CN108191605A - The technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol - Google Patents
The technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol Download PDFInfo
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- CN108191605A CN108191605A CN201711380449.5A CN201711380449A CN108191605A CN 108191605 A CN108191605 A CN 108191605A CN 201711380449 A CN201711380449 A CN 201711380449A CN 108191605 A CN108191605 A CN 108191605A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol, is related to preparing the production technology of methyl ethyl carbonate, which catalyzes and synthesizes methyl ethyl carbonate, diethyl carbonate and ethylene glycol with the multi-functional compound direct step of basic matterial catalyst.Azeotropic separation, which synchronizes, while reactive distillation carries out, and carries out extraction and separation to product without solvent, enormously simplifies the technological process of conventional methyl ethyl carbonate Lipase absobed, while multicomponent can be made disposably to detach, separation purity is high.Methyl ethyl carbonate selectively can reach 70% in crude product obtained by the reaction.By-product dimethyl carbonate and diethyl carbonate can be directly separated as product, also can be recycled, and the reaction was continued generates methyl ethyl carbonate, and by-product ethylene glycol is separated as largeization raw material by simple distillation.Entire reaction process cleaning, efficient, pollution-free, no any waste generation.
Description
Technical field
The present invention relates to a kind of production technology for preparing methyl ethyl carbonate, more particularly to one-step synthesis methyl ethyl carbonate simultaneously
The technique of coproduction ethylene glycol.
Background technology
Methyl ethyl carbonate（Methyl Ethyl Carbonate, abbreviation MEC）, molecular formula：C4H8O3, colourless transparent liquid,
1.01 g/mL of density, -55 DEG C of fusing point, 107 DEG C of boiling point is flammable, can be mixed with arbitrary proportion with organic solvent such as alcohol, ketone, ester,
It is a kind of excellent solvent, methyl ethyl carbonate due to having methyl and ethyl simultaneously in its molecular structure, so it has carbonic acid concurrently
The characteristic of dimethyl ester, diethyl carbonate, can be as certain special organic synthesis reagents, while it is also the molten of extraordinary fragrance
Agent.
Since the viscosity of methyl ethyl carbonate is small, dielectric constant is big, strong to the dissolubility of lithium salts, therefore it is a kind of excellent
Lithium ion battery electrolyte solvent can improve the energy density and discharge capacity of battery, can more improve the safety of battery
Energy and service life.
Consulting literatures are it is found that methyl ethyl carbonate is mainly the following synthetic method at present：
（One）Phosgenation
Phosgenation is the process using phosgene and methanol/ethanol as Material synthesis methyl ethyl carbonate, and reaction equation is as follows：
COCl2 + CH3OH→CH3OCOCl.................(1)
CH3OCOCl + C2H5OH→CH3OCOOC2H5.......(2)
COCl2 +C2H5OH→C2H5OCOCl..........(3)
C2H5OCOCl + CH3OH→CH3OCOOC2H5.........(4)
The method Catalysts of Preparing Methyl Ethyl Carbonate byproduct of reaction is more（Main By product is dimethyl carbonate, diethyl carbonate, chloro-carbonic acid
Methyl esters, ethyl chloroformate）, operating difficulties generates the hydrogen chloride of strong corrosive during simultaneous reactions, it is desirable that equipment has corrosion resistant
Corrosion increases equipment investment.Phosgene has hypertoxicity, and great risk, and the method are caused to the health of operating personnel
Methyl ethyl carbonate yield is relatively low, therefore is gradually eliminated.
（Two）Oxidative carbonylation
Oxidative carbonylation is using carbon monoxide, oxygen, methanol and ethyl alcohol as raw material, in certain temperature and pressure and in catalyst
Under existence condition, Catalysts of Preparing Methyl Ethyl Carbonate, reaction equation is as follows：
CH3OH + C2H5OH + CO + O2→CH3OCOOC2H5 + H2O.........(5)
The method major defect is that byproduct of reaction is more（Main By product has dimethyl carbonate, diethyl carbonate, water）, follow-up point
From purification difficult, production cost is increased.
