CN108129310A - By the technique of ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol - Google Patents
By the technique of ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol Download PDFInfo
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- CN108129310A CN108129310A CN201711380523.3A CN201711380523A CN108129310A CN 108129310 A CN108129310 A CN 108129310A CN 201711380523 A CN201711380523 A CN 201711380523A CN 108129310 A CN108129310 A CN 108129310A
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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
- C07C68/04—Preparation of esters of carbonic or haloformic acids from carbon dioxide or inorganic carbonates
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- 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
- C07C29/1285—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis of esters of organic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
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- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/32—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D317/34—Oxygen atoms
- C07D317/36—Alkylene carbonates; Substituted alkylene carbonates
- C07D317/38—Ethylene carbonate
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Abstract
By the technique of ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, it is related to the technique of Catalysts of Preparing Methyl Ethyl Carbonate, technique azeotropic separation while reactive distillation, which synchronizes, to be carried out, extraction and separation are carried out to product without solvent, enormously simplify the technological process of conventional methyl ethyl carbonate Lipase absobed, multicomponent can be made disposably to detach simultaneously, 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.140 155 DEG C of optimum temperatures that ethylene glycol is detached for T4 ethylene glycol batch fractionating tower, tower reactor ethylene glycol content is up to more than 96% under this condition.
Description
Technical field
The present invention relates to the technique by Catalysts of Preparing Methyl Ethyl Carbonate, more particularly to one kind by ethylene oxide one-step synthesis carbonic acid
The technique of methyl ethyl ester co-production 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 titanium dioxide reaction again, and propene carbonate needs propylene oxide and carbon dioxide reaction
It prepares, above-mentioned reaction route need to be segmented progress, each elementary reaction object conversion ratio and selectivity of product are low, simultaneously because each
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.
Invention content
The purpose of the present invention is to provide a kind of works by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol
Skill, due to ethylene oxide/propylene oxide and carbon dioxide reaction, the ethylene carbonate/propylene carbonate and methanol ester of generation are handed over
Reaction and subsequent dimethyl carbonate is changed to be catalyzed, therefore we carry with the available basic catalyst of ethyl alcohol ester exchange reaction
Go out a kind of production technology of one-step synthesis method methyl ethyl carbonate.The production technology of the one-step synthesis methyl ethyl carbonate, synthesis path
Short, technological process is simple, selectivity of product and high income, and relatively current technique can significantly more efficient production methyl ethyl carbonate.
The purpose of the present invention is what is be achieved through the following technical solutions：
By the technique of ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, the technique includes procedure below：
Specific one-step synthesis method methyl ethyl carbonate reaction equation is as follows：
Raw material is respectively ethylene oxide, carbon dioxide, methanol and ethyl alcohol, glycol product and carbonic ester molar ratio 1：1 generation, second
Glycol is the bulk chemical that a kind of China largely relies on import, can effectively a large amount of coproduction ethylene glycol using the path；
Methyl ethyl carbonate production technology, including：The carbon dioxide and ethylene oxide mixture of raw material liquid are by metering pump P-1 through vapour
After changing device V-1 gasifications, into the bottom of first reactor T1；Another way material benzenemethanol, the preheated device V-2 of mixture of ethyl alcohol are pre-
By first reactor top feed after heat；The generation that contacts with each other of the catalyst member in two-way raw material portion in the first reactor is anti-
Should, the first mixture is obtained, the first mixture includes carbon dioxide, ethylene oxide, methanol, ethyl alcohol, methyl ethyl carbonate, carbonic acid two
Methyl esters, diethyl carbonate and ethylene glycol；Light component at the top of first reactor out is such as：Carbon dioxide, ethylene oxide, methanol and
Ethyl alcohol returns to first reactor, and the reaction was continued, and another part higher component such as dimethyl carbonate and methanol azeotrope, carbon
