CN114507136A - Efficient synthesis method of lithium ion battery electrolyte mixed solvent - Google Patents
Efficient synthesis method of lithium ion battery electrolyte mixed solvent Download PDFInfo
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Abstract
The invention relates to a high-efficiency synthesis method of a lithium ion battery electrolyte mixed solvent, which takes methanol, ethanol, carbon monoxide and oxygen as raw materials, simultaneously generates products such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and the like under the action of a nano copper catalyst, and the products are separated and purified by a filter, a rectifying tower with a material stream extraction side line, a dimethyl carbonate refining tower, a dehydrating tower, a pressurizing tower and other equipment after being cooled by a quick cooler, namely, the lithium ion battery electrolyte mother liquor product is obtained through the steps of light and weight removal, dimethyl carbonate refining, dimethyl carbonate pressurization, and methyl ethyl carbonate and diethyl carbonate dehydration. In the method, the sample injection ratio of the methanol and the ethanol is adjusted, and the methanol and the ethanol react with oxygen and carbon monoxide to generate the raw materials of the electrolytes such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and the like, so the method has the outstanding advantages of simple process and high reaction efficiency.
Description
Technical Field
The invention belongs to the field of lithium ion battery electrolyte, and particularly relates to a high-efficiency synthesis method of a lithium ion battery electrolyte mixed solvent.
Background
The globalization of energy revolution drives the rapid development of new energy field, and promotes the new energy technology to enter the full-scale outbreak period. In recent years, the demand of new energy automobiles, digital products and energy storage industries for lithium ion batteries is rapidly increased. The lithium ion battery mainly comprises a positive electrode material, a negative electrode material, a diaphragm, electrolyte and the like. The electrolyte is a carrier for ion transmission in the lithium ion battery, and is generally prepared from raw materials such as a high-purity organic solvent, lithium salt, necessary additives and the like according to a certain proportion under a certain condition. The electrolyte of the lithium ion battery is formed by mixing two or more organic solvents according to a certain proportion, and comprises dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC), Ethylene Carbonate (EC), Propylene Carbonate (PC) and the like. Wherein, the chain carbonic ester (DMC, DEC and EMC) has low viscosity and good electrochemical stability and can improve the low-temperature performance of the electrolyte. The mixed solvent composed of DMC, DEC and EMC is a common lithium ion battery electrolyte, and the traditional preparation process comprises the following steps: firstly, respectively synthesizing various high-purity single solvents DMC, DEC and EMC, and then mixing the three solvents according to a proper proportion. For example, in patent CN103413970A, four carbonate solvents consist of EC, DMC, EMC and PC in a mass ratio of 2: 3: 5: 1; in patent CN112366361A, the electrolyte of the lithium ion battery is obtained by uniformly mixing EC, EMC, DMC, DEC and PC in a volume ratio of 1: 1; the lithium ion battery electrolyte in patent CN106785035A comprises 6-8 parts of EC, 6-8 parts of PC, 3-5 parts of DEC, 5-6 parts of DEC, 4-8 parts of ethylene carbonate, 6-8 parts of EMC and 6-8 parts of organic solvent; in patent CN105355977A, the electrolyte of the lithium ion battery consists of EC, EMC, DMC, DEC and butylene sulfite with the mass ratio of 6: 4: 1: 8; in patent CN103682435A, the lithium ion battery electrolyte comprises 27% -36% of EC, 9% -17% of DMC, 8% -16% of DEC, 31% -40% of EMC and the like.
The preparation process is complicated, long in production period and high in separation cost, so that the production efficiency is low, the cost is high and the market competitiveness is poor. Therefore, the development of an economical and efficient lithium ion battery electrolyte preparation process is crucial to the development of new energy technology.
Disclosure of Invention
The invention provides a high-efficiency synthesis method of a lithium ion battery electrolyte mixed solvent, aiming at solving the problems of complex preparation process, long production period and high separation cost in the prior art.
