CN108863801A - By the method for separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process - Google Patents
By the method for separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- C07—ORGANIC CHEMISTRY
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- C07C68/08—Purification; Separation; Stabilisation
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Abstract
By the method for separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, it is related to the method for a kind of separating dimethyl carbonate and methanol, using dimethyl carbonate and ethyl alcohol as raw material, it reacts in reactive distillation column with solid base catalyst, tower top dimethyl carbonate and Methanol product mixture are produced with azeotropic mixture, it reacts in the reactor with solid acid catalyst, methanol dehydration generates dimethyl ether and water, gas phase dimethyl ether is separated from liquid phase, and azeotropic by rectification under vacuum does not isolate dimethyl carbonate recycling for liquid phase dimethyl carbonate and water.The method of the one step separating dimethyl carbonate and methanol, method process is simple, product yield high, pollution-free environmental protection, by the solid acid catalyst of coprecipitation method preparation in fixed bed continuous reactor separating dimethyl carbonate and methanol process, when air speed is 2h‑1, when reaction temperature is 100 DEG C, methanol conversion can reach 100%, and 5000h non-inactivation is used continuously in catalyst.
Description
Technical field
The present invention relates to a kind of methods of separating dimethyl carbonate and methanol, more particularly to one kind by lithium electricity methyl ethyl carbonate
The method of continuous separating dimethyl carbonate and methanol in ester production process.
Background technique
Methyl ethyl carbonate（Methyl Ethyl Carbonate, abbreviation MEC）, molecular formula：C4H8O3, colourless transparent liquid,
Density 1.01 g/mL, it is -55 DEG C of fusing point, 107 DEG C of boiling point, flammable, it can be mixed with arbitrary proportion with organic solvent such as alcohol, ketone, ester,
It is a kind of excellent solvent, methyl ethyl carbonate is 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 used 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 be improved the energy density and discharge capacity of battery, more can be improved 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 using phosgene and methanol/ethanol as the process of 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, causes great risk, and the method to the health of operator
Methyl ethyl carbonate yield is lower, 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）, subsequent point
From purification difficult, production cost is increased.
（Three）Ester-interchange method
1, 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 the disadvantage is that used poison
Property higher methylchloroformate, simultaneous reactions generate corrosive hydrogen chloride gas, the high requirements on the equipment.
2, dimethyl carbonate and diethyl carbonate ester-interchange method
Load metal oxide such as SnO of the land Shen Zhen et al. using load on alumina2/Al2O3、MoO3/Al2O3、TiO2/
Al2O3Deng being used 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
50-100 DEG C of reaction temperature, 2-48 h is carried out under normal pressure by the 0.1%-10% of total amount, and methyl ethyl carbonate yield is 43.6%.The route
The advantages of be that reaction process is simple, non-environmental-pollution, but the disadvantage is that the reaction time it is long, the catalyst activity reported at this stage compared with
It is low.
3, 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 nontoxicity, reaction condition is mild, no pollution to the environment, therefore has very by the report of this route Catalysts of Preparing Methyl Ethyl Carbonate
More, reaction equation involved by the route is as follows：
CH3OCOOCH3 + CH3CH2OH→CH3OCOOCH2CH3 + CH3OH......................(7)
CN1900047 A is using aluminium oxide, active carbon, molecular sieve as carrier, carrying alkali metal oxide, alkaline-earth metal oxygen
One kind of compound and rare-earth oxide, although separation problem is not present in catalyst, activity is not so good as homogeneous catalyst.
CN101289395 A is with NaOH, KOH, CH3ONa、CH3The highly basic such as OK substance is as catalyst, and the catalyst is in reaction solution
Solubility is bad, and easily precipitating, easy fouling.CN103483200 A is 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 catalysis with the ionic liquid of imidazoles
Agent, recoverable, the service life is long, but catalyst recycling is needed by specially treated.US5962720 is with SmL2、Li、CH3OLi
And CaH2Deng for catalyst, but reaction reaches balance and needs three days.