Sour methyl ethyl ester enters the preheating of V-3 preheating cans again after being condensed with ethyl alcohol azeotropy article and a small amount of diethyl carbonate etc. via condenser E-1
Compression rectification tower T2 is pumped by P-2 metering pumps；The high boiling component that first reactor bottom comes out is such as：Ethylene glycol, carbonic acid diethyl
Ester, a part enter after the condensation of E-2 condensers at the top of compression rectification tower T2, and the thick ethylene glycol of another part is directly entered ethylene glycol
Batch fractionating tower T4 adds water process to obtain ethylene glycol fine work；Into the component of compression rectification tower T2, normal pressure azeotropic composition originally
It is detached under high pressure, light component such as methanol comes back to the participation of T1 first reactors with dimethyl carbonate azeotrope and ethyl alcohol
Reaction, higher boiling composition continue to detach as carbon methyl ethyl carbonate, diethyl carbonate and ethylene glycol enter T3 atmospheric distillation towers；E-3
For cooling down methyl ethyl carbonate and diethyl carbonate, E-4 condensers are used to condense ethylene glycol condenser；Preheated tank V-4 height boilings
Point component enters T3 atmospheric distillation towers, and methyl ethyl carbonate is steamed by T3 tower tops and condenses to obtain pure methyl ethyl carbonate fine work through E-6；
And the diethyl carbonate and ethylene glycol mixture that T3 bottoms obtain enter T4 ethylene glycol batch fractionating towers through the condensation of E-7 condensers；
Thick ethylene glycol adds water process to obtain ethylene glycol fine work through T4 ethylene glycol batch fractionating towers, and diethyl carbonate steams direct receipts from tower top
Collection or return T1 first reactors continue to participate in reaction；
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；Using 5000h there is no deactivation phenomenom, usage amount is catalyst
The 0.1%~3% of the gross mass of the raw material；
The raw material ethylene oxide is with carbon dioxide with molar ratio 0.1:1-10:1 charging, vaporizer V1 temperature are 40-100 DEG C；
It beats liquid charging stock methanol with metering pump pump simultaneously to feed with ethyl alcohol, the two molar ratio 1:5-5:1；Preheating can V2 temperature is 25-60
℃；
The device of methyl ethyl carbonate is produced, including：T1 reacts first reactor, has from top to bottom in the T1 first reactors
Spaced apart catalyst inlet, material benzenemethanol and ethyl alcohol import and raw material CO2With ethylene oxide import, the T1 reactions 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.
The technique by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, the technological process,
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 CO2And ethylene oxide）Condensed device E-1 condensations are again introduced into T1 cycles；Other are compared with low-boiling point liquid
（Methanol, ethyl alcohol and its azeotropic mixture, methyl ethyl carbonate etc.）Separation, the light component of T2 tower tops are carried out into T2 compression rectifications tower
As methanol, ethyl alcohol and a small amount of azeotropic mixture composition return again to T1 reactor reactions.
The technique by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, the T1 first reactors
Tower pressure interior force for 0.01MPa~5MPa, tower top temperature is 64 DEG C~90 DEG C, and column bottom temperature is 130 DEG C~160 DEG C；It is described to add
The tower pressure interior force for pressing rectifying column T2 is 1MPa~15MPa, and tower top temperature is 50 DEG C~70 DEG C, and column bottom temperature is 130 DEG C~150
℃；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
It 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 top temperature 130
DEG C~160 DEG C, column bottom temperature is 140 DEG C~180 DEG C；When T1 first reactor tower reactor ethylene glycol contents reach more than 20%, kettle
Interior lower liquid enters T2 compression rectification towers through the condensation of E-2 condensers；When ethylene glycol content reaches more than 90%, T1 reactors
Bottom is to T4 ethylene glycol batch fractionating tower feed liquors.
The technique by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, the reactor and rectifying
It is 1 that the partition board of tower, which is arranged to the ratio between cross-sectional area for the cross-sectional area and side line section for making the fore-running section,:1-3:1.
The technique by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, it is described to state reactor fore-running
The number of plates of 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 to carry
The number of plates for evaporating section is 1~30 piece.
The technique by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, the reactor T1
One reactor, T2 compression rectifications tower, T3 atmospheric distillation towers, T4 ethylene glycol batch fractionating tower are plate column, packed tower or board-like-fill out
Expect mixing column.
