the rectifying tower T2 through a reflux pump P5 for reflux, part of the mixture of methanol and ethanol is sent to a fixed bed reactor R1 for reaction, and the residual liquid at the bottom of the rectifying tower T2 is discharged from the bottom;
4) after the feed sent to the third rectifying tower T3 in the step 2) transfers heat and mass in the tower, the gas phase at the top is condensed by a condenser E7, then the condensate enters a reflux tank V5, part of the condensate is sent to the rectifying tower T3 through a reflux pump P7 for reflux, part of the condensate is extracted as the product of ethyl methyl carbonate, and the residual liquid at the bottom of the rectifying tower T3 is discharged from the bottom.
In the above embodiment, the process of the present invention, step 1), methanol: ethanol: the molar ratio of carbon monoxide to oxygen is 2: 1-1.5: 1-1.2: 0.5; the temperature of the fixed bed reactor R1 is 110-130 ℃, and the pressure is 2.0-3.0 MPa; the fixed bed reactor is filled with a catalyst, the catalyst is a mixed catalyst of zinc oxide, cuprous chloride and nitrogen-containing Schiff base with activated carbon as a carrier, and the weight ratio of the zinc oxide to the cuprous chloride to the nitrogen-containing Schiff base is 1: 5-20: 5-10, wherein the nitrogen-containing Schiff base is N-ethyl carbazole Schiff base; the operating pressure of the rectifying tower T1 in the step 2) is normal pressure, the temperature of the top of the tower is 70-75 ℃, and the reflux ratio is 1-3: 1; the operating pressure of the rectifying tower T2 in the step 3) is normal pressure, the temperature of the top of the tower is 65-70 ℃, and the reflux ratio is 1-3: 1; the operating pressure of the rectifying tower T3 in the step 3) is normal pressure, the tower top temperature is 105-110 ℃, and the reflux ratio is 1-3: 1.
the technical scheme of the invention has the following beneficial effects:
the method for synthesizing the methyl ethyl carbonate by one step not only can synthesize the methyl ethyl carbonate by one step, but also can continuously produce the high-purity methyl ethyl carbonate. The advantages thereof also include that,
1. the high-purity ethylene carbonate can be obtained through the process route;
2. the process uses a large amount of carbon monoxide as a raw material, and contributes to carbon neutralization;
3. the process is one-step synthesis and rectification continuous operation, and can ensure stable product quality and further improve the capacity of the device.
Drawings
FIG. 1 is a schematic flow diagram of a one-step synthesis process of the present invention.
Detailed Description
The invention is further described below in connection with representative examples to assist in understanding the nature of the invention, but not to limit the scope of the invention in any way.
The reaction scheme of the following example is schematically shown in FIG. 1.
One of the catalyst components adopted in the embodiment is an N-ethyl carbazole Schiff base which is a self-made product and is prepared by synthesizing N-ethyl carbazole-3-formaldehyde (NECD) and Ethylenediamine (EDA), and the preparation method refers to (the synthesis of the N-ethyl carbazole Schiff base EDA-NECD and the recognition research on Cu2 +) (functional materials 1588-1590 in No. 9 of 2011).
EXAMPLE 1 preparation of methyl Ethyl carbonate
The process comprises the following steps:
1) carbon monoxide, oxygen, methanol, ethanol and sodium ethoxide solution dissolved in ethanol are fed into a fixed bed reactor R1 for reaction, wherein the ratio of methanol: ethanol: the molar ratio of carbon monoxide to oxygen is 2: 1.3: 1.1: 0.5, a mixed catalyst which is composed of zinc oxide taking active carbon as a carrier, cuprous chloride and N-ethyl carbazole Schiff base (the weight ratio is 1: 10: 8) is filled in the fixed bed reactor, and a reaction product is obtained after the reaction. Unreacted carbon monoxide and oxygen carry partial liquid to be condensed from the top through a condenser E1, condensate (containing methanol and ethanol) enters a flash tank V1, non-condensable gas is discharged from the top of V1, and the condensate is sent to a methanol and ethanol feeding pipeline of a fixed bed reactor R1 through a reflux pump P1 to continue to react.
