CN106748792A - The method and apparatus that azeotropic reaction rectification method produces methyl ethyl carbonate - Google Patents
The method and apparatus that azeotropic reaction rectification method produces methyl ethyl carbonate Download PDFInfo
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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Abstract
The present invention relates to the method and apparatus that azeotropic reaction rectification method produces methyl ethyl carbonate, the azeotropic reaction rectification method produces the device of methyl ethyl carbonate, including azeotropic reactive distillation column, point flow container, methanol purification tower and next door tower.Azeotropic reaction rectification method of the invention produces the device of methyl ethyl carbonate, reaction and rectifying and the separation of azeotropic mixture are integrated in azeotropic reactive distillation column and carried out, and using next door tower separating dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate ternary mixture, save energy consumption, technological process is enormously simplify, equipment investment is saved.
Description
Technical field
The present invention relates to chemical technology field, and in particular to a kind of method that azeotropic reaction rectification method produces methyl ethyl carbonate
And device.
Background technology
Methyl ethyl carbonate is a kind of water white transparency flammable liquid, immiscible with water, slightly the fragrance of ethanol, does not have toxicity,
It is a kind of green chemical that is emerging, possessing in chemical field broader application prospect.In recent years it is found that carbonic acid first
The solvent that ethyl ester serves as lithium cell electrolyte cobalt acid lithium, LiMn2O4 etc. has significant excellent compared with other carbonates materials
Point, when methyl ethyl carbonate is used as the solvent of lithium cell electrolyte cobalt acid lithium, LiMn2O4 etc., it is possible to increase lithium ion conduction from
Electron conductivity, enhancing lithium battery reliability, security performance and memory effect, while when can also extend the use of lithium battery
Between.Recently as lithium ion battery every field extensive use, the compound probability of methyl ethyl carbonate also obtained rapidly
Development.Methyl ethyl carbonate ester molecule possesses two kinds of asymmetric alkane groups simultaneously simultaneously：Methoxyl group, ethyoxyl, so that carbonic acid
Methyl ethyl ester possesses the part chemical property of dimethyl carbonate and diethyl carbonate, and methyl ethyl carbonate can be as raw material reaction thing
It is applied in special organic synthesis, according to the demand of the special reaction, selects different groups to participate in reaction.Carbonic acid first
Ethyl ester has good intersolubility with organic compound, therefore methyl ethyl carbonate can uniformly be mixed with organic solvent alcohol, ketone and ester
Close, while methyl ethyl carbonate can also be applied to fragrance industry and serve as chemical intermediate solvent, therefore methyl ethyl carbonate has
Larger market.
Preparing the conventional process of methyl ethyl carbonate has three kinds, respectively phosgenation, oxidation carbonyl process and ester-interchange method.
During phosgenation prepares dimethyl carbonate, although the conversion ratio of reactant phosgene, methyl alcohol or ethanol is higher, but this is anti-
The selectivity answered is poor, may generate more accessory substance, while need substantial amounts of methyl alcohol or ethanol, improve industry into
This.Additionally, accessory substance methylchloroformate and ethyl ester have severe toxicity, severe contamination can be caused to natural ecosystems, current this side
Method is superseded；Carbonyl process prepares methyl ethyl carbonate mainly with ethanol/phenol, oxygen and carbon monoxide as raw material, is given birth to by reaction
Into organic carbonate, the process of water.But in this process, side reaction is a lot, increased difficulty for the separating-purifying in later stage, together
When increased the industrial costs such as the energy consumption of production technology, equipment investment, personal expenditures.Further, since process production carbonic acid first
The selectivity of ethyl ester is not high, therefore when chemical industry industrialization is applied to, possesses significant limitation.
The content of the invention
It is an object of the present invention to propose that a kind of azeotropic reaction rectification method produces the device of methyl ethyl carbonate.
Azeotropic reaction rectification method of the invention produces the device of methyl ethyl carbonate, including azeotropic reactive distillation column, point
Flow container, methanol purification tower and next door tower；The azeotropic reactive distillation column is arranged at intervals with first charging aperture, catalyst from top to bottom
Charging aperture, second charging aperture and the 3rd charging aperture, the tower top of the azeotropic reactive distillation column are provided with the first discharging opening, described common
The bottom of towe for boiling reactive distillation column is provided with the second discharging opening；The 4th charging aperture is provided with described point of flow container with the described first discharging
5th charging aperture of mouth connection, and the 3rd discharging opening and the connected with the first charging aperture the 4th are provided with described point of flow container
Discharging opening；The 6th charging aperture connected with the 3rd discharging opening, and the methanol purification are provided with the methanol purification tower
The 5th discharging opening and the 6th discharging opening connected with the 4th charging aperture are provided with tower；The next door tower include fore-running section,
King-tower area, public rectifying section and public stripping section, the fore-running section are provided with the 7th charging connected with second discharging opening
Mouthful, the public stripping section is provided with the 7th discharging opening, and the king-tower area is provided with the 8th discharging opening, and the public rectifying section sets
It is equipped with the 9th discharging opening connected with the second charging aperture.
Azeotropic reaction rectification method according to embodiments of the present invention produces the device of methyl ethyl carbonate, will reaction and rectifying and
The separation of azeotropic mixture is integrated in azeotropic reactive distillation column and carries out, and using next door tower separating dimethyl carbonate, diethyl carbonate,
Methyl ethyl carbonate ternary mixture, saves energy consumption, enormously simplify technological process, saves equipment investment.