The invention is realized by the following technical scheme: a high-efficiency synthesis method of a lithium ion battery electrolyte mixed solvent comprises the following steps:
(1) reaction preparation: placing methanol, ethanol and a nano copper catalyst in a closed reaction container, introducing carbon monoxide to purge and remove air in the closed reaction container, continuously introducing the carbon monoxide and oxygen after the reaction is finished, heating, preserving heat and stirring for reaction; after the reaction is finished, cooling to room temperature, and discharging gas in the closed reaction container to obtain a reaction product;
(2) light weight removal and heavy weight removal: filtering the obtained reaction product to primarily separate the nano-copper catalyst from the reaction mixed liquid, returning the filtered nano-copper catalyst to the reaction container, and performing a circular reaction;
conveying the reaction mixed liquid to a first rectifying tower with a side line, separating in the first rectifying tower, obtaining light component products containing methylal, acetaldehyde, methyl formate, dimethyl carbonate and methanol at the top of the tower after separation, condensing the light component products by a condenser, and then feeding the light component products into a first light component tank, wherein one part of materials in the tank reflows to the first rectifying tower, and the other part of the materials is fed into a second rectifying tower to refine the dimethyl carbonate;
heavy component products containing diethyl carbonate, ethyl methyl carbonate and water are obtained from the tower bottom of the first rectifying tower, the heavy component products flow into the first heavy component tank, and the heavy component products in the first heavy component tank are conveyed into the dehydrating tower and are dehydrated in the tower;
an azeotropic mixture of ethanol and ethyl acetate on the upper tower wall of the first rectifying tower is extracted from a side line, discharged from a discharge hole at the middle upper part of the tower wall and then sent into an ethanol storage tank for storage;
(3) refining dimethyl carbonate: the feed liquid in the first light component tank is conveyed to a second rectifying tower to carry out secondary separation of methylal, methyl formate and the like, light component products such as methanol and methylal are obtained at the tower top, the light component products enter the second light component tank after being condensed by a condenser, one part of the feed liquid in the second light component tank reflows to the second rectifying tower to be recycled as reflux liquid, and the other part of the feed liquid is sent to a methanol storage tank to be stored; heavy components of dimethyl carbonate containing methanol are obtained at the bottom of the second rectifying tower and are conveyed to a second heavy component tank and then conveyed to the pressurizing tower for further separation;
(4) and (3) dehydrating: diethyl carbonate and methyl ethyl carbonate containing water obtained from the tower kettle of the first rectifying tower enter a dehydrating tower and are dehydrated in the dehydrating tower; obtaining mixed liquid of diethyl carbonate and ethyl methyl carbonate at the tower bottom of a dehydrating tower, conveying the mixed liquid into a third heavy component tank, sending one part of feed liquid in the third heavy component tank into an electrolyte mother liquid tank, heating the other part of the feed liquid by a reboiler, then sending the other part of the feed liquid back into the dehydrating tower, condensing the water mixed liquid with the diethyl carbonate and the ethyl methyl carbonate at the tower top by a tower top condenser, and then conveying the condensed water mixed liquid into a fourth light component tank, wherein one part of the feed liquid in the fourth light component tank is used as reflux liquid to flow back into the dehydrating tower, and the other part of the feed liquid is used as discharged wastewater dehydration treatment process;
(5) and (3) pressurized azeotropic distillation: the material in the second heavy component tank is conveyed into a pressurizing tower, the pressurizing tower is used for pressurizing azeotropic distillation, methanol with dimethyl carbonate is obtained at the tower top after the material is separated by the pressurizing tower, a methanol azeotrope containing dimethyl carbonate is discharged from an exhaust port at the tower top and is cooled by a condenser to obtain a liquid methanol azeotrope containing dimethyl carbonate, the liquid methanol azeotrope enters a third light component tank, one part of the material in the third light component tank reflows to the pressurizing tower from a reflux port for recycling, and the other part of the material is discharged into a methanol storage tank; discharging the pure dimethyl carbonate from a discharge port of the tower bottom of the pressurizing tower, sending the pure dimethyl carbonate to a fourth heavy component tank, and further sending the pure dimethyl carbonate to an electrolyte mother liquor tank, thereby obtaining electrolyte mixed solvent mother liquor of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
As a further improvement of the technical scheme of the invention, in the step (1), the feeding mass ratio of the methanol to the ethanol is 2: 8.
As a further improvement of the technical scheme of the invention, in the step (1), the mass ratio of the total volume of the methanol and the ethanol to the nano-copper catalyst is 1000 ml to 20 g.
As a further improvement of the technical scheme of the invention, in the step (1), after the carbon monoxide and the oxygen are introduced, the pressure in the closed reaction container is 3-7 MPa, the reaction temperature in the closed reaction container is 120-170 ℃, and the reaction time is kept at 2 h.
As a further improvement of the technical scheme of the invention, in the step (1), the nano-copper catalyst is a copper-loaded nano-particle catalyst taking nitrogen-doped graphene as a carrier.
As a further improvement of the technical scheme, the number of theoretical plates of the first rectifying tower is 70-100, the absolute operating pressure is 130 kpa, the reflux ratio at the top of the tower is 8-15, the operating temperature range at the top of the tower is 64-70 ℃, a reboiler is arranged at the bottom of the tower, and the temperature range at the bottom of the tower is 110-115 ℃.
As a further improvement of the technical scheme of the invention, the second rectifying tower is operated under normal pressure, the reflux ratio at the top of the tower is 1-6, a condenser is arranged at the top of the tower, the operation temperature at the top of the tower is 65-70 ℃, and the temperature of a tower kettle ranges from 99-103 ℃.