The reaction product contains methyl ethyl carbonate, dimethyl carbonate, water, unreacted methanol and ethanol, and the contents of the components are as follows: 22 wt% of methanol, 6 wt% of ethanol, 58 wt% of Ethyl Methyl Carbonate (EMC), 8 wt% of water and 6 wt% of dimethyl carbonate (DMC), wherein a reaction product flows out of the bottom of a fixed bed reactor R1 and is condensed by a condenser E2, a condensate enters an intermediate tank V2, and a non-condensable gas is discharged from the top of an intermediate tank V2. The temperature of the fixed bed reactor R1 was 120 ℃ and the pressure was 2.5 MPa.
2) Sending the condensate of the intermediate tank V2 in the step 1) to a rectifying tower T1 through a material pump P2 for rectification, condensing a gas phase at the top of the T1 through a condenser E3, then sending the condensate into a reflux tank V3, returning the condensate to the rectifying tower T1 through a reflux pump P3 part for reflux, wherein the return amount is such that the reflux ratio of the rectifying tower T1 is kept at about 2: 1, the remainder is sent to a rectification column T2 as feed. The liquid phase at the bottom of the first rectifying tower T1 is sent to a third rectifying tower T3 for rectification through a material pump P4. The operating pressure of the rectification column T1 is normal pressure, the temperature at the top of the column is about 72 ℃, and the reflux ratio is about 2: 1.
3) after the feed sent to the rectifying tower T2 in the step 2) is subjected to heat and mass transfer rectification in the tower, the gas phase at the top is condensed by a condenser E5, a condensate (containing methanol and ethanol, the methanol is more than or equal to 85 percent, the ethanol is less than 15 percent, and the water is less than or equal to 0.1 percent) enters a reflux tank V4, and then a part of the condensate returns to the rectifying tower T2 through a reflux pump P5 to reflux, wherein the return amount is such that the reflux ratio of the rectifying tower T2 is kept at about 2: 1, the remaining part is sent to a feeding pipeline of methanol and ethanol of a fixed bed reactor R1, and the residual liquid in the bottom kettle is discharged from the bottom. The operating pressure of the rectification column T2 was atmospheric, the overhead temperature was 67 ℃, and the reflux ratio was about 2: 1.
4) and (3) after the feed sent to the rectifying tower T3 in the step 2) transfers heat and mass in the tower, discharging residual liquid at the bottom of the rectifying tower T3 from the bottom. The gas phase at the top of the rectifying tower T3 is condensed by a condenser E7, then the condensate (methyl ethyl carbonate) enters a reflux tank V5, and then is pressurized by a reflux pump P7 and then partially returns to the rectifying tower T3 to reflux, and the return amount is such that the reflux ratio of the rectifying tower T3 is kept at about 2: 1 is better, the rest part is taken out as an EMC product, the extracted methyl ethyl carbonate is more than or equal to 99.99wt percent, the water is less than or equal to 0.003 percent, and the yield is 87.5 percent (rectification yield). Wherein the operating pressure of the rectifying tower T3 is normal pressure, the tower top temperature is 107 ℃, and the reflux ratio is about 2: 1.
example 2
Example 2 the process steps were identical to those of example 1, except that the parameters were different. In example 2, step 1), methanol: ethanol: carbon monoxide: the molar ratio of oxygen is 2: 1.5: 1.2: 0.5, the temperature of the fixed bed reactor R1 is 130 ℃, and the pressure is 2.0 MPa;
a mixed catalyst which is composed of zinc oxide, cuprous chloride and N-ethyl carbazole Schiff base (weight ratio is 1: 10: 8) and takes active carbon as a carrier is filled in the fixed bed reactor
In the step 2), the tower top temperature of the first rectifying tower T1 is 75 ℃, the reflux ratio is 1: 1;
in the step 3), the tower top temperature of the second rectifying tower T2 is 70 ℃, the reflux ratio is 3: 1;
in the step 4), the tower top temperature of the third rectifying tower T3 is 110 ℃, the reflux ratio is 3: 1.
wherein, the contents of the components at the bottom outlet of the fixed bed reactor R1 are 21 wt% of methanol, 10 wt% of ethanol, 52 wt% of ethyl methyl carbonate EMC, 8 wt% of water and 9 wt% of dimethyl carbonate DMC; the components of the mixture of methanol and ethanol extracted from the rectifying tower T2 are more than or equal to 85 percent of methanol, less than 15 percent of ethanol and less than or equal to 0.2 percent of water, the methyl ethyl carbonate extracted from the rectifying tower T3 is more than or equal to 99.99 percent by weight, the water is less than or equal to 0.003 percent, and the yield is 84.4 percent (the rectification yield).