Currently, being handed over mainly using ester-interchange method as mainstream synthetic route in all of above methyl ethyl carbonate synthetic method in ester
It changes in method：Using highly basic such as sodium methoxides as homogeneous catalyst, dimethyl carbonate and ethyl alcohol are reaction raw materials, and alkali catalyst is by methanol
It brings reaction system into, controls 60-80 DEG C of reaction temperature by rectifying column, tower top dimethyl carbonate and Methanol product mixture are with altogether
Object extraction is boiled, group becomes methanol 70%（wt）, dimethyl carbonate 30%（wt）.Tower reactor is a small amount of dimethyl carbonate, methyl ethyl carbonate
And diethyl carbonate, three's not azeotropic, can rectification under vacuum isolate product methyl ethyl carbonate.Alkali catalyst passes through separating treatment
Afterwards, tower kettle product recycles.The light component dimethyl carbonate and methanol of extraction need to separate because of azeotropic by pressure-variable adsorption.Transformation
Adsorption process energy consumption is higher, low separation efficiency.This patent proposes continuous separation of carbon in a kind of lithium electricity methyl ethyl carbonate production process
The method of dimethyl phthalate and methanol.The method of the one step separating dimethyl carbonate and methanol, method process is simple, product yield
Height, pollution-free environmental protection, relatively current method significantly more efficient can isolate dimethyl carbonate, and energy consumption is lower.
Summary of the invention
The purpose of the present invention is to provide by separating dimethyl carbonate continuous in lithium electricity methyl ethyl carbonate production process and first
The method of alcohol, the present invention react in reactive distillation column with solid base catalyst using dimethyl carbonate and ethyl alcohol as raw material,
Tower top dimethyl carbonate and Methanol product mixture are produced with azeotropic mixture, are reacted in the reactor with solid acid catalyst,
Process is simple, product yield high, pollution-free.
The purpose of the present invention is what is be achieved through the following technical solutions：
By the method for separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, the separation of one step of the method
The obtained dimethyl carbonate of the method for dimethyl carbonate and methanol reenters reaction system as reactant and participates in transesterification
Reaction；Using dimethyl carbonate and ethyl alcohol as raw material, in solid base catalyst existence condition next step Catalysts of Preparing Methyl Ethyl Carbonate, solid
Under body acid catalyst existence condition, continuous separating dimethyl carbonate and methanol；
Reaction equation is as follows：
CH3OCOOCH3 + CH3CH2OH→CH3OCOOCH2CH3 + CH3OH.......................(1)；
First rectifying column produces light component dimethyl carbonate and methanol passes through the fixed bed bed of solid acid catalyst, carbonic acid diformazan
Any reaction does not occur for ester, and methanol occurs dehydration and generates dimethyl ether（DME）And water, acidic catalyst are completely insoluble in raw material
And any pollutant, dimethyl ether is not present in product, reaction process（DME）It is gas phase in room temperature, is a kind of green combustion of high heating value
Material, easily separates with liquid phase dimethyl carbonate and water phase；Liquid phase dimethyl carbonate and water not azeotropic, are isolated by rectification under vacuum
Dimethyl carbonate reenters reaction system as reactant；Separating dimethyl carbonate and methanol reactive mode are fixed bed company
Continuous reactor.