As a further improvement of the technical scheme of the invention, the operation pressure in the dehydration tower is normal pressure, the reflux ratio is 6-15, a condenser is arranged at the top of the tower, the operation temperature at the top of the tower is 100-103 ℃, and the temperature range of the tower kettle is 105-115 ℃.
As a further improvement of the technical scheme of the invention, the operation temperature range of the top of the pressurizing tower is 120-130 ℃, the pressure of the top of the pressurizing tower is 0.80-1.00 Mpa, and the reflux ratio of the pressurizing tower is 2-4; the temperature of the tower kettle is 175-193 ℃, and the pressure of the tower kettle is 0.80-1.00 Mpa.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method adopts methanol, ethanol, CO and O2DMC, DEC and EMC are synthesized simultaneously by oxidation and carbonylation method under the action of nano copper catalyst, which has the advantages of greatly simplified process and easily modulated components, greatly reduced production cost, simple process and high reaction efficiency.
Wherein: the core reaction equation:
(1) CH3CH2OH+CH3OH+CO+O2→EMC+H2O
(2) 2CH3CH2OH+O2→DMC+H2O
(3) 2CH3CH2OH+CO+O2→DEC+H2O
(4) C2H5OCOOC2H5+CH3OCOOCH3→2EMC
side reaction:
(1)C2H5OH +1/2O2→CH3CHO+H2O
(2)CH3CHO +1/2O2→CH3COOH
(3) CH3COOH+C2H5OH→CH3COOC2H5
(2) in the methanol oxidation carbonylation process, how to effectively remove impurities such as methanol, methyl formate, methylal and the like in reaction output substances plays a vital role in the efficiency and the economy of the electrolyte production process. The invention adopts multi-tower continuous rectification when separating impurities, which not only fully ensures the product purity, but also can realize large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a schematic diagram of a process flow for preparing a mixed solution mother liquor of lithium ion battery electrolyte according to the present invention.
FIG. 2 is a schematic diagram of the process for separating and purifying the mother liquor of the electrolyte mixture according to the present invention.
In the figure, 1-a first rectifying tower, 2-a second rectifying tower, 3-a dehydrating tower, 4-a pressurizing tower, 5-a first light component tank, 6-a second light component tank, 7-a third light component tank, 8-a fourth light component tank, 9-a first heavy component tank, 10-a second heavy component tank, 11-a third heavy component tank, 12-a fourth heavy component tank, 13-a methanol storage tank, 14-an electrolyte mother liquor tank, 15-an ethanol storage tank, 16-a reaction kettle, 17-a quick cooler and 18-a filter.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
A high-efficiency synthesis method of a lithium ion battery electrolyte mixed solvent comprises the following steps:
(1) reaction preparation: placing methanol, ethanol and a nano copper catalyst in a closed reaction container, introducing carbon monoxide to purge and remove air in the closed reaction container, continuously introducing the carbon monoxide and oxygen after the reaction is finished, heating, preserving heat and stirring for reaction; after the reaction is finished, cooling to room temperature, and discharging gas in the closed reaction container to obtain a reaction product;
(2) light weight removal and heavy weight removal: filtering the obtained reaction product to primarily separate the nano-copper catalyst from the reaction mixed liquid, returning the filtered nano-copper catalyst to the reaction container, and performing a circular reaction;
the reaction mixed liquid is conveyed to a first rectifying tower 1 with a side line, the reaction mixed liquid is separated in the first rectifying tower 1, light component products containing methylal, acetaldehyde, methyl formate, dimethyl carbonate and methanol are obtained at the top of the tower after separation, the light component products enter a first light component tank 5 after being condensed by a condenser, one part of materials in the tank flow back to the first rectifying tower 1, and the other part of materials are conveyed to a second rectifying tower 2 for refining the dimethyl carbonate;
heavy component products containing diethyl carbonate, ethyl methyl carbonate and water are obtained from the tower bottom of the first rectifying tower 1, the heavy component products flow into the first heavy component tank 9, the heavy component products in the first heavy component tank 9 are conveyed to the dehydrating tower 3, and dehydration is carried out in the tower;
an azeotropic mixture of ethanol and ethyl acetate on the upper tower wall of the first rectifying tower 1 is extracted from a side line, discharged from a discharge hole at the middle upper part of the tower wall and then sent into an ethanol storage tank 15 for storage;
(3) refining dimethyl carbonate: the feed liquid in the first light component tank 5 is conveyed to a second rectifying tower 2 to carry out secondary separation of methylal, methyl formate and the like, light component products such as methanol and methylal are obtained at the tower top, the light component products enter a second light component tank 6 after being condensed by a condenser, one part of the feed liquid in the second light component tank 6 reflows to the second rectifying tower 2 to be recycled as reflux liquid, and the other part of the feed liquid is conveyed to a methanol storage tank 13 to be stored; heavy components of dimethyl carbonate containing methanol are obtained at the bottom of the second rectifying tower 2 and are conveyed to a second heavy component tank 10 and then conveyed to a pressurizing tower 4 for separation again;