In addition, producing the device of methyl ethyl carbonate according to the above-mentioned azeotropic reaction rectification method of the present invention, can also have such as
Lower additional technical characteristic：
Further, the device of described azeotropic reaction rectification method production methyl ethyl carbonate also includes the first blender, the
Two blenders, the 3rd blender, the first reboiler, the second reboiler, the 3rd reboiler, the 4th reboiler, the 5th reboiler,
One compressor, the second compressor, the first current divider, the second current divider and condenser；The output end of first blender and institute
First charging aperture connection is stated, the output end of second blender is connected with the second charging aperture, the 3rd blender
Output end is connected with the 4th charging aperture, and the input of first reboiler is connected with second discharging opening, and described
The output end of one reboiler is connected with the azeotropic reactive distillation column bottom of towe, the input of second reboiler and the described 6th
Discharging opening is connected, and the second end of second reboiler connects with the bottom of towe of the methanol purification tower, the 3rd reboiler
Input is connected with the 7th discharging opening, and the output end of the 3rd reboiler is connected with the public stripping section, and described
The input of four reboilers is connected with the output end of first compressor and the side line of the methanol purification tower, and the described 4th
The output end of reboiler is connected with the side line of the methanol purification tower and the input of first current divider, first pressure
The input of contracting machine is connected with the tower top of the methanol purification tower, the output end of first current divider and the 5th discharging opening
Tower top with the methanol purification tower is connected, and the input of the 5th reboiler distinguishes the tower of the azeotropic reactive distillation column
Bottom, the output end connection of second compressor, the output end of the 5th reboiler respectively with the azeotropic reactive distillation column
Bottom of towe, the input connection of second current divider, the input of second compressor connects with the 9th discharging opening,
Public rectifying section of the output end of second current divider respectively with the second charging aperture and the next door tower is connected；It is shown cold
The input of condenser is connected with first discharging opening, and the second end of the condenser connects with the 5th charging aperture.
Further, the compression ratio of first compressor is 2~5, and the compression ratio of second compressor is 2~5.
Further, the azeotropic reactive distillation column be plate column or packed tower, the methanol purification tower be plate column or
Packed tower, the next door tower is plate column or packed tower.
Further, the number of plates of the azeotropic reactive distillation column be 30~60, tower pressure interior force be 0.05MPa~
0.35MPa, tower top temperature is 33 DEG C~85 DEG C, and column bottom temperature is 80 DEG C~140 DEG C；Pressure in described point of flow container is
0.05MPa~0.2MPa, temperature is 30 DEG C~50 DEG C；The number of plates of the methanol purification tower is 25~50, and tower pressure interior force is
0.02MPa~0.2MPa, tower top temperature is 27 DEG C~82 DEG C, and column bottom temperature is 73 DEG C~120 DEG C；The fore-running section of the next door tower
The number of plates be 20~45, the number of plates in the king-tower area is equal with the number of plates of fore-running section, the public rectifying section
The number of plates is 5~15, and the number of plates of the public stripping section is 4~25, the tower pressure interior force of the next door tower for 0.05MPa~
0.3MPa, tower top temperature is 55 DEG C~107 DEG C, and column bottom temperature is 114 DEG C~170 DEG C.
It is another object of the present invention to propose a kind of method that azeotropic reaction rectification method produces methyl ethyl carbonate.
The method that methyl ethyl carbonate is produced using above-mentioned device of the invention, is comprised the following steps：By carbonic acid two
Methyl esters is added from the second charging aperture of the azeotropic reactive distillation column, and ethanol is added from the 3rd charging aperture of azeotropic reactive distillation column
Enter, catalyst added from the catalyst feeds, dimethyl carbonate and ethanol is reacted in the presence of catalyst,
Entrainer n-hexane is added into the reaction system of the reaction from the first charging aperture of azeotropic reactive distillation column simultaneously, the is obtained
One mixture and the second mixture；First mixture is mixed for dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate
Compound, second mixture is methyl alcohol and hexane mixture；By first mixture successively through second discharging opening,
7th charging aperture respectively obtains dimethyl carbonate, methyl ethyl carbonate and carbonic acid two into being separated in the next door tower
Ethyl ester；Second mixture is entered in point flow container through the first discharging opening and the 5th charging aperture successively, and to described point of flow container
Middle addition water obtains the 3rd mixture to isolate n-hexane；3rd mixture is the mixture of first alcohol and water；By described
Three mixtures successively through the 3rd discharging opening and the 6th charging aperture into being separated in the methanol purification tower, respectively
Obtain water and methyl alcohol.
The method that azeotropic reaction rectification method according to embodiments of the present invention produces methyl ethyl carbonate, by during the course of the reaction
N-hexane is added to inhibit dimethyl carbonate and methyl alcohol to form azeotropic mixture, so as to difficult separate dimethyl carbonate and methyl alcohol be mixed
Thing is separated.And the methyl ethyl carbonate and byproduct diethyl carbonate, the quality purity of methyl alcohol after separating are both greater than or are equal to
0.995, substantially increase separative efficiency.
In addition, the method that azeotropic reaction rectification method according to the above embodiment of the present invention produces methyl ethyl carbonate, can be with
With following additional technical characteristic：
Further, the molar feed ratio of the n-hexane, the dimethyl carbonate and the ethanol is (1~3):1.1:
1, the quality of the catalyst is the 0.05%~7.5% of the quality sum of the dimethyl carbonate and the ethanol.
Further, the catalyst is at least the one kind in sodium methoxide, NaOH and caustic alcohol.