Advantages of the present invention is with effect：
The present invention is by the technique of ethylene oxide, carbon dioxide, methanol and ethyl alcohol one-step synthesis methyl ethyl carbonate, synthetic route
Short, a step directly obtains target product.Contain dimethyl carbonate, methyl ethyl carbonate, carbonic acid diethyl in crude product obtained by the reaction
Ester and ethylene glycol, wherein, methyl ethyl carbonate selectively can reach 70%.By-product dimethyl carbonate and diethyl carbonate can
It is directly separated as product, also can be recycled, the reaction was continued generates methyl ethyl carbonate, and by-product ethylene glycol is as largeization original
Material is i.e. separable by simple distillation.Entire reaction process cleaning, efficient, pollution-free, the by-product produce without any low value
It is raw.
Description of the drawings
Fig. 1 is the process flow chart of one-step synthesis methyl ethyl carbonate co-production ethylene glycol of the present invention.
Specific embodiment
The following describes the present invention in detail with reference to examples.
For the present invention by the production technology of ethylene oxide, methanol, carbon dioxide and ethyl alcohol one-step synthesis methyl ethyl carbonate, this is anti-
The reaction equation answered is as follows：
The reaction is using multi-functional compound basic matterial as catalyst, by ethylene oxide（EO）, carbon dioxide, methanol (MeOH) and second
Alcohol (EtOH) is one step high selectivity methyl ethyl carbonate (EMC) of reaction raw materials, and it is former that basic catalyst is completely insoluble in reaction
Any pollutant is not present in material and product, reaction process, and glycol product (EG) is a kind of bulk chemical, has wide city
Field application prospect；The dimethyl carbonate (DMC) and diethyl carbonate (DEC) incidentally generated in reaction process can be used as product direct
Separation, also can be recycled, and the reaction was continued generates methyl ethyl carbonate.
The methyl ethyl carbonate production technology of protection, including：The carbon dioxide and ethylene oxide mixture of raw material liquid are by counting
Amount pump P-1 is after vaporizer V-1 gasifications, into the bottom of first reactor T1.The mixture warp of another way material benzenemethanol, ethyl alcohol
By first reactor top feed after preheater V-2 preheatings.The catalyst member in two-way raw material portion in the first reactor is mutual
Contact reacts, and obtains the first mixture, and the first mixture includes carbon dioxide, ethylene oxide, methanol, ethyl alcohol, carbonic acid first
Ethyl ester, dimethyl carbonate, diethyl carbonate and ethylene glycol.Light component at the top of first reactor out is such as：Carbon dioxide, epoxy
The reaction was continued for ethane, methanol and ethyl alcohol return first reactor, and another part higher component such as dimethyl carbonate and first
It is pre- that alcohol azeotropic mixture, methyl ethyl carbonate and ethyl alcohol azeotropy article and a small amount of diethyl carbonate etc. enter V-3 after being condensed via condenser E-1
Hot tank preheating is pumped into compression rectification tower T2 by P-2 metering pumps again.The high boiling component that first reactor bottom comes out is such as：Second two
Alcohol, diethyl carbonate, a part enter after the condensation of E-2 condensers at the top of compression rectification tower T2, and the thick ethylene glycol of another part is straight
It taps into and water process is added to obtain ethylene glycol fine work into ethylene glycol batch fractionating tower T4.Into the component of compression rectification tower T2, originally
Normal pressure azeotropic composition is detached under high pressure, and light component such as methanol and dimethyl carbonate azeotrope and ethyl alcohol come back to T1 the
One reactor participates in reaction, and higher boiling composition such as carbon methyl ethyl carbonate, diethyl carbonate and ethylene glycol enter T3 atmospheric distillation towers
Continue to detach.For cooling down methyl ethyl carbonate and diethyl carbonate, E-4 condensers are used to condense ethylene glycol E-3 condensers.Through pre-
Hot tank V-4 high boiling components enter T3 atmospheric distillation towers, and methyl ethyl carbonate is steamed by T3 tower tops and condenses to obtain pure carbonic acid through E-6
Methyl ethyl ester fine work.And the diethyl carbonate and ethylene glycol mixture that T3 bottoms obtain enter T4 ethylene glycol through the condensation of E-7 condensers
Batch fractionating tower.Thick ethylene glycol adds water process to obtain ethylene glycol fine work through T4 ethylene glycol batch fractionating towers, and diethyl carbonate is from tower
Top, which steams directly collection or returns to T1 first reactors, continues to participate in reaction.
