CN108033880A - By the technique of 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production - Google Patents
By the technique of 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production Download PDFInfo
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- CN108033880A CN108033880A CN201711380545.XA CN201711380545A CN108033880A CN 108033880 A CN108033880 A CN 108033880A CN 201711380545 A CN201711380545 A CN 201711380545A CN 108033880 A CN108033880 A CN 108033880A
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- 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
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
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- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
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Abstract
By propylene oxide one-step synthesis methyl ethyl carbonate co-production 1, the technique of 2 propane diols, it is related to the technique of Catalysts of Preparing Methyl Ethyl Carbonate, technique azeotropic separation while reactive distillation synchronously carries out, extract and separate is carried out to product without solvent, the technological process of conventional methyl ethyl carbonate Lipase absobed is enormously simplify, while multicomponent can be made disposably to separate, separation purity is high.When T1 reactor total raw materials mass flow is 2500 kg/h, T2 compression rectification towers reflux ratio is 3, and methyl ethyl carbonate mass fraction is up to 64% when pressure is 3MPa.150 157 DEG C are T41, and 2 propane diols batch fractionating towers separate the optimum temperature of 1,2 propane diols, and 1,2 content of propylene glycol of tower reactor is up to more than 97% under the conditions of being somebody's turn to do.Accessory substance 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 1,2 propane diols of accessory substance is separated as largeization raw material by simple distillation.Whole reaction process cleaning, efficient, pollution-free, no any discarded object generation.
Description
Technical field
The present invention relates to a kind of technique of Catalysts of Preparing Methyl Ethyl Carbonate, more particularly to one kind by propylene oxide one-step synthesis carbon
The technique of sour 1,2 propane diols of methyl ethyl ester co-production.
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 at the same time in its molecular structure, so it has carbonic acid concurrently
The characteristic of dimethyl ester, diethyl carbonate, can be as some special organic synthesis reagents, while it is also the molten of extraordinary spices
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, it is possible to increase the energy density and discharge capacity of battery, can more improve the security of battery
Energy and service life.
Consulting literatures understand that methyl ethyl carbonate is mainly the following synthetic method at present：
（One）Phosgenation
Phosgenation is as follows using process of the phosgene with methanol/ethanol as Material synthesis methyl ethyl carbonate, reaction equation：
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, the hydrogen chloride of severe corrosive is produced during simultaneous reactions, it is desirable to which equipment has corrosion resistant
Corrosion, adds 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 ethanol 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 added.
（Three）Ester-interchange method
1st, methylchloroformate and ethanol ester-interchange method
Edmund PWoo and Ichiro Minami etc. is reported using methylchloroformate and ethanol 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 produce 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 catalyst is used as, using dimethyl carbonate and diethyl carbonate as raw material, by Synthesis of Ethyl Methyl Carbonate by Transesterification, its
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 be the reaction time length, the catalyst activity reported at this stage compared with
It is low.
3rd, dimethyl carbonate and ethanol ester-interchange method
Using dimethyl carbonate and ethanol 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 gentle, 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 thing 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 the one or more in 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 ester exchange, and ethylene
Enester needs to prepare by ethylene oxide and titanium dioxide reaction again, and propene carbonate needs propylene oxide and carbon dioxide reaction
To prepare, above-mentioned reaction scheme need to be segmented progress, and each elementary reaction thing 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, operating cost increase.
The content of the invention
It is an object of the invention to provide a kind of by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production
Technique, the present invention due to ethylene oxide/propylene oxide and carbon dioxide reaction, the ethylene carbonate/propylene carbonate of generation and
Methanol ester exchange reaction, and follow-up dimethyl carbonate are catalyzed with the available basic catalyst of ethanol ester exchange reaction, because
This is it is proposed that 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 is short, and technological process is simple, selectivity of product and high income, and relatively current technique can significantly more efficient production carbonic acid first
Ethyl ester.