（Three）Ester-interchange method
1st, methylchloroformate and ethyl alcohol ester-interchange method
Edmund PWoo and Ichiro Minami etc. is reported using methylchloroformate and ethyl alcohol as raw material, passes through ester-interchange method
Catalysts of Preparing Methyl Ethyl Carbonate, reaction equation are as follows：
C2H5OH + CH3OCOCl→CH3OCOOC2H5 + HCl.........(6)
The catalysts are alkali（Such as pyridine, organic amine）, purer methyl ethyl carbonate can be obtained, but shortcoming is to have used poison
Property higher methylchloroformate, simultaneous reactions generate corrosive hydrogen chloride gas, higher to equipment requirement.
2nd, dimethyl carbonate and diethyl carbonate ester-interchange method
Load metal oxide such as SnO of the Shen Zhen lands et al. using load on alumina2/Al2O3、MoO3/Al2O3、TiO2/
Al2O3Deng as catalyst, using dimethyl carbonate and diethyl carbonate as raw material, by Synthesis of Ethyl Methyl Carbonate by Transesterification,
The mass percent of the catalyst metal oxide of preparation is 2%-30%, remaining is aluminium oxide, and the amount of metal oxide accounts for raw material
The 0.1%-10% of total amount, 50-100 DEG C of reaction temperature carry out 2-48 h under normal pressure, and methyl ethyl carbonate yield is 43.6%.The route
The advantages of be that reaction process is simple, non-environmental-pollution, but shortcoming is that the reaction time is long, the catalyst activity reported at this stage compared with
It is low.
3rd, dimethyl carbonate and ethyl alcohol ester-interchange method
Using dimethyl carbonate and ethyl alcohol as raw material, by Synthesis of Ethyl Methyl Carbonate by Transesterification, raw material used in the route is all
It is non-toxic, reaction condition is mild, environmentally safe, therefore has very by the report of this route Catalysts of Preparing Methyl Ethyl Carbonate
More, the reaction equation involved by the route is as follows：
CH3OCOOCH3 + CH3CH2OH→CH3OCOOCH2CH3 + CH3OH...............................
(7)
CN1900047 A are using aluminium oxide, activated carbon, molecular sieve as carrier, carrying alkali metal oxide, alkaline-earth metal oxide
One kind of object and rare-earth oxide, although separation problem is not present in catalyst, activity is not so good as homogeneous catalyst.
CN101289395 A are with NaOH, KOH, CH3ONa、CH3The strong alkaloids such as OK are as catalyst, and the catalyst is in reaction solution
Solubility is bad, and easily precipitation, easy fouling.CN103483200 A are using modified molecular sieve as catalyst, wherein modified member
Element is one or more of alkali metal, alkaline-earth metal, Fe, Zn, Ni, Cu, although catalyst preparation process is simple, reacts institute
The temperature needed is high.CN102850223 A, CN102863339 A and CN102850224 A are using the ionic liquid of imidazoles as catalysis
Agent, recoverable, long lifespan, but catalyst recycling is needed by specially treated.US5962720 is with SmL2、Li、CH3OLi
And CaH2Deng for catalyst, but reaction reaches balance needs three days.
At present, mainly using ester-interchange method as mainstream synthetic route in all of above methyl ethyl carbonate synthetic method, but ester is handed over
Changing the oxide spinel dimethyl ester of method need to be synthesized by ethylene carbonate or propene carbonate by methanol transesterification, and carbonic acid second
Enester needs to prepare by ethylene oxide and carbon dioxide reaction again, and propene carbonate needs ethylene oxide and carbon dioxide anti-
It should prepare, above-mentioned reaction route need to be segmented progress, each elementary reaction object conversion ratio and selectivity of product are low, simultaneously because respectively
A stage is required for carrying out complex distillation lock out operation to each product, and industrial processes energy consumption is big, and operating cost increases.
Due to ethylene carbonate/propylene carbonate and methanol ester exchange reaction and subsequent dimethyl carbonate and ethyl alcohol ester
The available basic catalyst of exchange reaction is catalyzed, therefore it is proposed that a kind of production work of one-step synthesis method methyl ethyl carbonate
Skill.The production technology of the one-step synthesis methyl ethyl carbonate, synthesis path is short, and technological process is simple, selectivity of product and high income,
Relatively current technique can significantly more efficient production methyl ethyl carbonate.
Invention content
The purpose of the present invention is to provide the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol, present invention production carbon
The method of sour methyl ethyl ester, reaction raw materials ethylene carbonate, methanol, ethyl alcohol enter T1 first reactors, direct single step reaction together
Catalysts of Preparing Methyl Ethyl Carbonate, diethyl carbonate and ethylene glycol.Azeotropic separation, which synchronizes, while reactive distillation carries out, without solvent pair
Product carries out extraction and separation, enormously simplifies the technological process of conventional methyl ethyl carbonate Lipase absobed, while multicomponent can be made primary
Property separation, separation purity is high.