Example 3
Example 3 the process steps were identical to those of example 1, except that the parameters were different. In example 2, step 1), methanol: ethanol: carbon monoxide: the molar ratio of oxygen is 2: 1.0: 1.0: 0.5, the temperature of the fixed bed reactor R1 is 110 ℃, and the pressure is 3.0 MPa;
a mixed catalyst which is composed of zinc oxide, cuprous chloride and N-ethyl carbazole Schiff base (weight ratio is 1: 10: 8) and takes active carbon as a carrier is filled in the fixed bed reactor
In the step 2), the tower top temperature of the first rectifying tower T1 is 70 ℃, the reflux ratio is 3: 1;
in the step 3), the tower top temperature of the second rectifying tower T2 is 65 ℃, the reflux ratio is 1: 1;
in the step 4), the tower top temperature of the third rectifying tower T3 is 105 ℃, and the reflux ratio is 1: 1.
wherein, the contents of the components at the bottom outlet of the fixed bed reactor R1 are 30 wt% of methanol, 4 wt% of ethanol, 51 wt% of ethyl methyl carbonate EMC, 8 wt% of water and 7 wt% of dimethyl carbonate DMC; the components of the mixture of methanol and ethanol extracted by the rectifying tower T2 are more than or equal to 85 percent of methanol, less than 15 percent of ethanol and less than or equal to 0.1 percent of water. (ii) a The methyl ethyl carbonate extracted from the rectifying tower T3 is more than or equal to 99.99 wt%, the water is less than or equal to 0.003%, and the yield is 85.6% (rectification yield)
Example 4
Example 4 the process steps were identical to those of example 1, except that the parameters were different. In example 2, step 1), methanol: ethanol: carbon monoxide: the molar ratio of oxygen is 2: 1.0: 1.0: 0.5, the temperature of the fixed bed reactor R1 is 110 ℃, and the pressure is 3.0 MPa; a mixed catalyst which is composed of zinc oxide taking active carbon as a carrier, cuprous chloride and N-ethyl carbazole Schiff base (the weight ratio is 1: 5: 10) is filled in the fixed bed reactor;
in the step 2), the tower top temperature of the first rectifying tower T1 is 70 ℃, the reflux ratio is 3: 1;
in the step 3), the tower top temperature of the second rectifying tower T2 is 65 ℃, the reflux ratio is 1: 1;
in the step 4), the tower top temperature of the third rectifying tower T3 is 105 ℃, and the reflux ratio is 1: 1.
wherein, the contents of the components at the bottom outlet of the fixed bed reactor R1 are 31 wt% of methanol, 4 wt% of ethanol, 50 wt% of ethyl methyl carbonate EMC, 7 wt% of water and 8 wt% of dimethyl carbonate DMC; the components of the mixture of methanol and ethanol extracted by the rectifying tower T2 are more than or equal to 85 percent of methanol, less than 15 percent of ethanol and less than or equal to 0.1 percent of water. (ii) a The ethyl methyl carbonate extracted from the rectifying tower T3 is more than or equal to 99.99 wt%, the water is less than or equal to 0.003%, and the yield is 83.2% (rectification yield).
Example 5
Example 5 was identical to the process steps of example 1, except that the parameters were different. In example 2, step 1), methanol: ethanol: carbon monoxide: the molar ratio of oxygen is 2: 1.5: 1.2: 0.5, the temperature of a fixed bed reactor R1 is 130 ℃, the pressure is 2.0Mpa, and a mixed catalyst which is composed of zinc oxide, cuprous chloride and N-ethyl carbazole Schiff base (weight ratio is 1: 20: 5) and takes active carbon as a carrier is filled in the fixed bed reactor;
in the step 2), the tower top temperature of the first rectifying tower T1 is 75 ℃, the reflux ratio is 1: 1;
in the step 3), the tower top temperature of the second rectifying tower T2 is 70 ℃, the reflux ratio is 3: 1;
in the step 4), the tower top temperature of the third rectifying tower T3 is 110 ℃, the reflux ratio is 3: 1.
