CN113582845B - Device and process for co-producing electronic grade methyl ethyl carbonate and diethyl carbonate by reaction rectification method - Google Patents
Device and process for co-producing electronic grade methyl ethyl carbonate and diethyl carbonate by reaction rectification method Download PDFInfo
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- CN113582845B CN113582845B CN202110897170.4A CN202110897170A CN113582845B CN 113582845 B CN113582845 B CN 113582845B CN 202110897170 A CN202110897170 A CN 202110897170A CN 113582845 B CN113582845 B CN 113582845B
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 title claims abstract description 157
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 278
- 238000007670 refining Methods 0.000 claims abstract description 173
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 159
- 238000000926 separation method Methods 0.000 claims abstract description 78
- 238000000746 purification Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 121
- 239000003054 catalyst Substances 0.000 claims description 45
- 238000000605 extraction Methods 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 34
- 238000010992 reflux Methods 0.000 claims description 32
- 239000000047 product Substances 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 238000005809 transesterification reaction Methods 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- -1 alkali metal salt Chemical class 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 239000001569 carbon dioxide Substances 0.000 claims description 9
- 239000000284 extract Substances 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000005192 partition Methods 0.000 claims description 7
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 3
- GYBMSOFSBPZKCX-UHFFFAOYSA-N sodium;ethanol;ethanolate Chemical compound [Na+].CCO.CC[O-] GYBMSOFSBPZKCX-UHFFFAOYSA-N 0.000 claims description 3
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 description 29
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 238000000066 reactive distillation Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a device for co-producing electronic grade methyl ethyl carbonate and diethyl carbonate by a reaction rectification method, which comprises the following components: the reaction rectifying unit, the dimethyl carbonate and methanol separating unit and the methyl ethyl carbonate and diethyl carbonate separating and purifying unit; the reaction rectifying unit comprises a reaction rectifying tower feeding buffer tank, a reaction rectifying tower and a filter press; the dimethyl carbonate and methanol separation unit comprises a dimethyl carbonate pressurizing and refining tower, a methanol refining tower and a dimethyl carbonate refining tower; the separation and purification unit for the methyl ethyl carbonate and the diethyl carbonate comprises a raw diethyl carbonate feeding buffer tank, a diethyl carbonate raw separation tower, a diethyl carbonate refining and purifying tower, a raw methyl ethyl carbonate feeding buffer tank, a methyl ethyl carbonate raw separation tower and a methyl ethyl carbonate refining and purifying tower. The invention also discloses a process for co-producing the electronic grade methyl ethyl carbonate and diethyl carbonate. The invention has reasonable process and high utilization rate of raw materials, and realizes one set of production of two electronic grade carbonic ester products.
Description
Technical Field
The invention belongs to the technical field of production of methyl ethyl carbonate and diethyl carbonate, and particularly relates to a device and a process for co-producing electronic grade methyl ethyl carbonate and diethyl carbonate by a reaction rectification method.
Background
The lithium battery electrolyte is used as a formula new material and mainly comprises an electrolyte solvent, electrolyte and an additive, wherein the electrolyte solvent accounts for 80% of the mass of the electrolyte, is a main raw material of the electrolyte and mainly comprises ethylene carbonate, dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate, and the total required amount of the four products accounts for more than 90% of the total required amount of the electrolyte solvent.
The methyl ethyl carbonate (EMC) is used as an environment-friendly green asymmetric carbonate, has wide application in the aspects of organic synthesis, medicine, fuel additives, solvents and the like, is particularly more outstanding in the aspect of lithium ion electrolyte, has strong lithium salt solubility, relatively large dielectric constant, small viscosity, high boiling point temperature and low melting point, and has good improvement effect on the performance of a battery in high-temperature and low-temperature states.
Diethyl carbonate (DEC) is an environment-friendly organic solvent and chemical intermediate, and is widely applied to the industrial fields of organic synthesis, medicine, pesticide, chemical industry and the like. The diethyl carbonate can be used as a solvent of the lithium battery electrolyte, has relatively low viscosity and good electrochemical stability, and can improve the low-temperature performance of the lithium battery electrolyte.
The purity of the lithium battery electrolyte solvent is closely related to the battery stabilizing voltage, and the higher the purity of the solvent is, the higher the oxidation potential of the solvent is, so that the oxidation potential has great significance for preventing overcharge and safety of the battery. Therefore, the electronic grade (purity is 99.99% and above) diethyl carbonate and ethylmethyl carbonate products are produced, the content of impurities such as moisture, methanol and the like is strictly controlled, and the method has great significance on the performance of the lithium battery.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a device and a process for co-producing electronic grade methyl ethyl carbonate and diethyl carbonate by a reactive distillation method.
The invention provides a device for co-producing electronic grade methyl ethyl carbonate and diethyl carbonate by a reaction rectification method, which comprises the following components: the reaction rectifying unit, the dimethyl carbonate and methanol separating unit and the methyl ethyl carbonate and diethyl carbonate separating and purifying unit;
the reaction rectifying unit comprises a reaction rectifying tower feeding buffer tank, a reaction rectifying tower and a filter press; the dimethyl carbonate and methanol separation unit comprises a dimethyl carbonate pressurizing and refining tower, a methanol refining tower and a dimethyl carbonate refining tower; the separation and purification unit for the methyl ethyl carbonate and the diethyl carbonate comprises a raw diethyl carbonate feeding buffer tank, a diethyl carbonate raw separation tower, a diethyl carbonate refining and purifying tower, a raw methyl ethyl carbonate feeding buffer tank, a methyl ethyl carbonate raw separation tower and a methyl ethyl carbonate refining and purifying tower.
Wherein the reaction rectifying tower feeding buffer tank is provided with an ethanol feeding port, a catalyst feeding port and a discharging port; the reaction rectifying tower is provided with a fresh dimethyl carbonate feed inlet, a catalyst and ethanol mixing feed inlet, a dimethyl carbonate and methanol azeotrope feed inlet, a tower top extraction outlet and a tower bottom extraction outlet; the filter press is provided with a liquid phase feed inlet, a carbon dioxide feed inlet and a filtrate outlet; the discharge port of the reaction rectifying tower feeding buffer tank is connected with the catalyst and ethanol mixing feed port, and the bottom extraction port of the reaction rectifying tower is connected with the liquid phase feed port of the filter press.