The purpose of the present invention is what is be achieved through the following technical solutions：
The technique of present invention production methyl ethyl carbonate has following technical characteristic：
The technique used catalyst is a kind of multi-functional compound basic matterial, and catalyst carrier is with the compound duct of Jie's micropore
Molecular sieve, load Determination of multiple metal elements is as active component.Deactivation phenomenom is not present using 5000h in catalyst performance stabilised,
Usage amount is the 0.1%~3% of the gross mass of the raw material.
The oxide spinel vinyl acetate is pumped by P-1 and fed, and vaporizer V1 temperature is 40-100 DEG C.It is pumped simultaneously with metering pump
It beats liquid charging stock methanol to feed with ethyl alcohol, the two molar ratio 1:5-5:1.Preheating can V2 temperature is 25-60 DEG C.
The device of present invention production methyl ethyl carbonate, including：T1 reacts first reactor, has in the T1 first reactors
There are from top to bottom spaced apart catalyst inlet, material benzenemethanol and ethyl alcohol import and oxide spinel vinyl acetate import, the T1
Bottom of towe of the tower top of first reactor with the first discharge port and T1 reaction first reactors is reacted with the second discharge port；
T2 compression rectification towers, have two second charging apertures being connected with first discharge port on the compression rectification tower, it is described plus
Bottom of towe of the tower lower part of rectifying column with the second discharge port and the compression rectification tower is pressed with third discharge port；T3 atmospheric distillations
Tower has the third feed inlet being connected with second and third described discharge port, the 4th discharging with tower top in the atmospheric distillation tower
Mouth, the 5th discharge port being connected with T4 ethylene glycol batch fractionating towers；T4 ethylene glycol batch fractionating towers, the ethylene glycol interval essence
The 4th feed inlet for having on tower and being connected with the 5th discharge port is evaporated, the ethylene glycol batch fractionating column overhead has the 6th to go out
Material mouth, lower part is with the 5th feed inlet and bottom of towe is with the 7th discharge port.
An example according to the present invention, in first reactor T1, raw material reacts under the effect of the catalyst, obtains
To the first mixture；The gaseous state light component of first mixture tower top（Predominantly methanol and ethyl alcohol）Condensed device E-1 condensations are again
It is recycled into T1.Other are compared with low-boiling point liquid（Methanol, ethyl alcohol and its azeotropic mixture, methyl ethyl carbonate etc.）Into T2 compression rectification towers
Separation is carried out, the light component such as methanol, ethyl alcohol of T2 tower tops and a small amount of azeotropic mixture composition return again to T1 reactor reactions.
The tower pressure interior force of the T1 first reactors is 0.01MPa~5MPa, and tower top temperature is 64 DEG C~90 DEG C, bottom of towe temperature
Spend is 130 DEG C~160 DEG C；The tower pressure interior force of the compression rectification tower T2 is 1MPa~15MPa, and tower top temperature is 50 DEG C~70
DEG C, column bottom temperature is 130 DEG C~150 DEG C；The tower pressure interior force of the atmospheric distillation tower T3 be 0.1MPa~0.5MPa, tower top temperature
It it is 105 DEG C~125 DEG C, column bottom temperature is 110 DEG C~130 DEG C；The tower pressure interior force of the ethylene glycol batch fractionating tower T4 is
0.1MPa~0.5MPa, tower top temperature are 130 DEG C~160 DEG C, and column bottom temperature is 140 DEG C~180 DEG C；When T1 first reactor towers
When kettle ethylene glycol content reaches more than 20%, lower liquid enters T2 compression rectification towers through the condensation of E-2 condensers in kettle；When second two
When alcohol content reaches more than 90%, T1 reactors bottom is to T4 ethylene glycol batch fractionating tower feed liquors.
The partition board of heretofore described reactor and rectifying column is arranged to the cross-sectional area for making the fore-running section and the side
The ratio between cross-sectional area of line segment is 1:1-3:1.
The number of plates of fore-running section is 1~30 piece, and the side line section number of plates is 1~30 piece, the number of plates of public rectifying section for 1~
30 pieces, the number of plates of public stripping section is 1~30 piece.