The purpose of the present invention is what is be achieved through the following technical solutions：
By the technique of 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, the technique includes procedure below：
Specific one-step synthesis method methyl ethyl carbonate reaction equation is as follows：
+CO2+CH3OH+CH3CH2OH→HOCH2CHOHCH3+CH3OCOOCH2CH3……(1)
Raw material is respectively propylene oxide, carbon dioxide, methanol and ethanol, product 1,2-PD and carbonic ester molar ratio 1：1 life
Into can effectively a large amount of coproduction 1,2-PDs using the path；
Methyl ethyl carbonate production technology, including：The carbon dioxide and propylene 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；The preheated device V-2 of another way material benzenemethanol, the mixture of ethanol is pre-
By first reactor its 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, propylene oxide, methanol, ethanol, methyl ethyl carbonate, carbonic acid two
Methyl esters, diethyl carbonate and 1,2- propane diols；Light component at the top of first reactor out is such as：Carbon dioxide, propylene oxide, first
The reaction was continued for alcohol and ethanol return first reactor, and another part higher component such as dimethyl carbonate and methanol azeotropic
It is pre- that thing, methyl ethyl carbonate and ethyl alcohol azeotropy article and a small amount of diethyl carbonate etc. enter V-3 preheating cans after being condensed via condenser E-1
Heat 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：1,2- propane diols,
Diethyl carbonate, a part enter at the top of compression rectification tower T2 after the condensation of E-2 condensers, and the thick 1,2-PD of another part is straight
Tap into and add water process to obtain 1,2- propane diols fine work into 1,2- propane diols batch fractionating towers T4；Into the group of compression rectification tower T2
Point, normal pressure azeotropic composition originally is separated under high pressure, light component such as methanol and dimethyl carbonate azeotrope and ethanol weight
The new T1 first reactors that return to participate in reaction, higher boiling composition such as carbon methyl ethyl carbonate, diethyl carbonate and 1,2-PD into
Enter T3 atmospheric distillation towers to continue to separate；E-3 condensers are used to cool down methyl ethyl carbonate and diethyl carbonate, and E-4 condensers are used for
Condense 1,2- propane diols；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 1,2- propylene glycol mixtures that T3 bottoms obtain are through E-7
Condenser condensation enters T41,2- propane diols batch fractionating towers；Thick 1,2- propane diols adds water through T41,2- propane diols batch fractionating towers
Processing obtains 1,2-PD fine work, and diethyl carbonate steams directly collection or return to T1 first reactors and continues to participate in from tower top
Reaction；
4 used catalysts are 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；Catalyst performance stabilised, deactivation phenomenom is not present using 5000h, it is used
Measure 0.1%~3% of the gross mass for the raw material；
Raw material propylene oxide is with carbon dioxide with molar ratio 0.1:1-10:1 charging, vaporizer V1 temperature are 40-100 DEG C；At the same time
Liquid charging stock methanol is beaten with metering pump pump to feed with ethanol, both molar ratios 1:5-5:1；Preheating can V2 temperature is 25-60 DEG C；
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 ethanol import and raw material CO2With propylene 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 the 3rd discharge port；T3 atmospheric distillation towers, it is described
There is the 3rd feed inlet being connected with second and third described discharge port, the 4th discharge port and T41 with tower top in atmospheric distillation tower,
The 5th discharge port that 2- propane diols batch fractionating towers are connected；T41,2- propane diols batch fractionating tower, between the 1,2-PD
Have a rest the 4th feed inlet for having on rectifying column and being connected with the 5th discharge port, the 1,2-PD batch fractionating column overhead tool
There is the 6th discharge port, lower part is with the 5th feed inlet and bottom of towe is with the 7th discharge port.
The technique by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, first reaction
In device T1, raw material reacts under the action of catalyst, obtains the first mixture；The gaseous state light component of first mixture tower top
（Predominantly CO2And propylene oxide）Condensed device E-1 condensations are again introduced into T1 circulations；Other are compared with low-boiling point liquid（Methanol, ethanol
And its azeotropic mixture, methyl ethyl carbonate etc.）Separation, the light component such as methanol, second of T2 tower tops are carried out into T2 compression rectifications tower
Alcohol and a small amount of azeotropic mixture composition return again to T1 reactor reactions.