Further, the number of plates of the azeotropic reactive distillation column be 30~60, tower pressure interior force be 0.05MPa~
0.35MPa, tower top temperature is 33 DEG C~85 DEG C, and column bottom temperature is 80 DEG C~140 DEG C；Pressure in described point of flow container is
0.05MPa~0.2MPa, temperature is 30 DEG C~50 DEG C；The number of plates of the methanol purification tower is 25~50, and tower pressure interior force is
0.02MPa~0.2MPa, tower top temperature is 27 DEG C~82 DEG C, and column bottom temperature is 73 DEG C~120 DEG C；The next door tower it is described just
It is 20~45 to evaporate the number of plates of section, and the number of plates in the king-tower area is equal with the number of plates of fore-running section, the public rectifying
The number of plates of section is 5~15, and the number of plates of the public stripping section is 4~25, and the tower pressure interior force of the next door tower is 0.05MPa
~0.3MPa, tower top temperature is 55 DEG C~107 DEG C, and column bottom temperature is 114 DEG C~170 DEG C.
Additional aspect of the invention and advantage will be set forth in part in the description, and will partly become from the following description
Obtain substantially, or recognized by practice of the invention.
Brief description of the drawings
Fig. 1 is the signal of the device of azeotropic reaction rectification method production methyl ethyl carbonate according to an embodiment of the invention
Figure；
Fig. 2 is the flow of the method for azeotropic reaction rectification method production methyl ethyl carbonate according to an embodiment of the invention
Figure；
Fig. 3 is the signal of the device of azeotropic reaction rectification method production methyl ethyl carbonate in accordance with another embodiment of the present invention
Figure.
Specific embodiment
Embodiments of the invention are described below in detail, the example of the embodiment is shown in the drawings, wherein from start to finish
Same or similar label represents same or similar element or the element with same or like function.Below with reference to attached
It is exemplary to scheme the embodiment of description, it is intended to for explaining the present invention, and be not considered as limiting the invention.
Fig. 1 shows that the azeotropic reaction rectification method of first embodiment of the invention produces the device of methyl ethyl carbonate.
Azeotropic reaction rectification method according to first embodiment of the invention produces the device of methyl ethyl carbonate, including：Azeotropic
Reactive distillation column 100, point flow container 200, methanol purification tower 300 and next door tower 400.
The azeotropic reactive distillation column 100 be arranged at intervals with from top to bottom first charging aperture 110, catalyst feeds 115,
The charging aperture 130 of second charging aperture 120 and the 3rd.The tower top of the azeotropic reactive distillation column 100 is provided with the first discharging opening 140,
The bottom of towe of the azeotropic reactive distillation column 100 is provided with the second discharging opening 150.
The 5th charging aperture that the 4th charging aperture 210 is connected with first discharging opening 140 is provided with described point of flow container 200
The 3rd discharging opening 230 and the 4th discharging opening connected with the first charging aperture 110 are provided with 220, and described point of flow container 200
240。
The 6th charging aperture 310 connected with the 3rd discharging opening 230, and institute are provided with the methanol purification tower 300
State the 6th discharging opening 330 for the 5th discharging opening 320 being provided with methanol purification tower 300 and being connected with the 4th charging aperture 210.
The next door tower 400 includes fore-running section 401, king-tower area 402, public rectifying section 404 and public stripping section 403.Institute
State fore-running section 401 and be provided with the 7th charging aperture 410 connected with second discharging opening 150, the public stripping section 403 is set
There is the 7th discharging opening 420, the king-tower area 402 is provided with the 8th discharging opening 430, and the public rectifying section 404 is provided with and institute
State the 9th discharging opening 440 of the connection of second charging aperture 120.
During reaction, dimethyl carbonate is added from the second charging aperture 120 of azeotropic reactive distillation column 100, and ethanol enters from the 3rd
Material mouth 130 is added, and catalyst is added from catalyst feeds 115, and dimethyl carbonate and ethanol occur in the presence of catalyst
Reaction, while adding entrainer just into the reaction system of the reaction from the first charging aperture 110 of azeotropic reactive distillation column 100
Hexane forms azeotropic mixture to suppress dimethyl carbonate and methyl alcohol, obtains the first mixture and the second mixture.Wherein, described first
Mixture is the mixture of dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, and second mixture is for methyl alcohol and just
Hexanes mixtures.
By first mixture successively through second discharging opening, the 7th charging aperture into entering in the next door tower
Row is separated, and respectively obtains dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate.
Second mixture is entered in point flow container 200 through the first discharging opening 140 and the 5th charging aperture 220 successively, and
To addition water in described point of flow container 200 to isolate n-hexane, and obtain the 3rd mixture.Wherein, the 3rd mixture is methyl alcohol
With the mixture of water；
3rd mixture is entered into the first through the 3rd discharging opening 230 and the 6th charging aperture 310 successively
Separated in alcohol purifying column 300, respectively obtained water and methyl alcohol.
Separated by 400 pairs of first mixtures of next door tower, respectively obtain methyl ethyl carbonate, diethyl carbonate and
Dimethyl carbonate.Methyl ethyl carbonate is flowed out from the 8th discharging opening 430, and dimethyl carbonate is entered by the 9th discharging opening 440 and second
Material mouth 120 is flowed into azeotropic reactive distillation column 100, and diethyl carbonate flows out from the 7th discharging opening 420.
Azeotropic reaction rectification method according to embodiments of the present invention produces the device of methyl ethyl carbonate, will reaction and rectifying and
The separation of azeotropic mixture is integrated in azeotropic reactive distillation column and carries out, and using next door tower separating dimethyl carbonate, diethyl carbonate,
Methyl ethyl carbonate ternary mixture, saves energy consumption, enormously simplify technological process, saves equipment investment.