(4) and (3) dehydrating: diethyl carbonate and methyl ethyl carbonate containing water obtained from the tower bottom of the first rectifying tower 1 enter a dehydrating tower 3, and are dehydrated in the dehydrating tower 3; mixed liquid of diethyl carbonate and ethyl methyl carbonate is obtained at the tower bottom of the dehydrating tower 3, the mixed liquid is conveyed into a third heavy component tank 11, one part of feed liquid in the third heavy component tank 11 is sent to an electrolyte mother liquid tank 14, the other part of feed liquid is heated by a reboiler and then sent back to the dehydrating tower 3, water with the diethyl carbonate and the ethyl methyl carbonate at the tower top is condensed by a tower top condenser and then conveyed into a fourth light component tank 8, one part of feed liquid in the fourth light component tank 8 is taken as reflux liquid to flow back into the dehydrating tower 3, and the other part of feed liquid is taken as discharged wastewater for dehydration treatment;
(5) and (3) pressurized azeotropic distillation: the material in the second heavy component tank 10 is conveyed into a pressurizing tower 4, the pressurizing tower 4 is used for pressurizing azeotropic distillation, methanol with dimethyl carbonate is obtained at the tower top after being separated by the pressurizing tower 4, the methanol azeotrope containing dimethyl carbonate is discharged from an exhaust port at the tower top and is cooled by a condenser to obtain liquid methanol azeotrope containing dimethyl carbonate, the liquid methanol azeotrope enters a third light component tank 7, one part of the material in the third light component tank 7 flows back to the pressurizing tower 4 from a reflux port for recycling, and the other part of the material is discharged into a methanol storage tank 13; pure dimethyl carbonate is discharged from a discharge port of the tower bottom of the pressurizing tower 4 and sent to a fourth heavy component tank 12, and further sent to an electrolyte mother liquor tank 14, so that electrolyte mixed solvent mother liquor of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate is obtained.
In one embodiment provided by the present invention, in step (1), the feed mass ratio of methanol to ethanol is 2: 8.
In another embodiment provided by the present invention, in the step (1), the mass ratio of the total volume of the methanol and the ethanol to the nano-copper catalyst is 1000 ml:20 g.
In one embodiment provided by the invention, in the step (1), after introducing carbon monoxide and oxygen, the pressure in the closed reaction container is 3-7 MPa, the reaction temperature in the closed reaction container is 120-170 ℃, and the reaction time is kept at 2 h; in another embodiment provided by the invention, after the carbon monoxide and the oxygen are introduced, the pressure in the closed reaction container is 4-6 MPa, the reaction temperature in the closed reaction container is 140-160 ℃, and the reaction time is kept at 2 h.
In one embodiment of the present invention, in step (1), the nano-copper catalyst is a copper nanoparticle-supported catalyst with nitrogen-doped graphene as a carrier. Specifically, the catalyst is a self-made catalyst, and the reference documents are as follows: controllable synthesis and catalytic performance research of graphene-supported copper nano-catalyst, university of tai rationality engineering, doctrine of doctrine, 2020.12.01, srina.
In one embodiment provided by the invention, the number of theoretical plates of the first rectifying tower 1 is 70-100, the absolute operating pressure is 130 kpa, the reflux ratio at the top of the tower is 8-15, the operating temperature range at the top of the tower is 64-70 ℃, a reboiler is arranged at the bottom of the tower, and the temperature range at the bottom of the tower is 110-115 ℃. In another embodiment provided by the invention, the number of theoretical plates of the first rectifying tower 1 is 80-90, the absolute operating pressure is 130 kpa, the reflux ratio at the top of the tower is 10-12, the operating temperature range at the top of the tower is 66-68 ℃, a reboiler is arranged at the bottom of the tower, and the temperature range at the bottom of the tower is 111-113 ℃.
In one embodiment provided by the invention, the second rectifying tower 2 is operated at normal pressure, the reflux ratio at the top of the tower is 1-6, a condenser is arranged at the top of the tower, the operation temperature at the top of the tower is 65-70 ℃, and the temperature of a tower kettle ranges from 99-103 ℃. In another embodiment provided by the invention, the second rectifying tower 2 is operated under normal pressure, the reflux ratio of the tower top is 2-5, a condenser is arranged at the tower top, the operation temperature of the tower top is 66-68 ℃, and the temperature range of a tower kettle is 100-102 ℃.