The technique by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, the T1 first are anti-
The tower pressure interior force for answering device is 0.01MPa~5MPa, and tower top temperature is 64 DEG C~90 DEG C, and column bottom temperature is 130 DEG C~160 DEG C；Institute
The tower pressure interior force for stating compression rectification tower T2 is 1MPa~15MPa, and tower top temperature is 50 DEG C~70 DEG C, column bottom temperature for 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, bottom of towe
Temperature is 110 DEG C~130 DEG C；The tower pressure interior force of the 1,2-PD batch fractionating tower T4 is 0.1MPa~0.5MPa, tower top
Temperature is 130 DEG C~160 DEG C, and column bottom temperature is 140 DEG C~180 DEG C；When T1 first reactor tower reactor 1,2- content of propylene glycol reaches
During to more than 20%, lower liquid enters T2 compression rectification towers through the condensation of E-2 condensers in kettle；When 1,2- content of propylene glycol reaches
When more than 90%, T1 reactors bottom is to T41,2- propane diols batch fractionating tower feed liquors.
The technique by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, the reactor and
It is 1 that the partition plate of rectifying column, 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 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, at the beginning of the reactor
The number of plates for evaporating 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.
The technique by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, the reactor T1
First reactor, T2 compression rectifications tower, T3 atmospheric distillation towers, T41,2- propane diols batch fractionating tower for plate column, packed tower or
Board-like-filler mixing column.
Advantages of the present invention is with effect：
Technique of the invention by propylene oxide, carbon dioxide, methanol and ethanol one-step synthesis methyl ethyl carbonate, it is characterised in that close
Short into route, a step directly obtains target product.React in obtained crude product containing dimethyl carbonate, methyl ethyl carbonate, carbon
Diethyl phthalate and 1,2-PD, wherein, methyl ethyl carbonate selectively can reach 70%.Accessory substance dimethyl carbonate and carbon
Diethyl phthalate can be directly separated as product, also can be recycled, the reaction was continued generation methyl ethyl carbonate, accessory substance 1,2- the third two
Alcohol is i.e. separable by simple distillation as largeization raw material.Whole reaction process cleans, is efficient, pollution-free, without any low
The accessory substance of value produces.
Brief description of the drawings
Fig. 1 is the process flow chart of one-step synthesis methyl ethyl carbonate co-production 1,2- propane diols of the present invention.
Embodiment
With reference to embodiment, the present invention is described in detail.
For the present invention by the production technology of propylene oxide, methanol, carbon dioxide and ethanol one-step synthesis methyl ethyl carbonate, this is anti-
The reaction equation answered is as follows：
+CO2+CH3OH+CH3CH2OH→HOCH2CHOHCH3+CH3OCOOCH2CH3……(8)
The reaction is using multi-functional compound basic matterial as catalyst, by propylene oxide（PO）, 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 product 1,2-PD (PG) is a kind of bulk chemical, has wide
Market application foreground；The dimethyl carbonate (DMC) and diethyl carbonate (DEC) incidentally produced in reaction process can be used as product
It is directly separated, also can be recycled, the reaction was continued generates methyl ethyl carbonate.
The methyl ethyl carbonate production technology of protection, including：The carbon dioxide and propylene 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, ethanol
By first reactor its 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, propylene oxide, methanol, ethanol, carbonic acid first
Ethyl ester, dimethyl carbonate, diethyl carbonate and 1,2- propane diols.Light component at the top of first reactor out is such as：Carbon dioxide,
The reaction was continued for propylene oxide, methanol and ethanol return first reactor, and another part higher component such as dimethyl carbonate
Enter after being condensed with methanol azeotrope, methyl ethyl carbonate and ethyl alcohol azeotropy article and a small amount of diethyl carbonate etc. via condenser E-1
The preheating of V-3 preheating cans 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：
1,2-PD, diethyl carbonate, a part enter at the top of compression rectification tower T2 after the condensation of E-2 condensers, and another part is thick
1,2- propane diols is directly entered 1,2- propane diols batch fractionating towers T4 and adds water process to obtain 1,2- propane diols fine work.Into pressurization essence
The component of tower T2 is evaporated, normal pressure azeotropic composition originally is separated under high pressure, light component such as methanol and dimethyl carbonate azeotropic
Thing and ethanol come back to T1 first reactors and participate in reaction, and higher boiling forms such as carbon methyl ethyl carbonate, diethyl carbonate and 1,
2- propane diols continues to separate into T3 atmospheric distillation towers.E-3 condensers are used to cool down methyl ethyl carbonate and diethyl carbonate, E-4
Condenser is used to condense 1,2- propane diols.Preheated tank V-4 high boiling components enter T3 atmospheric distillation towers, and methyl ethyl carbonate is by T3
Tower top is steamed to be condensed to obtain pure methyl ethyl carbonate fine work through E-6.And the diethyl carbonate and 1,2- propane diols that T3 bottoms obtain
Mixture enters T41,2- propane diols batch fractionating towers through the condensation of E-7 condensers.Thick 1,2- propane diols is through between T41,2- propane diols
Rectifying column of having a rest adds water process to obtain 1,2-PD fine work, and diethyl carbonate steams directly collection from tower top or return T1 first is anti-
Device is answered to continue to participate in reaction.