The raw diethyl carbonate feeding buffer tank is provided with a discharge port and three feed inlets; the diethyl carbonate crude separation tower is provided with a side feed inlet, a tower top discharge outlet and a tower bottom discharge outlet; the diethyl carbonate refining and purifying tower is provided with a side feed port, a top discharge port, a bottom discharge port and a side extraction port; the three feed inlets of the raw diethyl carbonate feed buffer tank are respectively connected with a filtrate outlet of the filter press, a top discharge port of the diethyl carbonate refining and purifying tower and a bottom discharge port of the diethyl carbonate refining and purifying tower; the bottom discharge port of the diethyl carbonate crude separation tower is connected with the side feed port of the diethyl carbonate refining and purifying tower;
the coarse methyl ethyl carbonate feeding buffer tank is provided with a discharge port and three feed inlets; the methyl ethyl carbonate crude separation tower is provided with a side feed inlet, a tower top discharge outlet and a tower bottom discharge outlet; the methyl ethyl carbonate refining and purifying tower is provided with a side feed inlet, a top discharge outlet, a bottom discharge outlet and a side extraction outlet; the three feed inlets of the crude methyl ethyl carbonate feed buffer tank are respectively connected with the top discharge port of the diethyl carbonate crude separation tower, the top discharge port of the methyl ethyl carbonate refining and purifying tower and the bottom discharge port of the methyl ethyl carbonate refining and purifying tower; the top discharge port of the methyl ethyl carbonate crude separation tower is connected with the dimethyl carbonate and methanol azeotrope feed port of the reaction rectifying tower; and a bottom discharge port of the methyl ethyl carbonate crude separation tower is connected with a side feed inlet of the methyl ethyl carbonate refining and purifying tower.
The dimethyl carbonate pressurizing refining tower is provided with a side feed inlet, a tower top extraction outlet and a tower bottom extraction outlet; the dimethyl carbonate refining tower is provided with a side feed inlet, a side extraction outlet, a tower top extraction outlet and a tower bottom extraction outlet; the methanol refining tower is provided with a side feed inlet, a top discharge outlet and a bottom discharge outlet; the side inlet of the dimethyl carbonate pressurizing and refining tower is connected with the top outlet of the reaction rectifying tower; the side feed inlet of the dimethyl carbonate refining tower is connected with the bottom extraction outlet of the dimethyl carbonate pressurizing refining tower; and a top discharge hole of the methanol refining tower is connected with a dimethyl carbonate and methanol azeotrope feed inlet of the reaction rectifying tower.
The invention also provides a process for producing electronic grade methyl ethyl carbonate and diethyl carbonate by adopting the device, which comprises the following steps:
s1, a certain amount of catalyst and ethanol respectively enter a reaction rectifying tower feed buffer tank from an ethanol feed port and a catalyst feed port of the reaction rectifying tower feed buffer tank, are uniformly mixed in the reaction rectifying tower feed buffer tank, then are sent into a reaction rectifying tower through a catalyst and ethanol mixed feed port at the lower side, a certain amount of dimethyl carbonate enters the reaction rectifying tower through a fresh dimethyl carbonate feed port at the upper side, dimethyl carbonate and ethanol in the reaction rectifying tower are subjected to two-step transesterification under the action of the catalyst, the first step is that the dimethyl carbonate and the ethanol are subjected to transesterification to generate methyl ethyl carbonate and methanol, the second step is that the generated methyl ethyl carbonate and the ethanol are continuously subjected to transesterification to generate diethyl carbonate and methanol, and after the two-step transesterification, the reaction rectifying tower contains unreacted complete dimethyl carbonate and ethanol, methyl ethyl carbonate, diethyl carbonate, water and the catalyst, and the dimethyl carbonate and methanol substances at the top of the reaction rectifying tower enter an azeotropic separation unit; the mixture of dimethyl carbonate, ethanol, methyl ethyl carbonate, diethyl carbonate, water and a catalyst is extracted from the bottom of the reaction rectifying tower and enters the methyl ethyl carbonate and diethyl carbonate separation and purification unit;
s2, enabling the dimethyl carbonate and methanol azeotrope obtained in the step 1 to enter a dimethyl carbonate pressurizing and refining tower, enabling the dimethyl carbonate and methanol azeotrope with higher methanol content obtained at the top of the dimethyl carbonate pressurizing and refining tower to enter a methanol refining tower, enabling the bottom of the methanol refining tower to obtain qualified byproduct methanol, and enabling the dimethyl carbonate and methanol azeotrope obtained at the top of the methanol refining tower to return to a reaction rectifying tower; the high-concentration dimethyl carbonate is extracted from the bottom of the dimethyl carbonate pressurizing refining tower and enters the dimethyl carbonate refining tower, the high-purity dimethyl carbonate is extracted from the lateral line of the dimethyl carbonate refining tower, and the dimethyl carbonate is extracted from the top and the bottom of the dimethyl carbonate refining tower and enters a tank area;
s3, enabling the mixture of the dimethyl carbonate, the ethanol, the methyl ethyl carbonate, the diethyl carbonate, the water and the catalyst which are obtained in the step 1 to enter a filter press, enabling the mixture to react with carbon dioxide in the filter press to generate alkali metal salt, removing the alkali metal salt after filter pressing, enabling filtrate to enter a diethyl carbonate crude separation tower through a crude diethyl carbonate feeding buffer tank, enabling a liquid phase obtained from the bottom of the diethyl carbonate crude separation tower to enter a diethyl carbonate refining and purifying tower, and enabling a lateral line of the diethyl carbonate refining and purifying tower to obtain an electronic grade diethyl carbonate product; the tower top and tower bottom extracts of the diethyl carbonate refining and purifying tower are circulated to a raw diethyl carbonate feeding buffer tank for continuous treatment; feeding a material rich in methyl ethyl carbonate extracted from the top of the diethyl carbonate crude separation tower into a methyl ethyl carbonate crude separation tower through the crude methyl ethyl carbonate feeding buffer tank, and recycling the material rich in dimethyl carbonate extracted from the top of the methyl ethyl carbonate crude separation tower to the reaction rectifying tower; and the ethyl methyl carbonate-rich material extracted from the bottom of the ethyl methyl carbonate crude separation tower enters the ethyl methyl carbonate refining and purifying tower, the electronic grade ethyl methyl carbonate product is extracted from the side line of the ethyl methyl carbonate refining and purifying tower, and the tower top and tower bottom extracts of the ethyl methyl carbonate refining and purifying tower are recycled to the crude ethyl methyl carbonate feeding buffer tank for continuous treatment.