Fig. 2 shows the method that the azeotropic reaction rectification method of first embodiment of the invention produces methyl ethyl carbonate, with this
The device of the azeotropic reaction rectification method production methyl ethyl carbonate of one embodiment of invention is corresponding.
The method that azeotropic reaction rectification method according to first embodiment of the invention produces methyl ethyl carbonate, including following step
Suddenly：
(1) dimethyl carbonate is added from the second charging aperture 120 of the azeotropic reactive distillation column 100, by ethanol from altogether
The 3rd charging aperture 130 for boiling reactive distillation column 100 is added, and catalyst is added from catalyst feeds 115, makes dimethyl carbonate
Reacted in the presence of catalyst with ethanol, while from the first charging aperture 110 of azeotropic reactive distillation column to the reaction
Reaction system in add entrainer n-hexane, obtain the first mixture and the second mixture.
Wherein, first mixture is the mixture of dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate, described
Second mixture is methyl alcohol and hexane mixture.
(2) first mixture is entered described through second discharging opening 150, the 7th charging aperture 410 successively
Separated in next door tower 400, respectively obtained dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate.
(3) second mixture is entered in point flow container 200 through the first discharging opening 140 and the 5th charging aperture 220 successively,
And to addition water in described point of flow container 200 to isolate n-hexane, and obtain the 3rd mixture.
Wherein, the 3rd mixture is the mixture of first alcohol and water.
(4) the 3rd mixture is entered described through the 3rd discharging opening 230 and the 6th charging aperture 310 successively
Separated in methanol purification tower 300, respectively obtained water and methyl alcohol.
Wherein, the 3rd mixture is n-hexane and methyl alcohol, and the 4th mixture is water and methyl alcohol.
Advantageously, the molar feed ratio of the n-hexane, the dimethyl carbonate and the ethanol is (1~3):1.1:1,
The quality of the catalyst is the 0.05%~7.5% of the quality sum of the dimethyl carbonate and the ethanol.
Advantageously, the catalyst is at least the one kind in sodium methoxide, NaOH and caustic alcohol.
Fig. 3 shows the device of the production methyl ethyl carbonate co-production diethyl carbonate of second embodiment of the invention, its
On the basis of the device of first embodiment of the invention, some servicing units are increased.
Specifically, described device also includes the first blender 501, the second blender 502, the 3rd blender 503, first again
Boiling device 511, the second reboiler 512, the 3rd reboiler 513, the 4th reboiler 514, the 5th reboiler 515, the first compressor
531st, the second compressor 532, the first current divider 541, the second current divider 542 and condenser 551.
The output end of first blender 501 is connected with the first charging aperture 110, second blender 502
Output end is connected with the second charging aperture 120, and output end and the 4th charging aperture 210 of the 3rd blender 503 connect
It is logical.
The input of first reboiler 511 is connected with second discharging opening 150, first reboiler 511
Output end is connected with the bottom of towe of azeotropic reactive distillation column 100, and the input of second reboiler 512 and the described 6th discharges
Mouth 330 is connected, and the second end of second reboiler 512 connects with the bottom of towe of the methanol purification tower 300, and the described 3rd boils again
The input of device 513 is connected with the 7th discharging opening 420, output end and the public stripping of the 3rd reboiler 513
The connection of section 403, the input of the 4th reboiler 514 and the output end and the methanol purification of first compressor 531
The side line of tower 300 is connected, the output end of the 4th reboiler 514 and the side line of the methanol purification tower 300 and described
The input of one current divider 541 is connected, the tower top of the input of first compressor 531 and the methanol purification tower 300
Connection, the output end of first current divider 541 is equal with the tower top of the 5th discharging opening 320 and the methanol purification tower 300
Connection, the input of the 5th reboiler 515 distinguishes bottom of towe, second compressor of the azeotropic reactive distillation column 100
Output end connection, the output end of the 5th reboiler bottom of towe respectively with the azeotropic reactive distillation column, described second point
The input connection of device is flowed, the input of second compressor 532 is connected with the 9th discharging opening 440, described second point
Public rectifying section 404 of the output end of device 542 respectively with the second charging aperture 120 and the next door tower is flowed to connect.It is described cold
The input of condenser 551 is connected with first discharging opening 140, the second end of the condenser and the 5th charging aperture 220
Connection.
In a second embodiment of the present invention, methanol purification tower and next door tower are by heat pump techniques and intermediate reboiler skill
Art integrated utilization, not only simplify technological process, and reduce equipment investment and energy consumption.
Advantageously, the compression ratio of first compressor 531 is 2~5, the compression ratio of second compressor 532 for 2~
5。
Advantageously, the azeotropic reactive distillation column 100 is plate column or packed tower, and the methanol purification tower 300 is board-like
Tower or packed tower, the next door tower 400 are plate column or packed tower.
In a second embodiment of the present invention, the number of plates of the azeotropic reactive distillation column 100 is 30~60, tower internal pressure
Power is 0.05MPa~0.35MPa, and tower top temperature is 33 DEG C~85 DEG C, and column bottom temperature is 80 DEG C~140 DEG C；Described point of flow container 200
Interior pressure is 0.05MPa~0.2MPa, and temperature is 30 DEG C~50 DEG C；The number of plates of the methanol purification tower 300 is 25~50,
Tower pressure interior force is 0.02MPa~0.2MPa, and tower top temperature is 27 DEG C~82 DEG C, and column bottom temperature is 73 DEG C~120 DEG C；The next door
Tower 400 includes fore-running section 401, king-tower area 402, public rectifying section 404 and public stripping section 403, the column plate of the fore-running section 401
Number is 20~45, and the number of plates in the king-tower area 402 is equal with the number of plates of fore-running section 401, the public rectifying section 404
The number of plates be 5~15, the number of plates of the public stripping section 403 is 4~25, and the tower pressure interior force of the next door tower 400 is
0.05MPa~0.3MPa, tower top temperature is 55 DEG C~107 DEG C, and column bottom temperature is 114 DEG C~170 DEG C.