Fig. 1 is the technique of one-step synthesis methyl ethyl carbonate co-production 1,2- propane diols.
The present invention production methyl ethyl carbonate method, reaction raw materials carbon dioxide, propylene oxide, methanol, ethanol together into
Enter T1 first reactors, direct single step reaction Catalysts of Preparing Methyl Ethyl Carbonate, diethyl carbonate and 1,2-PD.In reactive distillation
Azeotropic separation synchronously carries out at the same time, carries out extract and separate to product without solvent, enormously simplify conventional methyl ethyl carbonate Lipase absobed
Technological process, while multicomponent can be made disposably to separate, separation purity is high.
The technique of present invention production methyl ethyl carbonate has technical characteristic additional as follows：
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.Catalyst performance stabilised, deactivation phenomenom is not present using 5000h, its
Usage amount is the 0.1%~3% of the gross mass of the raw material.
The raw material propylene oxide is with carbon dioxide with molar ratio 0.1:1-10:1 charging, vaporizer V1 temperature is 40-100
℃.Beat liquid charging stock methanol with metering pump pump at the same time to feed with ethanol, both molar ratios 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 ethanol import and raw material CO2It is described with propylene 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 the 3rd discharge port；T3 normal pressures essence
Tower is evaporated, there is the 3rd 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 T41,2- propane diols batch fractionating towers；T41,2- propane diols batch fractionating tower, described 1,2-
There is the 4th feed inlet being connected with the 5th discharge port, the 1,2-PD batch fractionating on propane diols batch fractionating tower
Column overhead has the 6th discharge port, and 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 action of catalyst, obtains
To the first mixture；The gaseous state light component of first mixture tower top（Predominantly CO2And propylene oxide）Condensed device E-1 condensations are again
The secondary T1 that enters is circulated.Other are compared with low-boiling point liquid（Methanol, ethanol and its azeotropic mixture, methyl ethyl carbonate etc.）Into T2 compression rectifications
Tower carries out separation, and the light component such as methanol, ethanol 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 for 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 is 0.1MPa~0.5MPa, tower top temperature
For 105 DEG C~125 DEG C, column bottom temperature is 110 DEG C~130 DEG C；The tower pressure interior force of the 1,2- propane diols 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 1,2-PD content reaches more than 20%, lower liquid enters T2 compression rectification towers through the condensation of E-2 condensers in kettle；When
When 1,2-PD content reaches more than 90%, T1 reactors bottom is to T41,2- propane diols batch fractionating tower feed liquors.
The partition plate 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, T41,2- propane diols batch fractionating towers in the present invention
For plate column, 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
Obtain substantially, or recognized by the practice of the present invention.
Embodiment
Embodiment 1
Using carbon dioxide, propylene oxide, methanol and ethanol as raw material, reaction generation methyl ethyl carbonate, methanol and ethanol thing
The amount ratio of matter is 3：2, excessive carbon dioxide and propylene oxide recycle.
Catalyst is alkaline composite material 15%PdO-8%SrO2-3%Ga2O3/ Zn-meso-Y, and dosage is raw material gross mass
The ratio between cross-sectional area of the 3% of sum, fore-running section and side line section is 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, the tower of public stripping section
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.