Such as the technique of Fig. 1 one-step synthesis methyl ethyl carbonate co-production ethylene glycol.
The present invention production methyl ethyl carbonate method, reaction raw materials carbon dioxide, ethylene oxide, methanol, ethyl alcohol together into
Enter T1 first reactors, direct single step reaction Catalysts of Preparing Methyl Ethyl Carbonate, diethyl carbonate and ethylene glycol.While reactive distillation
Azeotropic separation, which synchronizes, to be carried out, and is carried out extraction and separation to product without solvent, is enormously simplified the work of conventional methyl ethyl carbonate Lipase absobed
Skill flow, while multicomponent can be made disposably to detach, separation purity is high.
The technique of present invention production methyl ethyl carbonate has following additional 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 raw material ethylene oxide is with carbon dioxide with molar ratio 0.1:1-10:1 charging, vaporizer V1 temperature are 40-100
℃.It beats liquid charging stock methanol with metering pump pump simultaneously to feed with ethyl alcohol, the two molar ratio 1:5-5:1.Preheating can V2 temperature is 25-
60℃。
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 raw material CO2It is described with ethylene oxide import
Bottom of towe of the tower top of T1 reaction first reactors with the first discharge port and T1 reaction first reactors is with the second discharging
Mouthful；T2 compression rectification towers have two second charging apertures being connected with first discharge port on the compression rectification tower, described
Bottom of towe of the tower lower part of compression rectification tower with the second discharge port and the compression rectification tower is with third discharge port；T3 normal pressures essence
Tower is evaporated, there is 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 CO2And ethylene oxide）Condensed device E-1 condensations are again
The secondary T1 that enters is recycled.Other are compared with low-boiling point liquid（Methanol, ethyl alcohol and its azeotropic mixture, methyl ethyl carbonate etc.）Into T2 compression rectifications
Tower carries out separation, and 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.
The additional aspect and advantage of the present invention will be set forth in part in the description, and will partly become from the following description
It obtains significantly or is recognized by the practice of the present invention.
Embodiment
Embodiment 1
Using carbon dioxide, ethylene oxide, methanol and ethyl alcohol as raw material, reaction generation methyl ethyl carbonate, methanol and ethyl alcohol object
The amount ratio of matter is 3：2, excessive carbon dioxide and ethylene oxide cycle utilize.
Catalyst is alkaline composite material 15%BaO-5%CaO-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 170 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 (6)
1. by the technique of ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, which is characterized in that the technique includes
Procedure below：
Specific one-step synthesis method methyl ethyl carbonate reaction equation is as follows：
Raw material is respectively ethylene oxide, carbon dioxide, methanol and ethyl alcohol, glycol product and carbonic ester molar ratio 1：1 generation, second
Glycol is the bulk chemical that a kind of China largely relies on import, can effectively a large amount of coproduction ethylene glycol using the path；
Methyl ethyl carbonate production technology, including：The carbon dioxide and ethylene oxide mixture of raw material liquid are by metering pump P-1 through vapour
After changing device V-1 gasifications, into the bottom of first reactor T1；Another way material benzenemethanol, the preheated device V-2 of mixture of ethyl alcohol are pre-
By first reactor top feed after heat；The generation that contacts with each other of the catalyst member in two-way raw material portion in the first reactor is anti-
Should, the first mixture is obtained, the first mixture includes carbon dioxide, ethylene oxide, methanol, ethyl alcohol, methyl ethyl carbonate, carbonic acid two
Methyl esters, diethyl carbonate and ethylene glycol；Light component at the top of first reactor out is such as：Carbon dioxide, ethylene oxide, methanol and
Ethyl alcohol returns to first reactor, and the reaction was continued, and another part higher component such as dimethyl carbonate and methanol azeotrope, carbon