T1 first reactors, T2 compression rectifications tower, T3 atmospheric distillation towers, T4 ethylene glycol batch fractionating tower are plate in the present invention
Formula tower, packed tower or board-like-filler mixing column.
Advantages of the present invention is with effect：
The additional aspect and advantage of the present invention will be set forth in part in the description, and partly will become bright from the following description
It shows or is recognized by the practice of the present invention.
The method of present invention production methyl ethyl carbonate, reaction raw materials ethylene carbonate, methanol, ethyl alcohol enter T1 first together
Reactor, direct single step reaction Catalysts of Preparing Methyl Ethyl Carbonate, diethyl carbonate and ethylene glycol.Azeotropic separation while reactive distillation
It is synchronous to carry out, extraction and separation are carried out to product without solvent, enormously simplify the technological process of conventional methyl ethyl carbonate Lipase absobed, together
When multicomponent can be made disposably to detach, separation purity is high.
Synthetic route of the present invention is short, and a step directly obtains target product.Contain carbonic acid diformazan in crude product obtained by the reaction
Ester, methyl ethyl carbonate, diethyl carbonate and ethylene glycol, wherein, methyl ethyl carbonate selectively can reach 70%.By-product carbon
Dimethyl phthalate and diethyl carbonate can be directly separated as product, also can be recycled, the reaction was continued generation methyl ethyl carbonate, pair
Glycol product is i.e. separable by simple distillation as largeization raw material.Entire reaction process cleans, is efficient, pollution-free,
The by-product of no any low value generates.
Description of the drawings
Fig. 1 is present invention process flow chart.
Specific embodiment
The following describes the present invention in detail with reference to examples.
A kind of production technology by ethylene carbonate, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate of the invention, the technique
The reaction equation of reaction is as follows：
The reaction is using multi-functional compound basic matterial as catalyst, by ethylene carbonate（EC）, methanol (MeOH) and ethyl alcohol
(EtOH) it is one step high selectivity methyl ethyl carbonate (EMC) of reaction raw materials, basic catalyst is completely insoluble in reaction raw materials
And any pollutant is not present in product, reaction process, glycol product (EG) is a kind of bulk chemical, is had a vast market
Application prospect；The dimethyl carbonate (DMC) and diethyl carbonate (DEC) incidentally generated in reaction process can directly divide as product
From, also can be recycled, the reaction was continued generation methyl ethyl carbonate.
The methyl ethyl carbonate production technology of protection, including：The ethylene carbonate of raw material liquid is by metering pump P-1 through vaporizer
After V-1 gasifications, into the bottom of first reactor T1.Another way material benzenemethanol, ethyl alcohol mixture preheated device V-2 preheatings after
By first reactor top feed.The catalyst member in portion contacts with each other and reacts two-way raw material in the first reactor, obtains
To the first mixture, the first mixture includes ethylene carbonate, methanol, ethyl alcohol, methyl ethyl carbonate, dimethyl carbonate, carbonic acid two
Ethyl ester and ethylene glycol.Light component at the top of first reactor out is such as：The reaction was continued for methanol and ethyl alcohol return first reactor, and
Another part higher component such as dimethyl carbonate and methanol azeotrope, methyl ethyl carbonate and ethyl alcohol azeotropy article and a small amount of carbonic acid
Diethylester etc. enters the preheating of V-3 preheating cans and is pumped into compression rectification tower T2 by P-2 metering pumps again after being condensed via condenser E-1.The
The high boiling component that one reactor bottom comes out is such as：Ethylene glycol, diethyl carbonate, a part enter after the condensation of E-2 condensers
At the top of compression rectification tower T2, the thick ethylene glycol of another part is directly entered ethylene glycol batch fractionating tower T4 and water process is added to obtain ethylene glycol
Fine work.Into the component of compression rectification tower T2, normal pressure azeotropic composition originally is detached under high pressure, light component such as methanol with
Dimethyl carbonate azeotrope and ethyl alcohol come back to T1 first reactors and participate in reacting, higher boiling composition such as carbon methyl ethyl carbonate,
Diethyl carbonate and ethylene glycol, which enter T3 atmospheric distillation towers, to be continued to detach.E-3 condensers are used to cool down methyl ethyl carbonate and carbonic acid
Diethylester, E-4 condensers are used to condense ethylene glycol.Preheated tank V-4 high boiling components enter T3 atmospheric distillation towers, methyl ethyl carbonate
Ester is steamed by T3 tower tops and condenses to obtain pure methyl ethyl carbonate fine work through E-6.And the diethyl carbonate and second two that T3 bottoms obtain
Alcohol mixture enters T4 ethylene glycol batch fractionating towers through the condensation of E-7 condensers.Thick ethylene glycol adds through T4 ethylene glycol batch fractionating towers
Water process obtains ethylene glycol fine work, and diethyl carbonate steams directly collection or return to T1 first reactors and continues to participate in instead from tower top
It should.