Preferably, the catalyst is an alkali metal or alkali metal salt; the addition amount of the catalyst is 0.1-2.0% of the total mass of the dimethyl carbonate and ethanol; the feeding mole ratio of the dimethyl carbonate to the ethanol is 1.05-1.3; the theoretical plate number of the reactive rectifying tower is 60-100, wherein the plate number of the reactive section accounts for 70% of the total theoretical plate number, the rectifying section adopts structured packing, the reactive section adopts tower plates, the operating pressure is 0.10-0.25Mpa, and the reflux ratio is 2-6.
Preferably, the operation pressure of the dimethyl carbonate pressurizing and refining tower is 0.5-0.8Mpa, and the reflux ratio is 1.0-2.0; the operation pressure of the dimethyl carbonate refining tower is normal pressure, and the reflux ratio is 20-40; the operating pressure of the methanol refining tower is normal pressure, and the reflux ratio is 2-5; the mass fraction of the methanol extracted from the bottom of the methanol refining tower is 99.9% or more; the mass fraction of the side-stream extraction of the dimethyl carbonate refining tower is 99.9% or more of dimethyl carbonate.
Preferably, the operation pressure of the diethyl carbonate crude separation tower is 0.10-0.35Mpa, and the reflux ratio is 1-3; the diethyl carbonate refining and purifying tower is a partition type rectifying tower, the operating pressure is 0.01-0.05Mpa, and the reflux ratio is 8-20; and the mass fraction of the side-stream extraction of the diethyl carbonate refining and purifying tower is 99.99% or more of diethyl carbonate products.
Preferably, the operation pressure of the methyl ethyl carbonate crude separation tower is 0.10-0.20Mpa, and the reflux ratio is 2-8; the operation pressure of the methyl ethyl carbonate refining and purifying tower is 0.01-0.05Mpa, and the reflux ratio is 20-30; and the mass fraction of the side stream of the ethyl methyl carbonate refining and purifying tower is 99.99% or more of ethyl methyl carbonate product.
Preferably, the dimethyl carbonate and the methanol azeotrope which are extracted from the top of the methanol refining tower are returned to the reaction section of the reactive rectifying tower, and the mass flow of the dimethyl carbonate and the methanol azeotrope which are extracted from the top of the methanol refining tower accounts for 40-60% of the total mass flow of the feeding material of the methanol refining tower; and the material rich in dimethyl carbonate, which is extracted from the top of the methyl ethyl carbonate crude separation tower, is returned to the reaction section of the reaction rectifying tower, and the mass flow of the material rich in dimethyl carbonate, which is extracted from the top of the reaction rectifying tower, accounts for 10-35% of the total mass flow of the material fed into the methyl ethyl carbonate crude separation tower.
Preferably, the tower top and tower bottom extracts of the diethyl carbonate refining and purifying tower are recycled to the crude diethyl carbonate feeding buffer tank, and the mass flow of the materials extracted from the tower top and the tower bottom accounts for 10-45% of the total mass flow of the materials fed to the diethyl carbonate refining and purifying tower; and the tower top and tower bottom extracts of the methyl ethyl carbonate refining and purifying tower are recycled to the crude methyl ethyl carbonate feeding buffer tank, and the mass flow of the materials extracted from the tower top and the tower bottom accounts for 3-30% of the total mass flow of the feeding of the methyl ethyl carbonate refining and purifying tower.
Preferably, the catalyst is specifically sodium methoxide, sodium ethoxide, sodium methoxide methanol solution or sodium ethoxide ethanol solution.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, industrial grade dimethyl carbonate and absolute ethyl alcohol are used as raw materials, reaction rectification is adopted to couple continuous rectification to co-produce electronic grade methyl ethyl carbonate and diethyl carbonate, the yield and purity of the methyl ethyl carbonate and the diethyl carbonate are flexibly adjusted by reasonably controlling the proportion of the dimethyl carbonate and the ethanol and the operation conditions of each tower, and a plurality of intermediate circulating flow strands are reasonably arranged to improve the conversion rate of the dimethyl carbonate. The invention has reasonable process flow and high utilization rate of raw materials, and realizes one set of production of two electronic grade carbonic ester products.
2. The invention takes excessive dimethyl carbonate and absolute ethyl alcohol as raw materials, adopts high-performance alkali metal catalyst, and flexibly adjusts the yield of methyl ethyl carbonate and diethyl carbonate by reasonably controlling the raw material feed proportion and the operation condition of a reaction rectifying tower.
3. The invention adopts a partition type rectifying tower in the ethyl methyl carbonate and diethyl carbonate refining and purifying unit, and the purity of ethyl methyl carbonate and diethyl carbonate products reaching 99.99% or above are extracted from the side line, so that the number of the rectifying towers is reduced, and the equipment investment cost and the energy consumption are reduced.
4. According to the invention, a plurality of intermediate circulating flow strands are reasonably arranged, and unreacted dimethyl carbonate is efficiently recycled to the reaction rectifying tower for cyclic utilization, so that the utilization rate of raw materials is effectively improved, and the material consumption is reduced.
5. The invention adopts carbon dioxide to recycle the catalyst and byproducts metal carbonate, thereby avoiding the catalyst from entering the product to influence the purity of the product.
6. The invention has reasonable process flow, good effect and high conversion rate, realizes the simultaneous production of two carbonate products in one set of device, and ensures that the purity of the products reaches the electronic grade requirement (the purity is 99.99 percent or more) in the relevant standard.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic diagram of an apparatus and a process for co-producing electronic grade methylethyl carbonate and diethyl carbonate by a reactive distillation method according to an embodiment of the present invention.
Wherein, the V1-reaction rectifying tower feeding buffer tank, the T1-reaction rectifying tower, the M1-filter press, the V2-crude diethyl carbonate feeding buffer tank, the T2-diethyl carbonate crude separation tower, the T3-diethyl carbonate refining and purifying tower, the V3-crude methyl ethyl carbonate feeding buffer tank, the T4-methyl ethyl carbonate crude separation tower, the T5-methyl ethyl carbonate refining and purifying tower, the T6-dimethyl carbonate pressurization and purifying tower, the T7-dimethyl carbonate refining tower and the T8-methanol refining tower.