The method by separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, it is described solid
Body acid catalyst is prepared as follows by the precipitation method：
1）It is mixed with a certain proportion of silica and deionized water to obtain mixed liquor first；
2）It takes the aluminum nitrate of carrier quality 0.1-50% to be dissolved in the deionized water of certain volume, is made into certain density aluminum nitrate
Solution, while certain density sodium carbonate alkaline solution is prepared, the mixed liquor that will be prepared stirs evenly, then certain
Bath temperature and intense agitation under, into mixed liquor simultaneously aluminum nitrate solution and sodium carbonate alkaline solution is added dropwise, be added dropwise
Solution pH value is controlled in the process；
3）After aluminum nitrate solution is added dropwise, will be coprecipitated after suspension continue stir certain time, then aging at room temperature；
4）The solution that aging is finished filters, and the precipitating then washed with the deionized water of certain volume is until cleaning solution PH
It is 7；
5）Washing dry certain time at 110-120 DEG C to the catalyst precursor after neutrality；
6）Catalyst precursor after drying is roasted at 550-650 DEG C to 3-5 h in Muffle furnace, obtains solid acid catalysis
Agent.
The method by separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, it is described total
Heavy alkaline solution, the additional amount of alkaline solution will at least flood all carriers, be 10-20 times or more of carrier bulk, most
It is 15 times well, it is 8-14 that solution PH value is controlled when coprecipitated, and preferably PH is 9；
Above-mentioned coprecipitation method bath temperature is -99 DEG C of room temperature, preferably 70 DEG C；Aging temperature is -80 DEG C of room temperature, ageing time 1
- 20 days, preferably 60 DEG C, ageing time 5 days hour；Catalyst detergent medium is preferably water, but is also not necessarily limited to water, and liquid medium is
2-10 times or more of catalyst volume, preferably 2-5 times, washing times are depending on washing efflux pH；
Catalyst drying temperature is -150 DEG C of room temperature, and the time is -10 days 1 hour, preferably 120 DEG C, 3-5 days dry；Maturing temperature
It is 150-800 DEG C, the time is 1-50 hours, preferably 500-700 DEG C, the time 30 hours.
The method by separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, described point
It is fixed bed continuous reactor, dimethyl carbonate and ethyl alcohol with molar ratio 1.2 from dimethyl carbonate and methanol reactive mode:1 into
Reactive distillation column, the dimethyl carbonate and methanol that top of tower comes out beat liquid into reactor, in above-mentioned solid acid catalyst with pump
Isolated dimethyl carbonate, air speed are 0.1-100 h to existence condition in next step-1, under conditions of 50-250 DEG C of reaction temperature,
Catalyst is solid acid catalyst, and catalyst amount is the 0.1-3wt% of material quality, and dimethyl carbonate mass fraction is not less than
90%；
During fixed bed reactors separating dimethyl carbonate and methanol, optimum condition is air speed 0.5-5 h-1, reaction temperature
60-120 DEG C of degree.
The method by separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, the carbon
The process flow of continuous separating dimethyl carbonate and methanol, the dimethyl carbonate and second of raw material liquid in sour first and second ester production process
Alcohol is pumped into main reaction rectifying column by metering pump, and raw material contacts with each other in main reaction rectifying column with solid base catalyst part generation
Reaction, in reactive distillation column, dimethyl carbonate is sufficiently reacted with ethyl alcohol, the first obtained mixture include methyl ethyl carbonate,
Dimethyl carbonate, diethyl carbonate and methanol；Reactive distillation column top of tower come out light component be dimethyl carbonate and methanol, two
Person is pumped into reactor by metering pump, is contacted with each other and is reacted with solid acid catalyst, and in the reactor, methanol dehydration generates two
Methyl ether and water, the dimethyl carbonate and water that reactor comes out are pumped into vacuum rectification tower by metering pump again, in vacuum rectification tower, tower
The light component that top comes out is only dimethyl carbonate, and high purity carbon dimethyl phthalate fine work is obtained after condenser condenses；Main reaction
The recombination that rectifying tower reactor bottom comes out is divided into：Methyl ethyl carbonate, diethyl carbonate and a small amount of dimethyl carbonate are pumped into via metering pump
Vacuum rectification tower, in vacuum rectification tower, the light component that top of tower comes out is only dimethyl carbonate, is obtained after condenser condenses
High-purity ethyl methyl carbonate fine work, the recombination that tower reactor comes out are divided into dimethyl carbonate and diethyl carbonate；Two parts are isolated
High purity carbon dimethyl phthalate return in main reaction rectifying column and continue to participate in ester exchange reaction, dimethyl carbonate, which obtains circulation, to be made
With.