Embodiment 1
Using ethylene carbonate, methanol and ethyl alcohol as raw material, reaction generates the amount ratio of methyl ethyl carbonate, methanol and ethanol material
It is 3：2, excessive ethylene carbonate recycles.
Catalyst is alkaline composite material 15%BaO-5%MgO-3%La2O3/ Cs-meso-EMT, dosage are raw material gross mass
The 3% of sum, the ratio between fore-running section and the cross-sectional area of side line section are 1：1.
Operating condition is as follows：
First reactor T1：Tower diameter 1000mm；Tower height 19000mm；Public rectifying section, fore-running section, side line section, public stripping section
The number of plates is respectively 10,20,30,15；Tower pressure interior force 5MPa；70 DEG C of tower top temperature；150 DEG C of the column bottom temperature of public stripping section；
130 DEG C of the column bottom temperature of side line section.
Compression rectification tower T2：Tower diameter 3000mm；Tower height 40000mm；Public rectifying section, fore-running section, side line section, public stripping
The number of plates of section is respectively 10,20,30,15；6 MPa of tower pressure interior force；60 DEG C of tower top temperature, the column bottom temperature of public stripping section
140℃；130 DEG C of the column bottom temperature of side line section.
Atmospheric distillation tower T3：Tower diameter 4000mm；Tower height 50000mm；Public rectifying section, fore-running section, public stripping section tower
Plate number is respectively 10,20,15；Tower pressure interior force 0.1MPa, 115 DEG C of tower top temperature, 130 DEG C of the column bottom temperature of public stripping section.
Ethylene glycol batch fractionating tower T4：Tower diameter 4500mm；Tower height 40000mm；Public rectifying section, fore-running section, public stripping
The number of plates of section is respectively 10,20,15；Tower pressure interior force 0.1MPa, 140 DEG C of tower top temperature, the column bottom temperature 160 of public stripping section
℃。
The results are shown in table below for the charging and discharging of first reactor T1：
The different total raw material mass flows of table 1 separate each group the influence of liquid mass ratio
Since the amount of the substance of EG is the sum of amount of substance of DMC, EMC and DEC, be not included in EG in table goes out liquid mass ratio.From
Table 1 can be seen that, start to increase as the increase of total raw material mass flow goes out methanol and ethanol content in liquid composition, into reactor
Reactant not up to react equilibrium state just distillated from reactor.Therefore 2500kg/h is best total raw material mass flow.
Embodiment 2
Under the operating condition of embodiment 1, total raw material mass flow is 2500kg/h, during rectifying pressure 3MPa, changes T2 pressurizations
Rectifier column reflux ratio, the variation of tower reactor bottom methyl ethyl carbonate mass fraction are as shown in table 2.
The influence that the different reflux ratios of table 2 change T2 compression rectification tower reactors bottom methyl ethyl carbonate mass fraction
As can be seen from Table 2, as reflux ratio increases, T2 compression rectification tower reactors bottom EMC mass fractions first increase increases speed afterwards
Significantly slow down.The reason is that with the increase of reflux ratio, the azeotropic mixture quilt of the more methanol of tower top, ethyl alcohol, DMC and DMC and methanol
Take away liquid phase, the DMC mass fractions in tower reactor fraction reduce, and the mass fraction of opposite EMC is with increase, but reflux ratio is more than
DEC mass fractions are basically unchanged after 3, the reason is that after split ratio reaches certain value, the composition of kettle liquid reflux has reached balance.
But excessive reflux ratio will also result in unit capacity reduction, therefore, reflux ratio control is best 3 during rectifying.
Embodiment 3
Under the operating condition of embodiment 1, when total raw material mass flow is 2500kg/h, change the pressure of T2 compression rectification towers,
The items composition mass fraction variation of tower reactor bottom is as shown in table 3.