1-catalyst, 2-absolute ethyl alcohol, 3-industrial grade dimethyl carbonate, 4-carbon dioxide, 5-metal carbonate filter residues, 6-electronic grade diethyl carbonate products, 7-electronic grade methyl ethyl carbonate products, 8-high-purity dimethyl carbonate and 9-methanol.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
Example 1
Referring to fig. 1, an apparatus for co-producing electronic grade methylethyl carbonate and diethyl carbonate by a reactive distillation method comprises: the reaction rectifying unit, the dimethyl carbonate and methanol separating unit and the methyl ethyl carbonate and diethyl carbonate separating and purifying unit;
the reaction rectifying unit comprises a reaction rectifying tower feeding buffer tank V1, a reaction rectifying tower T1 and a filter press M1; the dimethyl carbonate and methanol separation unit comprises a dimethyl carbonate pressurizing and refining tower T6, a methanol refining tower T8 and a dimethyl carbonate refining tower T7; the separation and purification unit for the methyl ethyl carbonate and the diethyl carbonate comprises a raw diethyl carbonate feeding buffer tank V2, a diethyl carbonate raw separation tower T2, a diethyl carbonate refining and purifying tower T3, a raw methyl ethyl carbonate feeding buffer tank V3, a methyl ethyl carbonate raw separation tower T4 and a methyl ethyl carbonate refining and purifying tower T5.
Wherein the reaction rectifying tower feeding buffer tank V1 is provided with an ethanol feeding port, a catalyst feeding port and a discharging port; the reaction rectifying tower T1 is provided with a fresh dimethyl carbonate feed inlet, a catalyst and ethanol mixing feed inlet, a dimethyl carbonate and methanol azeotrope feed inlet, a tower top extraction outlet and a tower bottom extraction outlet; the filter press M1 is provided with a liquid phase feed inlet, a carbon dioxide feed inlet and a filtrate outlet; the discharge port of the reaction rectifying tower feeding buffer tank V1 is connected with the catalyst and ethanol mixing feed port, and the bottom extraction port of the reaction rectifying tower T1 is connected with the liquid phase feed port of the filter press M1.
The raw diethyl carbonate feeding buffer tank V2 is provided with a discharge port and three feed inlets; the diethyl carbonate crude separation tower T2 is provided with a side feed inlet, a top discharge outlet and a bottom discharge outlet; the diethyl carbonate refining and purifying tower T3 is provided with a side feed inlet, a top discharge outlet, a bottom discharge outlet and a side extraction outlet; the three feed inlets of the raw diethyl carbonate feed buffer tank V2 are respectively connected with a filtrate outlet of the filter press M1, a top discharge port of the diethyl carbonate refining and purifying tower T3 and a bottom discharge port of the diethyl carbonate refining and purifying tower T3; the bottom discharge port of the diethyl carbonate crude separation tower T2 is connected with the side feed port of the diethyl carbonate refining and purifying tower T3.
The coarse methyl ethyl carbonate feeding buffer tank V3 is provided with a discharge port and three feed inlets; the methyl ethyl carbonate crude separation tower T4 is provided with a side feed inlet, a top discharge outlet and a bottom discharge outlet; the ethyl methyl carbonate refining and purifying tower T5 is provided with a side feed inlet, a top discharge outlet, a bottom discharge outlet and a side extraction outlet; the three feed inlets of the coarse methyl ethyl carbonate feed buffer tank V3 are respectively connected with the top discharge port of the diethyl carbonate coarse separation tower T2, the top discharge port of the methyl ethyl carbonate refining and purifying tower T5 and the bottom discharge port of the methyl ethyl carbonate refining and purifying tower T5; the top discharge port of the methyl ethyl carbonate crude separation tower T4 is connected with the dimethyl carbonate and methanol azeotrope feed port of the reaction rectifying tower T1; the bottom discharge port of the methyl ethyl carbonate crude separation tower T4 is connected with the side feed port of the methyl ethyl carbonate refining and purifying tower T5.
The dimethyl carbonate pressurizing and refining tower T6 is provided with a side feed inlet, a tower top extraction outlet and a tower bottom extraction outlet; the dimethyl carbonate refining tower T7 is provided with a side feed inlet, a side extraction outlet, a tower top extraction outlet and a tower bottom extraction outlet; the methanol refining tower T8 is provided with a side feed inlet, a top discharge outlet and a bottom discharge outlet; the side inlet of the dimethyl carbonate pressurizing and refining tower (T6) is connected with the top outlet of the reaction rectifying tower T1, the side inlet of the dimethyl carbonate refining tower T7 is connected with the bottom outlet of the dimethyl carbonate pressurizing and refining tower T6, and the top outlet of the methanol refining tower T8 is connected with the dimethyl carbonate and methanol azeotrope inlet of the reaction rectifying tower T1.