In one embodiment provided by the invention, the operation pressure in the dehydration tower 3 is normal pressure, the reflux ratio is 6-15, a condenser is arranged at the top of the tower, the operation temperature at the top of the tower is 100-103 ℃, and the temperature range of a tower kettle is 105-115 ℃. In another embodiment provided by the invention, the operation pressure in the dehydration tower 3 is normal pressure, the reflux ratio is 9-12, a condenser is arranged at the top of the tower, the operation temperature at the top of the tower is 102 ℃, and the temperature range of the bottom of the tower is 108-112 ℃.
In one embodiment provided by the invention, the operation temperature range of the top of the pressurizing tower 4 is 120-130 ℃, the pressure of the top of the pressurizing tower is 0.80-1.00 Mpa, and the reflux ratio of the pressurizing tower is 2-4; the temperature of the tower kettle is 175-193 ℃, and the pressure of the tower kettle is 0.80-1.00 Mpa. In another embodiment provided by the invention, the operation temperature range of the top of the pressurizing tower 4 is 124-128 ℃, the pressure of the top of the pressurizing tower is 0.80-1.00 Mpa, and the reflux ratio of the pressurizing tower is 3; the temperature of the tower kettle is 180-190 ℃, and the pressure of the tower kettle is 0.80-1.00 Mpa.
The technical solution of the present invention will be described in detail by the following specific examples.
Example 1
(1) Placing methanol, ethanol and a nano copper catalyst into a reaction kettle 16, and then sealing the container, wherein the mass ratio of the methanol to the ethanol is 2:8, the mass ratio of the total volume of the methanol and the ethanol to the nano copper catalyst is 1000 ml:20 g, and the nano copper catalyst is a copper-loaded nano particle catalyst taking nitrogen-doped graphene as a carrier;
then introducing carbon monoxide to purge and remove air in the container, continuously introducing the carbon monoxide and the oxygen to pressurize to 3 MPa after the carbon monoxide and the oxygen are completely removed, then heating the container to 120 ℃, starting a stirring and constant temperature device of the reaction kettle 16, and maintaining the reaction temperature; after the reaction is finished, the reaction kettle is cooled to room temperature through the rapid cooler 17, the reactant is discharged after the gas in the reaction kettle 16 is discharged, and then the product is purified.
(2) Light weight removal and heavy weight removal: outputting the obtained reaction product to a filter 18 for filtering, performing primary separation of the catalyst and the reaction mixed liquid, and returning the filtered catalyst slurry to the reaction kettle 16 for the next reaction; the resulting mixture was tested to yield a product consisting essentially of DMC, DEC, EMC, methanol, and ethanol (see Table 1 for composition and content). Then, conveying the mixed liquid obtained by separation into a first rectifying tower 1 with a side line, separating in the first rectifying tower 1, wherein the theoretical plate number of the first rectifying tower 1 is 70, the absolute operating pressure is 130 kpa, the reflux ratio at the top of the tower is 8, the operating temperature at the top of the tower is 65 ℃, the operating temperature at the bottom of the tower is 110 ℃, light component products containing methylal, acetaldehyde, methyl formate, dimethyl carbonate, methanol and the like are obtained at the top of the tower after separation, the mass fractions of the gas phase materials at the top of the tower are all more than 93 percent (the separated gas phase materials/the corresponding gas phase materials in the mixed liquid), the light component products enter a first light component tank 5 after being condensed by a condenser, one part of the materials in the first light component tank 5 flow back to the first rectifying tower 1, and the other part of the materials are conveyed into a second rectifying tower 2 for refining dimethyl carbonate; heavy components containing diethyl carbonate, ethyl methyl carbonate, water and the like are obtained at the bottom of the tower, the mass fractions of the heavy components are more than 87% (separated heavy component materials/corresponding heavy component materials in mixed liquid), the heavy components flow into a first heavy component tank 9, heavy component products in the first heavy component tank 9 are conveyed to a dehydrating tower 3, and dehydration is carried out in the tower; the azeotropic mixture of the ethanol and the ethyl acetate on the tower wall at the middle upper part of the first rectifying tower 1 is extracted from the side line, the mass fraction of the azeotropic mixture of the ethanol and the ethyl acetate obtained from the tower wall is more than 80 percent, and the azeotropic mixture of the ethanol and the ethyl acetate is discharged from a discharge hole at the middle upper part of the tower wall and then is sent into an ethanol storage tank 15 for storage.