The influence that 3 different pressures of table form T2 rectifying tower reactors bottom
From table 3 it can be seen that with the mass fraction of methanol and ethyl alcohol reduction in each liquid phase composition of the raising of reaction pressure, reason
It is that the boiling-point difference that azeotropic mixture forms under elevated pressures increases, azeotropic mixture is more prone to separate.But when pressure be higher than 3MPa when each group
Into being held essentially constant, since high pressure is higher for equipment requirement, input cost can be greatly increased, therefore 3MPa is the rectifying
The optimum condition of journey.
Embodiment 4
Under the operating condition of embodiment 1, the influence of the temperature of T4 ethylene glycol batch fractionating tower tower reactors to ethylene glycol separating effect
As shown in table 4.
Influence of the table 4T4 batch fractionating towers bottom temperature to ethylene glycol separating effect
From table 4, it can be seen that with the raising of bottom temperature, ethylene glycol, which contains, to be gradually risen, but the accordingly also corresponding increasing of raffinate ratio
It is high.Therefore control bottom temperature is 140-155 DEG C, otherwise can generate ethylene glycol monomethyl ether, diethylene glycol, tirethylene glycol etc.,
And temperature is higher, the amount of by-products of generation is bigger.
The above is only several embodiments of the application, any type of limitation is not done to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, make a little variation using the technology contents of the disclosure above or modification is equal to
Case study on implementation is imitated, is belonged in the range of technical solution.
Claims (9)
1. the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol, which is characterized in that the technique is ethylene carbonate, first
The technique of alcohol and ethyl alcohol one-step synthesis methyl ethyl carbonate, including procedure below：
Specific one-step synthesis method methyl ethyl carbonate reaction equation is as follows：
Raw material is respectively ethylene carbonate, methanol and ethyl alcohol, glycol product and carbonic ester molar ratio 1：1 generation, methyl ethyl carbonate
Ester production technology, including：After the ethylene carbonate ester admixture of raw material liquid is by metering pump P-1 heated device V-1 heating, into the
The bottom of one reactor T1；Another way material benzenemethanol, ethyl alcohol mixture preheated device V-2 preheatings after by the top of first reactor
Charging；The catalyst member in portion contacts with each other and reacts two-way raw material in the first reactor, obtains the first mixture, and first
Mixture includes ethylene carbonate, methanol, ethyl alcohol, methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and ethylene glycol；First
The light component that reactor head comes out is such as：The reaction was continued for methanol and ethyl alcohol return first reactor, and another part higher
Component such as dimethyl carbonate is with methanol azeotrope, methyl ethyl carbonate and ethyl alcohol azeotropy article and a small amount of diethyl carbonate etc. via condensation
Enter the preheating of V-3 preheating cans after device E-1 condensations and compression rectification tower T2 is pumped by P-2 metering pumps again；First reactor bottom comes out
High boiling component such as：Ethylene glycol, diethyl carbonate, a part enter after the condensation of E-2 condensers at the top of compression rectification tower T2,
The thick ethylene glycol of another part is directly entered ethylene glycol batch fractionating tower T4 and water process is added to obtain ethylene glycol fine work；Into compression rectification
The component of tower T2, normal pressure azeotropic composition originally are detached under high pressure, light component such as methanol and dimethyl carbonate azeotrope
T1 first reactors, which are come back to, with ethyl alcohol participates in reaction, higher boiling composition such as carbon methyl ethyl carbonate, diethyl carbonate and second two
Alcohol, which enters T3 atmospheric distillation towers, to be continued to detach；E-3 condensers are used to cool down methyl ethyl carbonate and diethyl carbonate, E-4 condensers
For condensing ethylene glycol；Preheated tank V-4 high boiling components enter T3 atmospheric distillation towers, methyl ethyl carbonate by T3 tower tops steam through
E-6 condenses to obtain pure methyl ethyl carbonate fine work；And the diethyl carbonate and ethylene glycol mixture that T3 bottoms obtain are condensed through E-7
Device condensation enters T4 ethylene glycol batch fractionating towers；Thick ethylene glycol adds water process to obtain ethylene glycol essence through T4 ethylene glycol batch fractionating towers
Product, diethyl carbonate steams directly collection or return to T1 first reactors from tower top continues to participate in reaction.