The method by separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, it is described to urge
Its usage amount of agent is the 0.3%~5% of total mass of raw material.
The method by separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, it is described anti-
The partition of device and rectifying column is answered to be arranged to that the ratio between cross-sectional area of the cross-sectional area of the fore-running section and the side line section is made to be 1:
1-3:1。
The method by separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, it is described anti-
The number of plates for answering device fore-running section is 1~30 piece, and the side line section number of plates is 1~30 piece, and the number of plates of public rectifying section is 1~30
Block, the number of plates of public stripping section are 1~30 piece.
The method by separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, it is described anti-
Answering main reaction rectifying column in device, vacuum rectification tower is plate column, packed tower or board-like-filler mixing column.
Detailed description of the invention
Fig. 1 is the method block diagram of continuous separating dimethyl carbonate and methanol in lithium electricity methyl ethyl carbonate production process.
Specific embodiment
The following describes the present invention in detail with reference to examples.
One kind of the invention is by dimethyl carbonate（DMC）And ethyl alcohol（EtOH）Transesterification prepares methyl ethyl carbonate（MEC）, life
Continuous separating dimethyl carbonate during production（DMC）And methanol（MeOH）Method, reaction equation is as follows：
CH3OCOOCH3 + CH3CH2OH→CH3OCOOCH2CH3 + CH3OH......................(7)
First rectifying column produces light component dimethyl carbonate and methanol passes through the fixed bed bed of solid acid catalyst, carbonic acid diformazan
Any reaction does not occur for ester, and methanol occurs dehydration and generates dimethyl ether（DME）And water, acidic catalyst are completely insoluble in raw material
And any pollutant, dimethyl ether is not present in product, reaction process（DME）It is gas phase in room temperature, is a kind of green combustion of high heating value
Material, has a vast market application prospect, easily separates with liquid phase dimethyl carbonate and water phase.Liquid phase dimethyl carbonate and water are not
Azeotropic can isolate dimethyl carbonate by rectification under vacuum, reenter reaction system as reactant.
The preparation of solid acid catalyst of the present invention uses coprecipitation method：
1）It is mixed with a certain proportion of silica and deionized water to obtain mixed liquor first.
2）It takes the aluminum nitrate of carrier quality 0.1-50% to be dissolved in the deionized water of certain volume, is made into certain density nitre
Sour aluminum solutions, while certain density sodium carbonate alkaline solution is prepared, the mixed liquor that will be prepared stirs evenly, then exists
Under certain bath temperature and intense agitation, aluminum nitrate solution and sodium carbonate alkaline solution is added dropwise simultaneously into mixed liquor,
Solution pH value is controlled during being added dropwise.
3）After aluminum nitrate solution is added dropwise, will be coprecipitated after suspension continue stir certain time, then at room temperature
Aging.
4）The solution that aging is finished filters, and the precipitating then washed with the deionized water of certain volume is until washing
Liquid PH is 7.
5）Washing dry certain time at 110-120 DEG C to the catalyst precursor after neutrality.
6）Catalyst precursor after drying is roasted at 550-650 DEG C to 3-5 h in Muffle furnace, solid acid is obtained and urges
Agent.
Coprecipitated alkaline solution of the present invention, the additional amount of alkaline solution will at least flood all carriers, can be
10-20 times or more of carrier bulk, preferably 15 times, it is 8-14 that solution PH value is controlled when coprecipitated, and preferably PH is 9.
Above-mentioned coprecipitation method bath temperature can be -99 DEG C of room temperature, preferably 70 DEG C；Aging temperature can be -80 DEG C of room temperature, aging
Time can be -20 days 1 hour, preferably 60 DEG C, ageing time 5 days；Catalyst detergent medium is preferably water, but is also not necessarily limited to water,
Liquid medium can be 2-10 times or more of catalyst volume, and preferably 2-5 times, washing times are depending on washing efflux pH.