Table 1 shows the composition of the product mixture obtained by preliminary separation after the reaction
(3) Refining dimethyl carbonate: the feed liquid in the first light component tank 5 is conveyed to a second rectifying tower 2 for secondary separation of methylal, methyl formate and the like, the operating pressure of the second rectifying tower 2 is normal pressure, the reflux ratio of the top of the tower is 3, the operating temperature of the top of the tower is 65 ℃, the operating temperature of a tower kettle is 100 ℃, light component products such as methanol and methylal are obtained at the top of the tower, the light component products are condensed by a condenser and then enter a second light component tank 6, one part of the feed liquid in the second light component tank 6 reflows to the rectifying tower to be recycled as reflux liquid, and the other part of the feed liquid is conveyed to a methanol storage tank 13 for storage; the heavy fraction of dimethyl carbonate containing 16 to 20wt% of methanol, which is an azeotrope of dimethyl carbonate and methanol, is obtained at the bottom of the column and is fed to a second heavy fraction tank 10 and then to a pressurized column 4 for further separation.
(4) And (3) dehydrating: diethyl carbonate and ethyl methyl carbonate containing water obtained from the bottom of the first rectifying tower 1 enter a dehydrating tower 3, and dehydration is carried out in the dehydrating tower 3. The operating pressure of the dehydrating tower 3 is normal pressure, the reflux ratio is set to 10, the temperature of the condenser at the top of the tower is 102 ℃, the operating temperature of the tower kettle is 110 ℃, obtaining mixed solution of diethyl carbonate and methyl ethyl carbonate at the bottom of the tower, wherein the mass fraction of the mixed materials of dimethyl carbonate and diethyl carbonate in the mixed solution is more than 95 percent, the mixed liquid is conveyed to a heavy component third heavy component tank 11, a reboiler is arranged at a tower kettle of the dehydrating tower 3, one part of the liquid in the third heavy component tank 11 is sent to an electrolyte mother liquid tank 14, the other part of the liquid is heated by the reboiler and then sent back to the dehydrating tower 3, the water mixed liquid with diethyl carbonate and ethyl methyl carbonate at the tower top is condensed by a tower top condenser and then conveyed to a fourth light component tank 8, one part of the liquid in the fourth light component tank 8 is used as reflux liquid to flow back into the dehydrating tower 3, and the other part of the liquid is used as discharged wastewater for a dehydration treatment process.
(5) And (3) pressurized azeotropic distillation: the material in the second heavy component tank 10 is conveyed into the pressurizing tower 4, and pressurized azeotropic distillation is carried out in the pressurizing tower 4, so that the azeotropic composition ratio of the methanol and the dimethyl carbonate can be changed by the pressurizing measure, and the methanol and the dimethyl carbonate can be effectively separated. The operation pressure at the top of the pressurizing tower 4 is 0.8 MPa, the reflux ratio of the pressurizing tower is 3, the operation temperature at the top of the pressurizing tower is 120 ℃, the operation pressure at the bottom of the pressurizing tower is 0.9 MPa, and the operation temperature is 180 ℃. After separation by the pressurizing tower 4, obtaining a methanol azeotrope with 8wt% -15 wt% of dimethyl carbonate at the tower top, discharging the methanol azeotrope containing a small amount of dimethyl carbonate from an exhaust port at the tower top, cooling by a condenser to obtain a liquid methanol azeotrope containing dimethyl carbonate, and then feeding the liquid methanol azeotrope into a third light component tank 7, wherein one part of materials in the third light component tank 7 reflows to the pressurizing tower 4 from a reflux port for recycling, and the other part of materials is discharged into a heavy component tank methanol storage tank 13; dimethyl carbonate with the mass fraction of more than 98 percent can be obtained at the tower bottom, and is discharged from a discharge hole of the tower bottom and sent to an electrolyte mother liquor tank 14; thus, an electrolyte mixed solvent mother liquor of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate was obtained.