2. the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol according to claim 1, which is characterized in that described
The technique used catalyst is a kind of multi-functional compound basic matterial, and catalyst carrier is the molecule with the compound duct of Jie's micropore
Sieve, load Determination of multiple metal elements is as active component；Its usage amount is the 0.1%~3% of the raw material gross mass.
3. the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol according to claim 1, which is characterized in that described
Oxide spinel vinyl acetate enters heater through P-1 pumps, and heater V1 temperature is 40-100 DEG C；Simultaneously liquid original is beaten with metering pump pump
Expect that methanol is fed with ethyl alcohol, the two molar ratio 1:5-5:1；Preheating can V2 temperature is 25-60 DEG C.
4. the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol according to claim 1, which is characterized in that described
The device of the production methyl ethyl carbonate of technique, including：T1 reacts first reactor, have in the T1 first reactors by up to
Under spaced apart catalyst inlet, material benzenemethanol and ethyl alcohol import and oxide spinel vinyl acetate import, T1 reaction first
Bottom of towe of the tower top of reactor with the first discharge port and T1 reaction first reactors is with the second discharge port；T2 pressurization essences
Tower is evaporated, there is two second charging apertures being connected with first discharge port, the compression rectification tower on the compression rectification tower
Bottom of towe of the tower lower part with the second discharge port and the compression rectification tower with third discharge port；T3 atmospheric distillation towers, it is described
There is the 4th discharge port of the third feed inlet being connected with second and third described discharge port and tower top and T4 second in atmospheric distillation tower
The 5th discharge port that glycol batch fractionating tower is connected；T4 ethylene glycol batch fractionating towers have on the ethylene glycol batch fractionating tower
There is the 4th feed inlet being connected with the 5th discharge port, the ethylene glycol batch fractionating column overhead has the 6th discharge port, under
Portion is with the 5th feed inlet and bottom of towe is with the 7th discharge port.
5. the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol according to claim 4, which is characterized in that described
The partition board of reactor and rectifying column is arranged to make the ratio between the cross-sectional area of the fore-running section and the cross-sectional area of the side line section are
1:1-3:1。
6. the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol according to claim 4, which is characterized in that described
The number of plates of fore-running section is 1~30 piece, and the side line section number of plates is 1~30 piece, and the number of plates of public rectifying section is 1~30 piece, public
The number of plates of stripping section is 1~30 piece altogether.
7. the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol according to claim 4, which is characterized in that described
T1 first reactors, T2 compression rectifications tower, T3 atmospheric distillation towers, T4 ethylene glycol batch fractionating tower are plate column, packed tower or plate
Formula-filler mixing column.
8. the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol according to claim 1, which is characterized in that described
In first reactor T1, raw material reacts under the effect of the catalyst, obtains the first mixture；The gas of first mixture tower top
State light component（Predominantly methanol and ethyl alcohol）Condensed device E-1 condensations are again introduced into T1 cycles；Other are compared with low-boiling point liquid（First
Alcohol, ethyl alcohol and its azeotropic mixture, methyl ethyl carbonate etc.）Separation is carried out into T2 compression rectifications tower, the light component of T2 tower tops is such as
Methanol, ethyl alcohol and a small amount of azeotropic mixture composition return again to T1 reactor reactions.
9. the technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol according to claim 1, which is characterized in that described
The tower pressure interior force of T1 first reactors be 0.01MPa~5MPa, tower top temperature be 64 DEG C~90 DEG C, column bottom temperature for 130 DEG C~
160℃；The tower pressure interior force of the compression rectification tower T2 is 1MPa~15MPa, and tower top temperature is 50 DEG C~70 DEG C, and column bottom temperature is
130 DEG C~150 DEG C；The tower pressure interior force of the atmospheric distillation tower T3 is 0.1MPa~0.5MPa, and tower top temperature is 105 DEG C~125
DEG C, column bottom temperature is 110 DEG C~130 DEG C；The tower pressure interior force of the ethylene glycol batch fractionating tower T4 be 0.1MPa~0.5MPa, tower
It is 130 DEG C~160 DEG C to push up temperature, and column bottom temperature is 140 DEG C~180 DEG C；When T1 first reactor tower reactor ethylene glycol contents reach
When more than 20%, lower liquid enters T2 compression rectification towers through the condensation of E-2 condensers in kettle；When ethylene glycol content reaches more than 90%
When, T1 reactors bottom is to T4 ethylene glycol batch fractionating tower feed liquors.
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