Example 2
Referring to fig. 1, a process for co-producing electronic grade methylethyl carbonate and diethyl carbonate by reactive distillation, employing the apparatus of example 1, comprises the steps of:
s1, a sodium methoxide-methanol solution (29% of sodium methoxide by mass) with a feed flow rate of 6kg/h and absolute ethyl alcohol 2 with a feed flow rate of 394kg/h enter a feed buffer tank V1 of a reaction rectifying tower, the catalyst and the ethanol are mixed uniformly in the feed buffer tank V1 of the reaction rectifying tower and then are sent into the reaction rectifying tower T1 through a mixing feed inlet of the catalyst on the lower side, industrial grade dimethyl carbonate 3 with the feed flow rate of 820kg/h enters the reaction rectifying tower T1 from a fresh dimethyl carbonate feed inlet on the upper side, the theoretical plate number of the reaction rectifying tower T1 is 76, the operating pressure is 0.12Mpa, a packing section is 24, a tower plate section is 50, the mass reflux ratio is 3.8, dimethyl carbonate and ethanol in the reaction rectifying tower T1 undergo two-step transesterification reaction under the action of the catalyst, the first step is that dimethyl carbonate and ethanol undergo transesterification reaction to generate methyl carbonate and methanol, the second step is that the dimethyl carbonate and ethanol undergo transesterification reaction to generate diethyl carbonate and methanol, the methyl carbonate and the methyl carbonate which are completely separated from the top of the reaction rectifying tower T1 and the methyl carbonate and the methanol which are completely separated from the methyl carbonate and the methanol which are completely distilled from the methanol and the methanol which are completely distilled from the top of the reaction rectifying tower T1; 840kg/h of methyl ethyl carbonate, diethyl carbonate, water, catalyst and a small amount of dimethyl carbonate and methanol are extracted from the bottom of the reaction rectifying tower T1 and enter the methyl ethyl carbonate and diethyl carbonate separation and purification unit;
s2, enabling 380kg/h dimethyl carbonate and methanol azeotrope obtained in the step 1 to enter a dimethyl carbonate pressurizing and refining tower T6, enabling the operation pressure of the dimethyl carbonate pressurizing and refining tower T6 to be 0.6Mpa, enabling the theoretical plate number to be 42, enabling the mass reflux ratio to be 1.2, enabling 293kg/h dimethyl carbonate and methanol azeotrope with 94% methanol content obtained from the top of the dimethyl carbonate pressurizing and refining tower T6 to enter a methanol refining tower T8; the operating pressure of the methanol refining tower T8 is 0.11Mpa, the theoretical plate number is 42, and the reflux ratio is 4; the bottom of the methanol refining tower T8 is used for extracting methanol 9 with the mass fraction of 99.92 percent, and the flow is 133kg/h; 160kg/h of dimethyl carbonate and methanol azeotrope extracted from the top of the methanol refining tower T8 are returned to the reaction rectifying tower T1; 87kg/h of dimethyl carbonate with the mass fraction of 95% is extracted from the bottom of the dimethyl carbonate pressurizing and refining tower T6 and enters a dimethyl carbonate refining tower T7; the operation pressure of the dimethyl carbonate refining tower T7 is 0.12Mpa, the theoretical plate number is 42, the mass reflux ratio is 30, the side extraction outlet of the dimethyl carbonate refining tower T7 is positioned on the 10 th theoretical plate, 70kg/h of high-purity dimethyl carbonate 8 with the mass fraction of 99.93% and the top and bottom of the dimethyl carbonate refining tower T7 are extracted from the side line of the dimethyl carbonate refining tower T7, and 17kg/h of dimethyl carbonate with the mass fraction of 95% is extracted from the total tower top and tower bottom of the dimethyl carbonate refining tower T7 and enters a tank area;
s3, allowing 840kg/h of mixture of dimethyl carbonate, ethanol, methyl ethyl carbonate, diethyl carbonate, water and catalyst which are obtained in the step 1 to enter a filter press M1, reacting with carbon dioxide 4 in the filter press M1 to generate alkali metal salt, removing the alkali metal salt after filter pressing to obtain metal carbonate filter residues 5, and allowing filtrate to enter a diethyl carbonate crude separation tower T2 through a crude diethyl carbonate feeding buffer tank V2; the operation pressure of the diethyl carbonate crude separation tower T2 is 0.12Mpa, the mass reflux ratio is 1.5, and the theoretical plate number is 74; 190kg/h of diethyl carbonate solution with the mass fraction of 95.4% extracted from the bottom of the diethyl carbonate crude separation tower T2 enters a diethyl carbonate refining and purifying tower T3, 650kg/h of ethyl methyl carbonate material with the mass fraction of 86.8% extracted from the top of the diethyl carbonate crude separation tower T2 enters a ethyl methyl carbonate crude separation tower T4 through a crude ethyl methyl carbonate feeding buffer tank V3; the diethyl carbonate refining and purifying tower T3 adopts a partition type packing tower, the operation pressure of two tower chambers is 0.02Mpa, the number of theoretical plates is 32, the mass reflux ratio is 15, 110kg/h of electronic grade diethyl carbonate product 6 with the mass fraction of 99.99% is extracted from the side line of the diethyl carbonate refining and purifying tower T3, 80kg/h of diethyl carbonate-containing material is extracted from the tower top and the tower bottom of the diethyl carbonate refining and purifying tower T3, and the diethyl carbonate-containing material is returned to the coarse diethyl carbonate feeding buffer tank V2 for continuous treatment; the operation pressure of the methyl ethyl carbonate crude separation tower T4 is 0.12Mpa, the theoretical plate number is 34, the mass reflux ratio is 3, 150kg/h of dimethyl carbonate-rich material extracted from the top of the methyl ethyl carbonate crude separation tower T4 is circulated to the reactive distillation tower T1; 500kg/h of ethyl methyl carbonate material with the mass fraction of 95.1% is extracted from the bottom of the ethyl methyl carbonate crude separation tower T4 and enters the ethyl methyl carbonate refining and purifying tower T5; the ethyl methyl carbonate refining and purifying tower T5 adopts a partition type packing tower, the operating pressure of two tower chambers is 0.02Mpa, the mass reflux ratio is 20, the theoretical plates are 52, 355kg/h of electronic grade ethyl methyl carbonate product 7 with the mass fraction of 99.99% is extracted from the 42 th plate side of the ethyl methyl carbonate refining and purifying tower T5, 145kg/h of materials are extracted from the tower top and the tower bottom of the ethyl methyl carbonate refining and purifying tower T5 in total, and the materials are circulated to the raw ethyl methyl carbonate feeding buffer tank V3 for continuous circulation treatment.