During reaction, in azeotropic reactive distillation column 100, conversion zone covers whole tower region, dimethyl carbonate logistics and
The dimethyl carbonate looped back from next door tower 400 is by being that dimethyl carbonate is fed from altogether after the mixing of the second blender 502
The middle part of boiling reactive distillation column 100 is added, and ethanol stream is circulated from the addition of tower bottom, entrainer n-hexane and from point flow container 200
The n-hexane returned is by being n-hexane charging from the tower top of azeotropic reactive distillation column 100 addition, tower after the mixing of the first blender 501
The steam of top methyl alcohol and hexane mixture after the condensation of condenser 551 by entering a point flow container 200.
The mixture of methyl alcohol and n-hexane carries out Liquid liquid Separation in the presence of extractant water, and light component n-hexane logistics is followed
Loopback azeotropic reactive distillation column 100 is utilized, and the mixture of first alcohol and water is separated into methanol purification tower 300.
, without condenser, overhead vapours is by after compressor compresses, being that the 4th reboiler 514 is provided for methanol purification tower 300
Thermal source, afterwards after pressure-reducing valve decrease temperature and pressure and the first current divider 541 are shunted, a part of methyl alcohol is another as overhead reflux
Part methyl alcohol is produced as overhead product, and the profit of point flow container 200 is entered after the isolated water of bottom of towe and the water mixing of supplement extractant
With.
The tower base stream of azeotropic reactive distillation column 100 is separated into next door tower 400, tower top frozen-free device, overhead vapor
Dropped by lowering the temperature by pressure-reducing valve for the 5th reboiler of azeotropic reactive distillation column 100 515 provides thermal source, afterwards after compressor compresses
Pressure, then by after the shunting of the second current divider 542, a part of dimethyl carbonate loops back azeotropic as overhead reflux, another part
Reactive distillation column 100 is utilized.The side line of next door tower 400 obtains the methyl ethyl carbonate of high-purity, and bottom of towe obtains the carbon of high-purity
Diethyl phthalate.
The present invention is described in detail below by specific embodiment.
Embodiment 1
The method that azeotropic reaction rectification method of the invention produces methyl ethyl carbonate, catalyst is first in azeotropic reactive distillation column
Sodium alkoxide, n-hexane logistics, dimethyl carbonate and ethanol are with 1:1.1:1 mol ratio respectively enters the top of azeotropic reactive distillation column
Portion, middle part and middle and lower part, azeotropy rectification column overhead vapours after condenser condensation by entering a point flow container.
Dividing flow container addition extractant water carries out Liquid liquid Separation, and light component n-hexane logistics loops back azeotropic reactive distillation column profit
With the mixture of first alcohol and water carries out isolated first alcohol and water, the isolated water of bottom of towe and supplement into methanol purification tower
Enter point flow container after the mixing of extractant water to utilize.Dimethyl carbonate that azeotropic reactive distillation column bottom of towe is obtained, methyl ethyl carbonate with
And the mixture stream passes of diethyl carbonate are separated into next door tower, tower top obtains dimethyl carbonate and loops back azeotropic reaction essence
Tower utilization is evaporated, side line obtains the methyl ethyl carbonate of high-purity, and bottom of towe obtains the diethyl carbonate of high-purity.
Azeotropic reactive distillation column is plate column, and total number of theoretical plate is 30 pieces, and conversion zone is Quan Ta regions, and operating pressure is
0.05MPa, tower top temperature is 33 DEG C, and column bottom temperature is 80 DEG C, and the operating pressure of point flow container is 0.05MPa, and temperature is 30 DEG C.First
Alcohol purifying column is plate column, and total number of theoretical plate is 25 pieces, and operating pressure is 0.02MPa, and tower top temperature is 27 DEG C, and column bottom temperature is
73℃.The compression ratio of the first compressor is 2, and logistics withdrawn position is the 20th piece of methanol purification tower, and extracted amount is at withdrawn position
The 1/3 of column plate amount of liquid phase.Next door tower is packed tower, and the fore-running section number of plates is 20 pieces, number of theoretical plate and the fore-running section phase in king-tower area
Number of theoretical plate Deng, public rectifying section is 5 pieces, and the number of theoretical plate of public stripping section is 4 pieces, and operating pressure is 0.05MPa, tower top
Temperature is 55 DEG C, and column bottom temperature is 114 DEG C, and side line methyl ethyl carbonate logistics extraction position is the 10th block of king-tower area column plate.Second
The compression ratio of compressor is 2.
Methyl ethyl carbonate logistics and diethyl carbonate logistics and methanol stream composition are as shown in table 1.
Each component quality purity in methyl alcohol, diethyl carbonate logistics, methyl ethyl carbonate logistics in the embodiment 1 of table 1
As can be seen from the results, the quality purity of product methyl ethyl carbonate is 0.9950, by-product carbinol and carbonic acid two
The quality purity of ethyl ester is 0.9950.
Embodiment 2
Identical with technological process described in embodiment 1, difference is that catalyst is hydrogen-oxygen in azeotropic reactive distillation column
Change sodium, n-hexane logistics, dimethyl carbonate and ethanol are with 1.5:1.1:1 mol ratio respectively enters the top of azeotropic reactive distillation column
Portion, middle part and middle and lower part.