Table 2 shows the product composition of the mother liquor of the electrolyte mixture
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A high-efficiency synthesis method of a lithium ion battery electrolyte mixed solvent is characterized by comprising the following steps:
(1) reaction preparation: placing methanol, ethanol and a nano copper catalyst in a closed reaction container, introducing carbon monoxide to purge and remove air in the closed reaction container, continuously introducing the carbon monoxide and oxygen after the reaction is finished, heating, preserving heat and stirring for reaction; after the reaction is finished, cooling to room temperature, and discharging gas in the closed reaction container to obtain a reaction product;
(2) light weight removal and heavy weight removal: filtering the obtained reaction product to primarily separate the nano-copper catalyst from the reaction mixed liquid, returning the filtered nano-copper catalyst to the reaction container, and performing a circular reaction;
the reaction mixed liquid is conveyed into a first rectifying tower (1) with a side line, the reaction mixed liquid is separated in the first rectifying tower (1), light component products containing methylal, acetaldehyde, methyl formate, dimethyl carbonate and methanol are obtained at the top of the tower after separation, the light component products enter a first light component tank (5) after being condensed by a condenser, one part of materials in the tank flow back into the first rectifying tower (1), and the other part of materials are conveyed into a second rectifying tower (2) for refining the dimethyl carbonate;
heavy component products containing diethyl carbonate, ethyl methyl carbonate and water are obtained at the tower bottom of the first rectifying tower (1), the heavy component products flow into a first heavy component tank (9), the heavy component products in the first heavy component tank (9) are conveyed into a dehydrating tower (3), and dehydration is carried out in the tower;
an azeotropic mixture of ethanol and ethyl acetate on the upper tower wall of the first rectifying tower (1) is extracted from a side line, discharged from a discharge hole on the middle upper part of the tower wall and then sent into an ethanol storage tank (15) for storage;
(3) refining dimethyl carbonate: the feed liquid in the first light component tank (5) is conveyed to a second rectifying tower (2) for secondary separation of methylal, methyl formate and the like, light component products such as methanol and methylal are obtained at the tower top, the light component products enter a second light component tank (6) after being condensed by a condenser, one part of the feed liquid in the second light component tank (6) reflows to the second rectifying tower (2) to be recycled as a reflux liquid, and the other part of the feed liquid is conveyed to a methanol storage tank (13) to be stored; heavy components of dimethyl carbonate containing methanol are obtained at the bottom of the second rectifying tower (2), and are conveyed to a second heavy component tank (10) and then conveyed to a pressurizing tower (4) for secondary separation;
(4) and (3) dehydrating: diethyl carbonate and methyl ethyl carbonate containing water obtained from the tower kettle of the first rectifying tower (1) enter a dehydrating tower (3) and are dehydrated in the dehydrating tower (3); mixed liquid of diethyl carbonate and ethyl methyl carbonate is obtained at the bottom of a dehydrating tower (3), the mixed liquid is conveyed into a third heavy component tank (11), one part of the liquid in the third heavy component tank (11) is sent into an electrolyte mother liquid tank (14), the other part of the liquid is heated by a reboiler and then sent back into the dehydrating tower (3), the water mixed liquid with the diethyl carbonate and the ethyl methyl carbonate at the top of the tower is condensed by a tower top condenser and then conveyed into a fourth light component tank (8), one part of the liquid in the fourth light component tank (8) is used as reflux liquid to flow back into the dehydrating tower (3), and the other part of the liquid is used as discharged wastewater for dehydration treatment;
(5) and (3) pressurized azeotropic distillation: the material in the second heavy component tank (10) is conveyed into a pressurizing tower (4), pressurizing azeotropic distillation is carried out in the pressurizing tower (4), methanol with dimethyl carbonate is obtained at the tower top after being separated by the pressurizing tower (4), a methanol azeotrope containing dimethyl carbonate is discharged from an exhaust port at the tower top and is cooled by a condenser to obtain a liquid methanol azeotrope containing dimethyl carbonate, and then the liquid methanol azeotrope enters a third light component tank (7), one part of the material in the third light component tank (7) reflows to the pressurizing tower (4) from a reflux port for recycling, and the other part of the material is discharged into a methanol storage tank (13); pure dimethyl carbonate is discharged from a discharge port of a tower bottom of the pressurizing tower (4) and sent to a fourth heavy component tank (12) and further sent to an electrolyte mother liquor tank (14), so that electrolyte mixed solvent mother liquor of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate is obtained.
2. The method for efficiently synthesizing the mixed solvent of the lithium ion battery electrolyte according to claim 1, wherein in the step (1), the feeding mass ratio of the methanol to the ethanol is 2: 8.
3. The efficient synthesis method of the lithium ion battery electrolyte mixed solvent according to claim 1, wherein in the step (1), the mass ratio of the total volume of the methanol and the ethanol to the nano-copper catalyst is 1000 ml:20 g.
4. The efficient synthesis method of the lithium ion battery electrolyte mixed solvent according to claim 1, characterized in that in the step (1), after carbon monoxide and oxygen are introduced, the pressure in the closed reaction container is 3-7 MPa, the reaction temperature in the closed reaction container is 120-170 ℃, and the reaction time is kept at 2 h.
5. The efficient synthesis method of the lithium ion battery electrolyte mixed solvent according to claim 1, wherein in the step (1), the nano-copper catalyst is a copper-supported nano-particle catalyst taking nitrogen-doped graphene as a carrier.
6. The efficient synthesis method of the lithium ion battery electrolyte mixed solvent according to claim 1, characterized in that the number of theoretical plates of the first rectifying tower (1) is 70-100, the absolute operating pressure is 130 kpa, the reflux ratio at the top of the tower is 8-15, the operating temperature at the top of the tower is 64-70 ℃, a reboiler is arranged at the bottom of the tower, and the temperature at the bottom of the tower is 110-115 ℃.
7. The efficient synthesis method of the lithium ion battery electrolyte mixed solvent according to claim 1, characterized in that the second rectification tower (2) is operated under normal pressure, the reflux ratio at the top of the tower is 1-6, a condenser is arranged at the top of the tower, the operation temperature at the top of the tower is 65-70 ℃, and the temperature at the bottom of the tower ranges from 99-103 ℃.