1,2- propane diols batch fractionating towers T4：Tower diameter 4500mm；Tower height 40000mm；It is public rectifying section, fore-running section, public
The number of plates of stripping section is respectively 10,20,15；Tower pressure interior force 0.1MPa, 140 DEG C of tower top temperature, the bottom of towe temperature of public stripping section
160 DEG C of degree.
The charging of first reactor T1 and discharging result are as shown in the table
Since the amount of the material of PG is the sum of amount of material of DMC, EMC and DEC, be not included in PG 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 optimal 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 change of tower reactor bottom methyl ethyl carbonate mass fraction are as shown in table 2.
As can be seen from Table 2, as reflux ratio increases, T2 compression rectification tower reactors bottom EMC mass fractions first increase and increase afterwards
Speed substantially slows down.The reason is that with the increase of reflux ratio, the more methanol of tower top, ethanol, DMC and the azeotropic of DMC and methanol
Thing is brought away from liquid phase, and the DMC mass fractions in tower reactor cut reduce, and the mass fraction of opposite EMC is with increase, but reflux ratio
DEC mass fractions are basically unchanged after more than 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, during rectifying reflux ratio controlled optimal 3.
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 every composition mass fraction change in tower reactor bottom is as shown in table 3.
From table 3 it can be seen that the mass fraction of methanol and ethanol reduces in being formed with each liquid phase of rise of reaction pressure,
The reason is that the boiling-point difference increase that azeotropic mixture forms under elevated pressures, azeotropic mixture are more prone to separate.But when pressure is higher than 3MPa
Each composition is held essentially constant, and since high pressure is higher for equipment requirement, can greatly increase input cost, therefore 3MPa is the essence
Evaporate the optimum condition of process.
Embodiment 4
Under the operating condition of embodiment 1, T41, the temperature of 2- propane diols batch fractionating tower tower reactors, which separates 1,2-PD, imitates
The influence of fruit is as shown in table 4.
From table 4, it can be seen that with the rise of bottom temperature, 1,2-PD, which contains, to be gradually risen, but raffinate ratio is corresponding
Also accordingly increase.Therefore it is 150-157 DEG C control bottom temperature, otherwise can generate 1,2-PD methyl ether, and one contracts 1,2- the third two
Alcohol, two contracting 1,2-PDs 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 with preferred embodiment disclose as above, but and be not used to limitation 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 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, it is characterised in that the technique bag
Include procedure below：
Specific one-step synthesis method methyl ethyl carbonate reaction equation is as follows：
+CO2+CH3OH+CH3CH2OH→HOCH2CHOHCH3+CH3OCOOCH2CH3……(1)
Raw material is respectively propylene oxide, carbon dioxide, methanol and ethanol, product 1,2-PD and carbonic ester molar ratio 1：1 life
Into can effectively a large amount of coproduction 1,2-PDs using the path；
Methyl ethyl carbonate production technology, including：The carbon dioxide and propylene 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；The preheated device V-2 of another way material benzenemethanol, the mixture of ethanol is pre-
By first reactor its 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, propylene oxide, methanol, ethanol, methyl ethyl carbonate, carbonic acid two
Methyl esters, diethyl carbonate and 1,2- propane diols；Light component at the top of first reactor out is such as：Carbon dioxide, propylene oxide, first
The reaction was continued for alcohol and ethanol return first reactor, and another part higher component such as dimethyl carbonate and methanol azeotropic
It is pre- that thing, methyl ethyl carbonate and ethyl alcohol azeotropy article and a small amount of diethyl carbonate etc. enter V-3 preheating cans after being condensed via condenser E-1
Heat 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：1,2- propane diols,
Diethyl carbonate, a part enter at the top of compression rectification tower T2 after the condensation of E-2 condensers, and the thick 1,2-PD of another part is straight
Tap into and add water process to obtain 1,2- propane diols fine work into 1,2- propane diols batch fractionating towers T4；Into the group of compression rectification tower T2
Point, normal pressure azeotropic composition originally is separated under high pressure, light component such as methanol and dimethyl carbonate azeotrope and ethanol weight
The new T1 first reactors that return to participate in reaction, higher boiling composition such as carbon methyl ethyl carbonate, diethyl carbonate and 1,2-PD into