Azeotropic reactive distillation column is packed tower, and total number of theoretical plate is 41 pieces, and conversion zone is Quan Ta regions, and operating pressure is
0.1MPa, tower top temperature is 50 DEG C, and column bottom temperature is 95 DEG C, and the operating pressure of point flow container is 0.11MPa, and temperature is 41 DEG C.First
Alcohol purifying column is packed tower, and total number of theoretical plate is 35 pieces, and operating pressure is 0.12MPa, and tower top temperature is 42 DEG C, and column bottom temperature is
99℃.The compression ratio of the first compressor is 3.5, and logistics withdrawn position is the 30th piece of methanol purification tower, and extracted amount is withdrawn position
The 2/5 of place's column plate amount of liquid phase.Next door tower is plate column, and the fore-running section number of plates is 34 pieces, number of theoretical plate and the fore-running section in king-tower area
Equal, the number of theoretical plate of public rectifying section is 9 pieces, and the number of theoretical plate of public stripping section is 13 pieces, and operating pressure is 0.12MPa,
Tower top temperature is 80 DEG C, and column bottom temperature is 124 DEG C, and side take-off position is the 18th block of king-tower area column plate, the pressure of the second compressor
Contracting is than being 3.
Methyl ethyl carbonate logistics and diethyl carbonate logistics and methanol stream composition are as shown in table 2.
Each component quality purity in methyl ethyl carbonate logistics, diethyl carbonate logistics, methanol stream in the embodiment 2 of table 2
As can be seen from the results, the quality purity of product methyl ethyl carbonate is 0.9960, and the quality of by-product carbinol is pure
It is 0.9970 to spend, and the quality purity of diethyl carbonate is 0.9950.
Embodiment 3
Identical with technological process described in embodiment 1, difference is that catalyst is ethanol in azeotropic reactive distillation column
Sodium, n-hexane logistics, dimethyl carbonate and ethanol are with 2.5:1.1:1 mol ratio respectively enters the top of azeotropic reactive distillation column
Portion, middle part and middle and lower part.
Azeotropic reactive distillation column is plate column, and total number of theoretical plate is 51 pieces, and conversion zone is Quan Ta regions, and operating pressure is
0.2MPa, tower top temperature is 68 DEG C, and column bottom temperature is 117 DEG C, and the operating pressure of point flow container is 0.15MPa, and temperature is 43 DEG C.First
Alcohol purifying column is plate column, and total number of theoretical plate is 42 pieces, and operating pressure is 0.17MPa, and tower top temperature is 71 DEG C, and column bottom temperature is
112℃.The compression ratio of the first compressor is 4, and logistics withdrawn position is the 37th piece of methanol purification tower, and extracted amount is at withdrawn position
The 1/2 of column plate amount of liquid phase.Next door tower is plate column, and the fore-running section number of plates is 39 pieces, number of theoretical plate and the fore-running section phase in king-tower area
Number of theoretical plate Deng, public rectifying section is 13 pieces, and the number of theoretical plate of public stripping section is 20 pieces, and operating pressure is 0.25MPa, tower
Top temperature is 95 DEG C, and column bottom temperature is 148 DEG C, and side take-off position is the 19th block of king-tower area column plate.The compression of the second compressor
Than being 3.6.
Methyl ethyl carbonate logistics and diethyl carbonate logistics and methanol stream composition are as shown in table 3.
Each component quality purity in methyl ethyl carbonate logistics, diethyl carbonate logistics, methanol stream in the embodiment 3 of table 3
As can be seen from the results, the quality purity of product methyl ethyl carbonate is 0.9951, and the quality of by-product carbinol is pure
It is 0.9955 to spend, and the quality purity of diethyl carbonate is 0.9960.
Embodiment 4
Identical with technological process described in embodiment 1, difference is that catalyst is methyl alcohol in azeotropic reactive distillation column
Sodium, n-hexane logistics, dimethyl carbonate and ethanol are with 3:1.1:1 mol ratio respectively enter azeotropic reactive distillation column top,
Middle part and middle and lower part.
Azeotropic reactive distillation column is plate column, and total number of theoretical plate is 60 pieces, and conversion zone is Quan Ta regions, and operating pressure is
0.35MPa, tower top temperature is 85 DEG C, and column bottom temperature is 140 DEG C, and the operating pressure of point flow container is 0.2MPa, and temperature is 50 DEG C.First
Alcohol purifying column is plate column, and total number of theoretical plate is 50 pieces, and operating pressure is 0.2MPa, and tower top temperature is 82 DEG C, and column bottom temperature is
120℃.The compression ratio of the first compressor is 5, and logistics withdrawn position is the 45th piece of methanol purification tower, and extracted amount is at withdrawn position
The 3/5 of column plate amount of liquid phase.Next door tower is plate column, and the fore-running section number of plates is 45 pieces, number of theoretical plate and the fore-running section phase in king-tower area
Number of theoretical plate Deng, public rectifying section is 15 pieces, and the number of theoretical plate of public stripping section is 25 pieces, and operating pressure is 0.3MPa, tower
Top temperature is 107 DEG C, and column bottom temperature is 170 DEG C, and side take-off position is the 25th block of king-tower area column plate.The compression of the second compressor
Than being 5.
Methyl ethyl carbonate logistics and diethyl carbonate logistics and methanol stream composition are as shown in table 4.
Each component quality purity in methyl ethyl carbonate logistics, diethyl carbonate logistics, methanol stream in the embodiment 4 of table 4
As can be seen from the results, the quality purity of product methyl ethyl carbonate is 0.9970, and the quality of by-product carbinol is pure
It is 0.9960 to spend, and the quality purity of diethyl carbonate is 0.9970.