Example 3
Referring to fig. 1, a process for co-producing electronic grade methylethyl carbonate and diethyl carbonate by reactive distillation, employing the apparatus of example 1, comprises the steps of:
s1, a sodium ethoxide-ethanol solution (the mass fraction of sodium ethoxide is 29%) with the feed flow rate of 6kg/h, a catalyst 1 and an absolute ethanol 2 with the feed flow rate of 396kg/h enter a feed buffer tank V1 of a reaction rectifying tower, the catalyst and the ethanol are mixed uniformly in the feed buffer tank V1 of the reaction rectifying tower, the catalyst and the ethanol are mixed through a feed inlet on the lower side and are sent into the reaction rectifying tower T1, an industrial grade dimethyl carbonate 3 with the feed flow rate of 820kg/h enters the reaction rectifying tower T1 from a fresh dimethyl carbonate feed inlet on the upper side, the theoretical plate number of the reaction rectifying tower T1 is 82, the operating pressure is 0.12Mpa, a packing section is 32, a tower plate section is 50, the mass reflux ratio is 3.8, the dimethyl carbonate and the ethanol in the reaction rectifying tower T1 undergo two-step transesterification reaction under the action of the catalyst, the first step is that dimethyl carbonate and ethanol undergo transesterification reaction to generate methyl carbonate and methanol, the second step is that the dimethyl carbonate and ethanol undergo transesterification reaction to generate diethyl carbonate and methanol, the methyl carbonate and the ethyl carbonate which are completely separated from the top of the reaction rectifying tower T1, the methyl carbonate and the methyl carbonate is completely distilled from the top of the reaction rectifying tower, the methyl carbonate and the methyl carbonate is completely distilled from the top of the reaction rectifying tower, and the methyl carbonate is completely distilled from the methyl carbonate and the methyl carbonate; 835kg/h of methyl ethyl carbonate, diethyl carbonate, water, catalyst and a small amount of dimethyl carbonate and methanol which are extracted from the bottom of the reaction rectifying tower T1 enter the methyl ethyl carbonate and diethyl carbonate separation and purification unit;
s2, 387kg/h of dimethyl carbonate and methanol azeotrope extracted in the step 1 enter a dimethyl carbonate pressurizing and refining tower T6, the operation pressure of the dimethyl carbonate pressurizing and refining tower T6 is 0.6Mpa, the theoretical plate number is 42, the mass reflux ratio is 1.2, 295kg/h of dimethyl carbonate and methanol azeotrope with the methanol content of 94% are extracted from the top of the dimethyl carbonate pressurizing and refining tower T6 and enter a methanol refining tower T8; the operating pressure of the methanol refining tower T8 is 0.11Mpa, the theoretical plate number is 42, and the reflux ratio is 4; the bottom of the methanol refining tower T8 is used for extracting methanol 9 with the mass fraction of 99.92 percent, and the flow is 161kg/h; 134kg/h of dimethyl carbonate and methanol azeotrope extracted from the top of the methanol refining tower T8 are returned to the reaction rectifying tower T1; 92kg/h of dimethyl carbonate with the mass fraction of 98.7% is extracted from the bottom of the dimethyl carbonate pressurizing and refining tower T6 and enters the dimethyl carbonate refining tower T7; the operation pressure of the dimethyl carbonate refining tower T7 is 0.12Mpa, the theoretical plate number is 42, the mass reflux ratio is 30, the side extraction outlet of the dimethyl carbonate refining tower T7 is positioned on the 10 th theoretical plate, 85kg/h of high-purity dimethyl carbonate 8 with the mass fraction of 99.99% and the quality fraction of 83.2% is extracted from the side line of the dimethyl carbonate refining tower T7, and 7kg/h of dimethyl carbonate is extracted from the total tower top and tower bottom of the dimethyl carbonate refining tower T7 and enters a tank area;
s3, 835kg/h of dimethyl carbonate, ethanol, methyl ethyl carbonate, diethyl carbonate, water and catalyst mixture obtained in the step 1 enter a filter press M1, alkali metal salt generated by reaction with carbon dioxide 4 in the filter press M1 is removed after filter pressing to obtain metal carbonate filter residues 5, and filtrate enters a diethyl carbonate crude separation tower T2 through a crude diethyl carbonate feeding buffer tank V2; the operation pressure of the diethyl carbonate crude separation tower T2 is 0.12Mpa, the mass reflux ratio is 1.5, and the theoretical plate number is 74; 188kg/h of diethyl carbonate solution with the mass fraction of 99.3% is extracted from the bottom of the diethyl carbonate crude separation tower T2 and enters the diethyl carbonate refining and purifying tower T3, 647kg/h of methyl ethyl carbonate material with the mass fraction of 89.1% is extracted from the top of the diethyl carbonate crude separation tower T2 and enters the methyl ethyl carbonate crude separation tower T4 through the crude methyl ethyl carbonate feeding buffer tank V3; the diethyl carbonate refining and purifying tower T3 adopts a partition type packing tower, the operation pressure of two tower chambers is 0.02Mpa, the number of theoretical plates is 32, the mass reflux ratio is 11, 160kg/h of electronic grade diethyl carbonate product 6 with the mass fraction of 99.99% is extracted from the side line of the diethyl carbonate refining and purifying tower T3, 28kg/h of diethyl carbonate-containing material is extracted from the tower top and the tower bottom of the diethyl carbonate refining and purifying tower T3, and the diethyl carbonate-containing material is returned to the coarse diethyl carbonate feeding buffer tank V2 for continuous treatment; the operation pressure of the methyl ethyl carbonate crude separation tower T4 is 0.12Mpa, the theoretical plate number is 34, the mass reflux ratio is 3, 125kg/h of material with 56.4% of dimethyl carbonate is extracted from the top of the methyl ethyl carbonate crude separation tower T4, and the material is circulated to the reactive rectifying tower T1; 522kg/h of ethyl methyl carbonate materials with the mass fraction of 99.8% are extracted from the bottom of the ethyl methyl carbonate crude separation tower T4 and enter the ethyl methyl carbonate refining and purifying tower T5; the ethyl methyl carbonate refining and purifying tower T5 adopts a partition type packing tower, the operating pressure of two tower chambers is 0.02Mpa, the mass reflux ratio is 15, the theoretical plates are 52, the 45 th plate side of the ethyl methyl carbonate refining and purifying tower T5 extracts 501kg/h of electronic grade ethyl methyl carbonate product 7, the total mass fraction of the top and the bottom of the ethyl methyl carbonate refining and purifying tower T5 extracts 21kg/h of materials, and the materials are circulated to a crude ethyl methyl carbonate feeding buffer tank V3 for continuous circulation treatment.
The foregoing is only the embodiments of the present invention, and therefore, the patent scope of the invention is not limited thereto, and all equivalent structures made by the description of the invention and the accompanying drawings are directly or indirectly applied to other related technical fields, which are all within the scope of the invention.