Enter T3 atmospheric distillation towers to continue to separate；E-3 condensers are used to cool down methyl ethyl carbonate and diethyl carbonate, and E-4 condensers are used for
Condense 1,2- propane diols；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 1,2- propylene glycol mixtures that T3 bottoms obtain are through E-7
Condenser condensation enters T41,2- propane diols batch fractionating towers；Thick 1,2- propane diols adds water through T41,2- propane diols batch fractionating towers
Processing obtains 1,2-PD fine work, and diethyl carbonate steams directly collection or return to T1 first reactors and continues to participate in from tower top
Reaction；
4 used catalysts are 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；Catalyst performance stabilised, deactivation phenomenom is not present using 5000h, it is used
Measure 0.1%~3% of the gross mass for the raw material；
Raw material propylene oxide is with carbon dioxide with molar ratio 0.1:1-10:1 charging, vaporizer V1 temperature are 40-100 DEG C；At the same time
Liquid charging stock methanol is beaten with metering pump pump to feed with ethanol, both molar ratios 1:5-5:1；Preheating can V2 temperature is 25-60 DEG C；
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 ethanol import and raw material CO2With propylene 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 the 3rd discharge port；T3 atmospheric distillation towers, it is described
There is the 3rd feed inlet being connected with second and third described discharge port, the 4th discharge port and T41 with tower top in atmospheric distillation tower,
The 5th discharge port that 2- propane diols batch fractionating towers are connected；T41,2- propane diols batch fractionating tower, between the 1,2-PD
Have a rest the 4th feed inlet for having on rectifying column and being connected with the 5th discharge port, the 1,2-PD batch fractionating column overhead tool
There is the 6th discharge port, lower part is with the 5th feed inlet and bottom of towe is with the 7th discharge port.
2. the technique according to claim 1 by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, its
It is characterized in that, in the first reactor T1, raw material reacts under the action of catalyst, obtains the first mixture；First
The gaseous state light component of mixture tower top（Predominantly CO2And propylene oxide）Condensed device E-1 condensations are again introduced into T1 circulations；Other
Compared with low-boiling point liquid（Methanol, ethanol and its azeotropic mixture, methyl ethyl carbonate etc.）Separation, T2 are carried out into T2 compression rectifications tower
The light component of tower top such as methanol, ethanol and a small amount of azeotropic mixture composition return again to T1 reactor reactions.
3. the technique according to claim 2 by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, its
It is characterized in 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 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 is 0.1MPa~0.5MPa, tower top temperature
For 105 DEG C~125 DEG C, column bottom temperature is 110 DEG C~130 DEG C；The tower pressure interior force of the 1,2- propane diols 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 1,2-PD content reaches more than 20%, lower liquid enters T2 compression rectification towers through the condensation of E-2 condensers in kettle；When
When 1,2-PD content reaches more than 90%, T1 reactors bottom is to T41,2- propane diols batch fractionating tower feed liquors.
4. the technique according to claim 3 by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, its
It is characterized in that, the cross-sectional area that the partition plate of the reactor and rectifying column is arranged to make the fore-running section is with the horizontal stroke of the side line section
The ratio between sectional area is 1:1-3:1.
5. the technique according to claim 4 by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, its
It is characterized in that, the number of plates of the 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 5 by 1,2 propane diols of propylene oxide one-step synthesis methyl ethyl carbonate co-production, its
It is characterized in that, the reactor T1 first reactors, T2 compression rectifications tower, T3 atmospheric distillation towers, T41,2- propane diols interval essence
It is plate column, packed tower or board-like-filler mixing column to evaporate tower.
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| CN109647497A (en) * | 2018-11-30 | 2019-04-19 | 中国科学院山西煤炭化学研究所 | For epoxides, the catalyst of methanol and carbon dioxide preparation dimethyl carbonate and preparation method and application |
| CN113248379A (en) * | 2021-06-04 | 2021-08-13 | 重庆微而易科技有限公司 | Method for preparing methyl ethyl carbonate by adopting pipeline continuous reactor |
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