The method and apparatus that azeotropic reaction rectification method according to embodiments of the present invention produces methyl ethyl carbonate, by reaction and essence
Evaporate and the separation of azeotropic mixture is integrated in a tower and carries out, using next door tower separating dimethyl carbonate, diethyl carbonate, carbonic acid
Methyl ethyl ester ternary mixture, saves energy consumption, enormously simplify technological process, saves equipment investment, and product purity very
It is high.Additionally, methanol purification tower and next door tower utilize heat pump techniques and intermediate reboiler Integration ofTechnology, equipment investment is reduced
And energy consumption.
In the description of the invention, term " first ", " second " are only used for describing purpose, and it is not intended that indicating or dark
Show relative importance or the implicit quantity for indicating indicated technical characteristic.Thus, " first ", the feature of " second " are defined
Can express or implicitly include one or more this feature.In the description of the invention, " multiple " is meant that two
More than individual, unless otherwise expressly limited specifically.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means to combine specific features, structure, material or spy that the embodiment or example are described
Point is contained at least one embodiment of the invention or example.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.And, the specific features of description, structure, material or feature can be with office
Combined in an appropriate manner in one or more embodiments or example.Additionally, in the case of not conflicting, the skill of this area
Art personnel can be tied the feature of the different embodiments or example described in this specification and different embodiments or example
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (9)
1. a kind of azeotropic reaction rectification method produces the device of methyl ethyl carbonate, it is characterised in that including azeotropic reactive distillation column, divide
Flow container, methanol purification tower and next door tower；
The azeotropic reactive distillation column be arranged at intervals with from top to bottom first charging aperture, catalyst feeds, second charging aperture and
3rd charging aperture, the tower top of the azeotropic reactive distillation column is provided with the first discharging opening, the bottom of towe of the azeotropic reactive distillation column
It is provided with the second discharging opening；
The 5th charging aperture that the 4th charging aperture is connected with first discharging opening, and described point of flow container are provided with described point of flow container
On be provided with the 3rd discharging opening and the 4th discharging opening connected with the first charging aperture；
It is provided with the methanol purification tower on the 6th charging aperture connected with the 3rd discharging opening, and the methanol purification tower
It is provided with the 5th discharging opening and the 6th discharging opening connected with the 4th charging aperture；
The next door tower includes fore-running section, king-tower area, public rectifying section and public stripping section, the fore-running section be provided with it is described
7th charging aperture of the second discharging opening connection, the public stripping section is provided with the 7th discharging opening, and the king-tower area is provided with the
Eight discharging openings, the public rectifying section is provided with the 9th discharging opening connected with the second charging aperture.
2. azeotropic reaction rectification method according to claim 1 produces the device of methyl ethyl carbonate, it is characterised in that also include
First blender, the second blender, the 3rd blender, the first reboiler, the second reboiler, the 3rd reboiler, the 4th reboiler,
5th reboiler, the first compressor, the second compressor, the first current divider, the second current divider and condenser；
The output end of first blender is connected with the first charging aperture, the output end of second blender and described
Two charging apertures are connected, and the output end of the 3rd blender is connected with the 4th charging aperture, the input of first reboiler
End is connected with second discharging opening, and the output end of first reboiler is connected with the azeotropic reactive distillation column bottom of towe, institute
The input for stating the second reboiler is connected with the 6th discharging opening, the second end and the methanol purification of second reboiler
The bottom of towe connection of tower, the input of the 3rd reboiler is connected with the 7th discharging opening, the output of the 3rd reboiler
End connects with the public stripping section, the input of the 4th reboiler and the output end and the first of first compressor
The side line of alcohol purifying column is connected, the output end of the 4th reboiler and the side line of the methanol purification tower and described first point
The input for flowing device is connected, and the input of first compressor is connected with the tower top of the methanol purification tower, and described first
The output end of current divider is connected with the tower top of the 5th discharging opening and the methanol purification tower, the 5th reboiler it is defeated
Enter the end bottom of towe of the azeotropic reactive distillation column, the connection of the output end of second compressor respectively, the 5th reboiler
Output end bottom of towe respectively with the azeotropic reactive distillation column, the input of second current divider are connected, second compression
The input of machine is connected with the 9th discharging opening, the output end of second current divider respectively with the second charging aperture and institute
State the public rectifying section connection of next door tower；The input of shown condenser is connected with first discharging opening, the condenser
Second end connects with the 5th charging aperture.
3. azeotropic reaction rectification method according to claim 2 produces the device of methyl ethyl carbonate, it is characterised in that described the
The compression ratio of one compressor is 2~5, and the compression ratio of second compressor is 2~5.
4. the azeotropic reaction rectification method according to claim any one of 1-3 produces the device of methyl ethyl carbonate, and its feature exists
In the azeotropic reactive distillation column is plate column or packed tower, and the methanol purification tower is plate column or packed tower, the next door
Tower is plate column or packed tower.