Claims (7)
1. A process for co-producing electronic grade methyl ethyl carbonate and diethyl carbonate by a reaction rectification method is characterized in that the device comprises: the reaction rectifying unit, the dimethyl carbonate and methanol separating unit and the methyl ethyl carbonate and diethyl carbonate separating and purifying unit;
the reaction rectifying unit comprises a reaction rectifying tower feeding buffer tank (V1), a reaction rectifying tower (T1) and a filter press (M1); the dimethyl carbonate and methanol separation unit comprises a dimethyl carbonate pressurizing and refining tower (T6), a methanol refining tower (T8) and a dimethyl carbonate refining tower (T7); the separation and purification unit of the methyl ethyl carbonate and the diethyl carbonate comprises a raw diethyl carbonate feeding buffer tank (V2), a diethyl carbonate raw separation tower (T2), a diethyl carbonate refining and purifying tower (T3), a raw methyl ethyl carbonate feeding buffer tank (V3), a methyl ethyl carbonate raw separation tower (T4) and a methyl ethyl carbonate refining and purifying tower (T5);
wherein the reaction rectifying tower feeding buffer tank (V1) is provided with an ethanol feeding port, a catalyst feeding port and a discharge port; the reaction rectifying tower (T1) is provided with a fresh dimethyl carbonate feed inlet, a catalyst and ethanol mixing feed inlet, a dimethyl carbonate and methanol azeotrope feed inlet, a tower top extraction outlet and a tower bottom extraction outlet; the filter press (M1) is provided with a liquid phase feed inlet, a carbon dioxide feed inlet and a filtrate outlet; the discharge port of the reaction rectifying tower feeding buffer tank (V1) is connected with the catalyst and ethanol mixing feed port, and the bottom discharge port of the reaction rectifying tower (T1) is connected with the liquid phase feed port of the filter press (M1);
the raw diethyl carbonate feeding buffer tank (V2) is provided with a discharge port and three feed inlets; the diethyl carbonate crude separation tower (T2) is provided with a side feed inlet, a tower top discharge outlet and a tower bottom discharge outlet; the diethyl carbonate refining and purifying tower (T3) is provided with a side feed inlet, a top discharge outlet, a bottom discharge outlet and a side extraction outlet; three feed inlets of the coarse diethyl carbonate feed buffer tank (V2) are respectively connected with a filtrate outlet of the filter press (M1), a top discharge outlet of the diethyl carbonate refining and purifying tower (T3) and a bottom discharge outlet of the diethyl carbonate refining and purifying tower (T3); the bottom discharge port of the diethyl carbonate crude separation tower (T2) is connected with the side feed port of the diethyl carbonate refining and purifying tower (T3); the diethyl carbonate refining and purifying tower (T3) is a dividing wall type rectifying tower;
the coarse methyl ethyl carbonate feeding buffer tank (V3) is provided with a discharge port and three feed inlets; the methyl ethyl carbonate crude separation tower (T4) is provided with a side feed inlet, a tower top discharge outlet and a tower bottom discharge outlet; the methyl ethyl carbonate refining and purifying tower (T5) is provided with a side feed inlet, a top discharge outlet, a bottom discharge outlet and a side extraction outlet; three feed inlets of the coarse ethyl methyl carbonate feed buffer tank (V3) are respectively connected with a top discharge port of the diethyl carbonate coarse separation tower (T2), a top discharge port of the ethyl methyl carbonate refining and purifying tower (T5) and a bottom discharge port of the ethyl methyl carbonate refining and purifying tower (T5); the top discharge port of the methyl ethyl carbonate crude separation tower (T4) is connected with the dimethyl carbonate and methanol azeotrope feed port of the reaction rectifying tower (T1); the bottom discharge port of the methyl ethyl carbonate crude separation tower (T4) is connected with the side feed port of the methyl ethyl carbonate refining and purifying tower (T5); the methyl ethyl carbonate refining and purifying tower (T5) adopts a partition type packing tower;
the dimethyl carbonate pressurizing and refining tower (T6) is provided with a side feed inlet, a tower top extraction outlet and a tower bottom extraction outlet; the dimethyl carbonate refining tower (T7) is provided with a side feed inlet, a side extraction outlet, a tower top extraction outlet and a tower bottom extraction outlet; the methanol refining tower (T8) is provided with a side feed inlet, a top discharge outlet and a bottom discharge outlet; the side inlet of the dimethyl carbonate pressurizing and refining tower (T6) is connected with the top extraction outlet of the reaction rectifying tower (T1); a side inlet of the dimethyl carbonate refining tower (T7) is connected with a bottom extraction outlet of the dimethyl carbonate pressurizing refining tower (T6); the top discharge port of the methanol refining tower (T8) is connected with the dimethyl carbonate and methanol azeotrope feed port of the reaction rectifying tower (T1);
the process comprises the following steps:
s1, a certain amount of catalyst and ethanol respectively enter a reaction rectifying tower feed buffer tank (V1) from an ethanol feed port and a catalyst feed port of the reaction rectifying tower feed buffer tank (V1), after being uniformly mixed in the reaction rectifying tower feed buffer tank (V1), the catalyst and ethanol are fed into the reaction rectifying tower (T1) through a catalyst and ethanol mixed feed port on the lower side, a certain amount of dimethyl carbonate enters the reaction rectifying tower (T1) through a fresh dimethyl carbonate feed port on the upper side, dimethyl carbonate and ethanol in the reaction rectifying tower (T1) undergo two-step transesterification under the action of the catalyst, the first step is that the dimethyl carbonate and the ethanol undergo transesterification to generate methyl ethyl carbonate and methanol, the second step is that the generated methyl ethyl carbonate and ethanol undergo transesterification to generate diethyl carbonate and methanol, after the two-step transesterification, the reaction rectifying tower (T1) contains unreacted and complete dimethyl carbonate and ethanol, methyl ethyl carbonate, diethyl carbonate, water and the catalyst, and the reaction rectifying tower top (T1) is fed into an azeotropic separation unit; the mixture of dimethyl carbonate, ethanol, methyl ethyl carbonate, diethyl carbonate, water and catalyst is extracted from the bottom of the reaction rectifying tower (T1) and enters the methyl ethyl carbonate and diethyl carbonate separation and purification unit;