8. The efficient synthesis method of the lithium ion battery electrolyte mixed solvent according to claim 1, characterized in that the operating pressure in the dehydration tower (3) is normal pressure, the reflux ratio is 6-15, a condenser is arranged at the top of the tower, the operating temperature at the top of the tower is 100-103 ℃, and the temperature at the bottom of the tower is 105-115 ℃.
9. The efficient synthesis method of the lithium ion battery electrolyte mixed solvent according to claim 1, characterized in that the operation temperature range of the top of the pressurizing tower (4) is 120-130 ℃, the pressure at the top of the pressurizing tower is 0.80-1.00 Mpa, and the reflux ratio of the pressurizing tower is 2-4; the temperature of the tower kettle is 175-193 ℃, and the pressure of the tower kettle is 0.80-1.00 Mpa.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439857A (en) * | 2015-12-09 | 2016-03-30 | 辽阳百事达化工有限公司 | Method and apparatus for producing methyl ethyl carbonate |
| CN110372512A (en) * | 2019-07-29 | 2019-10-25 | 太原理工大学 | A kind of process for separating and purifying of dimethyl carbonate |
| CN110845334A (en) * | 2019-11-15 | 2020-02-28 | 山东石大胜华化工集团股份有限公司 | Device and method for producing battery-grade ethyl methyl carbonate by using dimethyl carbonate and ethanol |
| CN111072481A (en) * | 2020-01-08 | 2020-04-28 | 凯瑞环保科技股份有限公司 | Device and method for producing high-concentration dimethyl carbonate |
| CN111909036A (en) * | 2020-08-21 | 2020-11-10 | 湖北三宁化工股份有限公司 | DMC production system and method |
| CN113045420A (en) * | 2020-12-21 | 2021-06-29 | 天津市众天科技发展有限公司 | Dimethyl carbonate liquid-phase synthesis method and corresponding synthesis reaction system |
| CN113248379A (en) * | 2021-06-04 | 2021-08-13 | 重庆微而易科技有限公司 | Method for preparing methyl ethyl carbonate by adopting pipeline continuous reactor |
| CN113387810A (en) * | 2021-06-11 | 2021-09-14 | 重庆微而易科技有限公司 | Method for synthesizing methyl ethyl carbonate by one step |
| CN113429290A (en) * | 2021-07-16 | 2021-09-24 | 南京延长反应技术研究院有限公司 | DMC preparation system and method |
-
2022
- 2022-04-13 CN CN202210381635.5A patent/CN114507136B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439857A (en) * | 2015-12-09 | 2016-03-30 | 辽阳百事达化工有限公司 | Method and apparatus for producing methyl ethyl carbonate |
| CN110372512A (en) * | 2019-07-29 | 2019-10-25 | 太原理工大学 | A kind of process for separating and purifying of dimethyl carbonate |
| CN110845334A (en) * | 2019-11-15 | 2020-02-28 | 山东石大胜华化工集团股份有限公司 | Device and method for producing battery-grade ethyl methyl carbonate by using dimethyl carbonate and ethanol |
| CN111072481A (en) * | 2020-01-08 | 2020-04-28 | 凯瑞环保科技股份有限公司 | Device and method for producing high-concentration dimethyl carbonate |
| CN111909036A (en) * | 2020-08-21 | 2020-11-10 | 湖北三宁化工股份有限公司 | DMC production system and method |
| CN113045420A (en) * | 2020-12-21 | 2021-06-29 | 天津市众天科技发展有限公司 | Dimethyl carbonate liquid-phase synthesis method and corresponding synthesis reaction system |
| CN113248379A (en) * | 2021-06-04 | 2021-08-13 | 重庆微而易科技有限公司 | Method for preparing methyl ethyl carbonate by adopting pipeline continuous reactor |
| CN113387810A (en) * | 2021-06-11 | 2021-09-14 | 重庆微而易科技有限公司 | Method for synthesizing methyl ethyl carbonate by one step |
| CN114163333A (en) * | 2021-06-11 | 2022-03-11 | 重庆微而易科技有限公司 | Method for synthesizing methyl ethyl carbonate by one step |
| CN113429290A (en) * | 2021-07-16 | 2021-09-24 | 南京延长反应技术研究院有限公司 | DMC preparation system and method |
Non-Patent Citations (2)
| Title |
|---|
| ZHU MINYAN等: ""Design and control of a middle-vessel batch distillation for separating DMC-EMC-DEC mixture"", 《CHINESE JOURNAL OF CHEMICAL ENGINEERING》 * |
| 李新 等: ""我国碳酸二甲酯生产技术现状及发展建议"", 《辽宁化工》 * |
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