wherein, the contents of all components at the bottom outlet of the fixed bed reactor R1 are 25 wt% of methanol, 9 wt% of ethanol, 50 wt% of ethyl methyl carbonate EMC, 7 wt% of water and 9 wt% of dimethyl carbonate DMC; the components of the mixture of methanol and ethanol extracted from the rectifying tower T2 are more than or equal to 85 percent of methanol, less than 15 percent of ethanol and less than or equal to 0.2 percent of water, the methyl ethyl carbonate extracted from the rectifying tower T3 is more than or equal to 99.99 percent by weight, the water is less than or equal to 0.002 percent, and the yield is 82.9 percent (the rectification yield).
Comparative example 1
Comparative example 1 is identical to the process steps of example 1, except that the parameters are different. In comparative example 1, step 1), methanol: ethanol: carbon monoxide: the molar ratio of oxygen is 3: 1.0: 1.0: 0.4, the temperature of the fixed bed reactor R1 is 100 ℃, and the pressure is 2.0 MPa;
a mixed catalyst which is composed of zinc oxide taking active carbon as a carrier, cuprous chloride and N-ethyl carbazole Schiff base (the weight ratio is 1: 10: 8) is filled in the fixed bed reactor;
in the step 2), the tower top temperature of the first rectifying tower T1 is 65 ℃, the reflux ratio is 2: 1;
in the step 3), the tower top temperature of the second rectifying tower T2 is 72 ℃, the reflux ratio is 3: 1;
in the step 4), the tower top temperature of the third rectifying tower T3 is 115 ℃, and the reflux ratio is 1: 1.
wherein, the contents of the components at the bottom outlet of the fixed bed reactor R1 are 35 wt% of methanol, 3 wt% of ethanol, 39 wt% of ethyl methyl carbonate EMC, 7 wt% of water and 16 wt% of dimethyl carbonate DMC; the methyl ethyl carbonate extracted by the rectifying tower T3 is 97.2 wt%, the water content is 2.4%, and the DMC content is 0.4%, so that a methyl ethyl carbonate product meeting the electronic grade requirement cannot be obtained.
Comparative example 2
Comparative example 2 is identical to the process steps of example 1, except that the parameters are different. In example 2, step 1), methanol: ethanol: carbon monoxide: the molar ratio of oxygen is 2: 1.5: 1.2: 0.5, the temperature of the fixed bed reactor R1 is 130 ℃, and the pressure is 2.0 MPa;
a mixed catalyst which is composed of cuprous chloride and N-ethyl carbazole Schiff base (weight ratio is 5: 4) and takes active carbon as a carrier is filled in the fixed bed reactor
In the step 2), the tower top temperature of the first rectifying tower T1 is 75 ℃, the reflux ratio is 1: 1;
in the step 3), the tower top temperature of the second rectifying tower T2 is 70 ℃, the reflux ratio is 3: 1;
in the step 4), the tower top temperature of the third rectifying tower T3 is 110 ℃, the reflux ratio is 3: 1.
wherein, the contents of the components at the bottom outlet of the fixed bed reactor R1 are 41 wt% of methanol, 12 wt% of ethanol, 29 wt% of ethyl methyl carbonate EMC, 8 wt% of water and 10 wt% of dimethyl carbonate DMC; the components of the mixture of methanol and ethanol extracted from the rectifying tower T2 are more than or equal to 85 percent of methanol, less than 15 percent of ethanol and less than or equal to 0.2 percent of water, the methyl ethyl carbonate extracted from the rectifying tower T3 is more than or equal to 99.99 percent by weight, the water is less than or equal to 0.004 percent, and the yield is 82.1 percent (the rectification yield).
The effect of comparative examples 1 and 2 is obviously inferior to that of examples 1-5, the product ethyl methyl carbonate of comparative example 1 not only has low selectivity and the product purity does not meet the requirement of electronic purity, but the product of comparative example 2 has purity meeting the requirement of electronic purity, but the conversion rate of ethyl methyl carbonate is only 29%.
The above examples are representative only, and any variations and simple changes that can be made within the spirit of the invention are intended to be within the scope of the invention.