5. azeotropic reaction rectification method according to claim 4 produces the device of methyl ethyl carbonate, it is characterised in that described common
The number of plates for boiling reactive distillation column is 30~60, and tower pressure interior force is 0.05MPa~0.35MPa, and tower top temperature is 33 DEG C~85 DEG C,
Column bottom temperature is 80 DEG C~140 DEG C；
Pressure in described point of flow container is 0.05MPa~0.2MPa, and temperature is 30 DEG C~50 DEG C；
The number of plates of the methanol purification tower be 25~50, tower pressure interior force be 0.02MPa~0.2MPa, tower top temperature be 27 DEG C~
82 DEG C, column bottom temperature is 73 DEG C~120 DEG C；
The number of plates of the fore-running section of the next door tower is 20~45, the number of plates of the number of plates in the king-tower area and the fore-running section
Equal, the number of plates of the public rectifying section is 5~15, and the number of plates of the public stripping section is 4~25, the next door tower
Tower pressure interior force is 0.05MPa~0.3MPa, and tower top temperature is 55 DEG C~107 DEG C, and column bottom temperature is 114 DEG C~170 DEG C.
6. the method that methyl ethyl carbonate is produced using the device as described in claim any one of 1-5, it is characterised in that including such as
Lower step：
Dimethyl carbonate is added from the second charging aperture of the azeotropic reactive distillation column, ethanol is added from the 3rd charging aperture
Enter, catalyst added from the catalyst feeds, dimethyl carbonate and ethanol is reacted in the presence of catalyst,
Entrainer n-hexane is added into the reaction system of the reaction from the first charging aperture of azeotropic reactive distillation column simultaneously, the is obtained
One mixture and the second mixture；First mixture is mixed for dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate
Compound, second mixture is methyl alcohol and hexane mixture；
By first mixture successively through second discharging opening, the 7th charging aperture into being divided in the next door tower
From respectively obtaining dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate；
Second mixture is entered in point flow container through the first discharging opening and the 5th charging aperture successively, and in described point of flow container
Water is added to isolate n-hexane, and obtains the 3rd mixture；3rd mixture is the mixture of first alcohol and water；
3rd mixture is entered in the methanol purification tower through the 3rd discharging opening and the 6th charging aperture successively
Separated, respectively obtained water and methyl alcohol.
7. the method that azeotropic reaction rectification method according to claim 6 produces methyl ethyl carbonate, it is characterised in that it is described just
The molar feed ratio of hexane, the dimethyl carbonate and the ethanol is (1~3):1.1:1, the quality of the catalyst is institute
State the 0.05%~7.5% of the quality sum of dimethyl carbonate and the ethanol.
8. the method that azeotropic reaction rectification method according to claim 6 produces methyl ethyl carbonate, it is characterised in that described to urge
Agent is at least the one kind in sodium methoxide, NaOH and caustic alcohol.
9. the method that azeotropic reaction rectification method according to claim 6 produces methyl ethyl carbonate, it is characterised in that described common
The number of plates for boiling reactive distillation column is 30~60, and tower pressure interior force is 0.05MPa~0.35MPa, and tower top temperature is 33 DEG C~85 DEG C,
Column bottom temperature is 80 DEG C~140 DEG C；
Pressure in described point of flow container is 0.05MPa~0.2MPa, and temperature is 30 DEG C~50 DEG C；
The number of plates of the methanol purification tower be 25~50, tower pressure interior force be 0.02MPa~0.2MPa, tower top temperature be 27 DEG C~
82 DEG C, column bottom temperature is 73 DEG C~120 DEG C；
The number of plates of the fore-running section of the next door tower is 20~45, the tower of the number of plates in the king-tower area and the fore-running section
Plate number is equal, and the number of plates of the public rectifying section is 5~15, and the number of plates of the public stripping section is 4~25, the next door
The tower pressure interior force of tower is 0.05MPa~0.3MPa, and tower top temperature is 55 DEG C~107 DEG C, and column bottom temperature is 114 DEG C~170 DEG C.
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| CN107573227A (en) * | 2017-08-30 | 2018-01-12 | 中国石油大学(华东) | Acetone vapour phase condensation prepares the device and method of isophorone |
| CN111773755A (en) * | 2020-07-16 | 2020-10-16 | 河北工业大学 | Method and device for preparing methyl ethyl carbonate by using bulkhead reaction rectifying tower |
| CN113461527A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | Method for dehydrating side-stream withdrawn material flow of methyl methacrylate device primary distillation tower |
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| CN114436840A (en) * | 2022-02-21 | 2022-05-06 | 江苏思派新能源科技有限公司 | Method for industrially producing methyl ethyl carbonate by reacting diethyl carbonate and dimethyl carbonate |
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| CN107573227A (en) * | 2017-08-30 | 2018-01-12 | 中国石油大学(华东) | Acetone vapour phase condensation prepares the device and method of isophorone |
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| CN113461527A (en) * | 2020-03-30 | 2021-10-01 | 中石油吉林化工工程有限公司 | Method for dehydrating side-stream withdrawn material flow of methyl methacrylate device primary distillation tower |
| CN113461527B (en) * | 2020-03-30 | 2023-10-17 | 中石油吉林化工工程有限公司 | Method for dehydrating side-stream of primary distillation tower of methyl methacrylate device |
| CN111773755A (en) * | 2020-07-16 | 2020-10-16 | 河北工业大学 | Method and device for preparing methyl ethyl carbonate by using bulkhead reaction rectifying tower |
| CN113582845A (en) * | 2021-08-05 | 2021-11-02 | 中建安装集团有限公司 | Device and process for co-producing electronic grade ethyl methyl carbonate and diethyl carbonate by reactive distillation method |
| CN113582845B (en) * | 2021-08-05 | 2023-12-05 | 中建安装集团有限公司 | Device and process for co-producing electronic grade methyl ethyl carbonate and diethyl carbonate by reaction rectification method |
| CN114436840A (en) * | 2022-02-21 | 2022-05-06 | 江苏思派新能源科技有限公司 | Method for industrially producing methyl ethyl carbonate by reacting diethyl carbonate and dimethyl carbonate |
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