Sour methyl ethyl ester enters the preheating of V-3 preheating cans again after being condensed with ethyl alcohol azeotropy article and a small amount of diethyl carbonate etc. via condenser E-1
Compression rectification tower T2 is pumped by P-2 metering pumps；The high boiling component that first reactor bottom comes out is such as：Ethylene glycol, carbonic acid diethyl
Ester, a part enter after the condensation of E-2 condensers at the top of compression rectification tower T2, and the thick ethylene glycol of another part is directly entered ethylene glycol
Batch fractionating tower T4 adds water process to obtain ethylene glycol fine work；Into the component of compression rectification tower T2, normal pressure azeotropic composition originally
It is detached under high pressure, light component such as methanol comes back to the participation of T1 first reactors with dimethyl carbonate azeotrope and ethyl alcohol
Reaction, higher boiling composition continue to detach as carbon methyl ethyl carbonate, diethyl carbonate and ethylene glycol enter T3 atmospheric distillation towers；E-3
For cooling down methyl ethyl carbonate and diethyl carbonate, E-4 condensers are used to condense ethylene glycol condenser；Preheated tank V-4 height boilings
Point component enters T3 atmospheric distillation towers, and methyl ethyl carbonate is steamed by T3 tower tops and condenses to obtain pure methyl ethyl carbonate fine work through E-6；
And the diethyl carbonate and ethylene glycol mixture that T3 bottoms obtain enter T4 ethylene glycol batch fractionating towers through the condensation of E-7 condensers；
Thick ethylene glycol adds water process to obtain ethylene glycol fine work through T4 ethylene glycol batch fractionating towers, and diethyl carbonate steams direct receipts from tower top
Collection or return T1 first reactors continue to participate in reaction；
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；Using 5000h there is no deactivation phenomenom, usage amount is catalyst
The 0.1%~3% of the gross mass of the raw material；
The raw material ethylene oxide is with carbon dioxide with molar ratio 0.1:1-10:1 charging, vaporizer V1 temperature are 40-100 DEG C；
It beats liquid charging stock methanol with metering pump pump simultaneously to feed with ethyl alcohol, the two molar ratio 1:5-5:1；Preheating can V2 temperature is 25-60
℃；
The device of methyl ethyl carbonate is produced, including：T1 reacts first reactor, has from top to bottom in the T1 first reactors
Spaced apart catalyst inlet, material benzenemethanol and ethyl alcohol import and raw material CO2With ethylene oxide import, the T1 reactions 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.
2. the technique according to claim 1 by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, special
Sign is that the technological process, in first reactor T1, raw material reacts under the effect of the catalyst, and it is mixed to obtain first
Close object；The gaseous state light component of first mixture tower top（Predominantly CO2And ethylene oxide）Condensed device E-1 condensations are again introduced into T1
Cycle；Other are compared with low-boiling point liquid（Methanol, ethyl alcohol and its azeotropic mixture, methyl ethyl carbonate etc.）Added into T2 compression rectification towers
Pressure separation, 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.
3. the technique according to claim 2 by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, special
Sign is that 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.
4. the technique according to claim 3 by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, special
Sign is, the partition board of the reactor and rectifying column is arranged to make the transversal of the cross-sectional area of the fore-running section and the side line section
Area ratio is 1:1-3:1.
5. the technique according to claim 4 by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, special
Sign is that the number of plates for stating reactor fore-running section is 1~30 piece, and the side line section number of plates is 1~30 piece, public rectifying section
The number of plates is 1~30 piece, and the number of plates of public stripping section is 1~30 piece.
6. the technique according to claim 1 by ethylene oxide one-step synthesis methyl ethyl carbonate co-production ethylene glycol, special
Sign is that the reactor T1 first reactors, T2 compression rectifications tower, T3 atmospheric distillation towers, T4 ethylene glycol batch fractionating towers are
Plate column, packed tower or board-like-filler mixing column.
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