Claims (7)
1. A one-step synthesis method of methyl ethyl carbonate, comprising:
1) reacting methanol, ethanol, carbon monoxide and oxygen at high temperature and high pressure in the presence of a catalyst to generate methyl ethyl carbonate, wherein the catalyst is a mixed catalyst which takes active carbon as a carrier and consists of zinc oxide, cuprous chloride and nitrogen-containing Schiff base, and the weight ratio of the zinc oxide to the cuprous chloride to the nitrogen-containing Schiff base is 1: 5-20: 5-10;
2) rectifying and separating the reaction product containing the methyl ethyl carbonate to obtain electronic grade methyl ethyl carbonate with the content of more than or equal to 99.99 percent,
wherein, in the step 1), the mol ratio of methanol, ethanol, carbon monoxide and oxygen is 2: 1-1.5: 1-1.2: 0.5, wherein the nitrogen-containing Schiff base is N-ethyl carbazole Schiff base.
2. The method according to claim 1, wherein in the step 1), the high temperature and the high pressure are 110 to 130 ℃ and 2.0 to 3.0 MPa.
3. The method according to claim 1 or 2, comprising in particular the steps of:
a) sending ethanol, methanol, carbon monoxide and oxygen dissolved with sodium ethoxide into a fixed bed reactor R1 for reaction to obtain a reaction product, condensing ethyl methyl carbonate EMC, dimethyl carbonate DMC, water and unreacted methanol and ethanol from the bottom of the fixed bed reactor R1 through a condenser E2, then entering an intermediate tank V2, and discharging non-condensable gas from the top of the intermediate tank V2;
b) condensing the reaction product in the step a), sending the condensate to a first rectifying tower for rectification, and sending the liquid phase part of the first rectifying tower to a third rectifying tower for rectification;
c) after condensing the gas phase at the top of the first rectifying tower, returning one part of the gas phase to the first rectifying tower for refluxing, sending the other part of the gas phase to the second rectifying tower for rectifying, condensing the gas phase at the top of the second rectifying tower, returning one part of condensate to the second rectifying tower for refluxing, sending one part of mixture containing methanol and ethanol to the fixed bed reactor for reacting, and discharging residual liquid at the bottom of the tower;
d) and after the gas phase at the top of the third rectifying tower is condensed, returning a part of condensate to the third rectifying tower for reflux, taking the other part of condensate as a product of ethyl methyl carbonate for extraction, and discharging heavy components from the bottom of the tower.
4. The method of claim 3, further comprising the step of taking the carbon monoxide, the oxygen and the entrained part of liquid of the carbon monoxide and the oxygen which are not reacted in the step a) from the top of the fixed bed reactor, cooling the liquid, returning the condensed liquid to the fixed bed reactor to continue reacting, and discharging the non-condensable gas from the top of the V1.
5. The method according to claim 3, wherein the operating pressure of the first rectifying tower in the step b) is normal pressure, the tower top temperature is 70-75 ℃, and the reflux ratio is 1-3: 1.
6. the method as claimed in claim 3, wherein the operation pressure of the second rectifying tower in the step c) is normal pressure, the tower top temperature is 65-70 ℃, and the reflux ratio is 1-3: 1.
7. the method as claimed in claim 1, wherein the operation pressure of the third rectifying tower in the step d) is normal pressure, the tower top temperature is 105-110 ℃, and the reflux ratio is 1-3: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114380692A (en) * | 2022-03-23 | 2022-04-22 | 天津科技大学 | Preparation method of energy-saving electronic grade carbonic ester |
| CN114507136A (en) * | 2022-04-13 | 2022-05-17 | 太原理工大学 | Efficient synthesis method of lithium ion battery electrolyte mixed solvent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380692A (en) * | 2022-03-23 | 2022-04-22 | 天津科技大学 | Preparation method of energy-saving electronic grade carbonic ester |
| CN114507136A (en) * | 2022-04-13 | 2022-05-17 | 太原理工大学 | Efficient synthesis method of lithium ion battery electrolyte mixed solvent |
| CN114507136B (en) * | 2022-04-13 | 2022-06-21 | 太原理工大学 | Efficient synthesis method of lithium ion battery electrolyte mixed solvent |
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| CN114163333B (en) | 2023-09-19 |
| CN113387810A (en) | 2021-09-14 |
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