s2, enabling the dimethyl carbonate and methanol azeotrope obtained in the step 1 to enter a dimethyl carbonate pressurizing and refining tower (T6), enabling the dimethyl carbonate and methanol azeotrope with higher methanol content obtained from the top of the dimethyl carbonate pressurizing and refining tower (T6) to enter a methanol refining tower (T8), enabling the bottom of the methanol refining tower (T8) to obtain qualified byproduct methanol, and enabling the dimethyl carbonate and methanol azeotrope obtained from the top of the methanol refining tower (T8) to return to a reaction rectifying tower (T1); the high-concentration dimethyl carbonate is extracted from the bottom of the dimethyl carbonate pressurizing refining tower (T6) and enters the dimethyl carbonate refining tower (T7), the high-purity dimethyl carbonate is extracted from the lateral line of the dimethyl carbonate refining tower (T7), and the dimethyl carbonate is extracted from the top and the bottom of the dimethyl carbonate refining tower (T7) and enters a tank area;
s3, enabling the mixture of the dimethyl carbonate, the ethanol, the methyl ethyl carbonate, the diethyl carbonate, the water and the catalyst which are extracted in the step 1 to enter a filter press (M1), enabling the mixture to react with carbon dioxide in the filter press (M1) to generate alkali metal salt, removing the alkali metal salt after the alkali metal salt is filtered, enabling filtrate to enter a diethyl carbonate crude separation tower (T2) through a crude diethyl carbonate feeding buffer tank (V2), enabling a liquid phase extracted from the bottom of the diethyl carbonate crude separation tower (T2) to enter a diethyl carbonate refining and purifying tower (T3), and enabling a side line of the diethyl carbonate refining and purifying tower (T3) to extract an electronic grade diethyl carbonate product; the tower top and tower bottom extracts of the diethyl carbonate refining and purifying tower (T3) are recycled to a crude diethyl carbonate feeding buffer tank (V2) for continuous treatment; the material rich in methyl ethyl carbonate extracted from the top of the diethyl carbonate crude separation tower (T2) enters the methyl ethyl carbonate crude separation tower (T4) through the crude methyl ethyl carbonate feeding buffer tank (V3), and the material rich in dimethyl carbonate extracted from the top of the methyl ethyl carbonate crude separation tower (T4) is circulated to the reaction rectifying tower (T1); the ethyl methyl carbonate-rich material extracted from the bottom of the ethyl methyl carbonate crude separation tower (T4) enters the ethyl methyl carbonate refining and purifying tower (T5), an electronic grade ethyl methyl carbonate product is extracted from the side line of the ethyl methyl carbonate refining and purifying tower (T5), and the tower top and tower bottom extracts of the ethyl methyl carbonate refining and purifying tower (T5) are circulated to a crude ethyl methyl carbonate feeding buffer tank (V3) for continuous treatment;
wherein, the azeotrope of dimethyl carbonate and methanol extracted from the top of the methanol refining tower (T8) returns to the reaction section of the reaction rectifying tower (T1), and the mass flow of the azeotrope of dimethyl carbonate and methanol extracted from the top of the tower accounts for 40-60% of the total mass flow of the feeding of the methanol refining tower (T8); and the dimethyl carbonate-rich material extracted from the top of the methyl ethyl carbonate crude separation tower (T4) is returned to the reaction section of the reaction rectifying tower (T1), and the mass flow of the dimethyl carbonate-rich material extracted from the top of the reaction rectifying tower accounts for 10-35% of the total mass flow of the feed of the methyl ethyl carbonate crude separation tower (T4).
2. The process of claim 1 wherein the catalyst is an alkali metal or alkali metal salt; the addition amount of the catalyst is 0.1-2.0% of the total mass of the dimethyl carbonate and ethanol; the feeding mole ratio of the dimethyl carbonate to the ethanol is 1.05-1.3; the theoretical plate number of the reactive rectifying tower (T1) is 60-100, wherein the plate number of the reactive section accounts for 70% of the total theoretical plate number, the rectifying section adopts structured packing, the reactive section adopts tower plates, the operating pressure is 0.10-0.25Mpa, and the reflux ratio is 2-6.
3. The process according to claim 1, wherein the operation pressure of the dimethyl carbonate pressurized refining column (T6) is 0.5 to 0.8Mpa and the reflux ratio is 1.0 to 2.0; the operation pressure of the dimethyl carbonate refining tower (T7) is normal pressure, and the reflux ratio is 20-40; the operating pressure of the methanol refining tower (T8) is normal pressure, and the reflux ratio is 2-5; the mass fraction of the methanol extracted from the bottom of the methanol refining tower (T8) is 99.9 percent or more; the side-draw mass fraction of the dimethyl carbonate in the dimethyl carbonate purification column (T7) is 99.9% or more.
4. Process according to claim 1, characterized in that the diethyl carbonate crude separation column (T2) is operated at a pressure of 0.10-0.35Mpa and a reflux ratio of 1-3; the operating pressure of the diethyl carbonate refining and purifying tower (T3) is 0.01-0.05Mpa, and the reflux ratio is 8-20; the mass fraction of the side-stream extraction of the diethyl carbonate refining and purifying tower (T3) is 99.99 percent or more of diethyl carbonate products.
5. Process according to claim 1, characterized in that the methyl ethyl carbonate crude separation column (T4) is operated at a pressure of 0.10-0.20Mpa and a reflux ratio of 2-8; the operating pressure of the methyl ethyl carbonate refining and purifying tower (T5) is 0.01-0.05Mpa, and the reflux ratio is 20-30; the mass fraction of the side stream of the methyl ethyl carbonate refining and purifying tower (T5) is 99.99 percent or more of methyl ethyl carbonate products.
6. The process according to claim 1, wherein the top and bottom effluents of the diethyl carbonate purification column (T3) are recycled to the crude diethyl carbonate feed buffer tank (V2) and the mass flow of the material withdrawn from the top and bottom is 10-45% of the total mass flow of the feed to the diethyl carbonate purification column (T3); the tower top and tower bottom extracts of the methyl ethyl carbonate refining and purifying tower (T5) are recycled to the crude methyl ethyl carbonate feeding buffer tank (V3), and the mass flow of the materials extracted from the tower top and the tower bottom accounts for 3-30% of the total mass flow of the feeding of the methyl ethyl carbonate refining and purifying tower (T5).
7. The process according to claim 2, wherein the catalyst is in particular sodium methoxide, sodium ethoxide, sodium methoxide methanol solution or sodium ethoxide ethanol solution.
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