Catalyst drying temperature can be -150 DEG C of room temperature, and the time can be -10 days 1 hour, preferably 120 DEG C, 3-5 days dry；
Maturing temperature can be 150-800 DEG C, and the time can be 1-50 hours, preferably 500-700 DEG C, the time 30 hours.
The present invention is using dimethyl carbonate and ethyl alcohol as raw material, in solid base catalyst existence condition next step carbonate synthesis first
Ethyl ester, under solid acid catalyst existence condition, continuous separating dimethyl carbonate and methanol.Separating dimethyl carbonate and methanol are anti-
Answering mode is fixed bed continuous reactor.
Fixed bed continuous reactor specific embodiment of the present invention is：Dimethyl carbonate and ethyl alcohol are with molar ratio 1.2:1 into
Reactive distillation column, the dimethyl carbonate and methanol that top of tower comes out beat liquid into reactor, in above-mentioned solid acid catalyst with pump
Isolated dimethyl carbonate, air speed are 0.1-100 h to existence condition in next step-1, under conditions of 50-250 DEG C of reaction temperature,
Catalyst is the solid acid catalyst protected in the present invention, and catalyst amount is the 0.1-3wt% of material quality, dimethyl carbonate
Mass fraction is not less than 90%.
During with fixed bed reactors separating dimethyl carbonate and methanol, optimum condition is air speed 0.5-5 h-1,
60-120 DEG C of reaction temperature.
The method of continuous separating dimethyl carbonate and methanol in the lithium electricity methyl ethyl carbonate production process of protection, including：It is former
The dimethyl carbonate and ethyl alcohol of feed liquid state are pumped into main reaction rectifying column by metering pump, raw material in main reaction rectifying column with solid base
Catalyst member, which contacts with each other, to react, and in reactive distillation column, dimethyl carbonate is sufficiently reacted with ethyl alcohol, first obtained
Mixture includes methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and methanol.The light component that reactive distillation column top of tower comes out
For dimethyl carbonate and methanol, the two is pumped into reactor by metering pump, is contacted with each other and is reacted with solid acid catalyst, anti-
It answers in device, methanol dehydration generates dimethyl ether and water, and the dimethyl carbonate and water that reactor comes out are pumped into decompression essence by metering pump again
Tower is evaporated, in vacuum rectification tower, the light component that top of tower comes out is only dimethyl carbonate, obtains high-purity after condenser condenses
Dimethyl carbonate fine work.The recombination that main reaction rectifying tower reactor bottom comes out is divided into：Methyl ethyl carbonate, diethyl carbonate and a small amount of carbonic acid
Dimethyl ester is pumped into vacuum rectification tower via metering pump, and in vacuum rectification tower, the light component that top of tower comes out is only methyl ethyl carbonate
Ester, obtains high-purity ethyl methyl carbonate fine work after condenser condenses, and the recombination that tower reactor comes out is divided into dimethyl carbonate and carbonic acid
Diethylester.The isolated high purity carbon dimethyl phthalate of two parts returns in main reaction rectifying column that continue to participate in transesterification anti-
It answers, dimethyl carbonate is recycled.
The method block diagram of continuous separating dimethyl carbonate and methanol in Fig. 1 lithium electricity methyl ethyl carbonate production process.
The method that the present invention produces continuous separating dimethyl carbonate and methanol during methyl ethyl carbonate, with dimethyl carbonate
It is raw material with ethyl alcohol, under solid base catalyst existence condition, through transesterification Catalysts of Preparing Methyl Ethyl Carbonate, and methyl ethyl carbonate is produced
In the process, under solid acid catalyst existence condition, continuous separating dimethyl carbonate and methanol.The reactive distillation of the synthetic method
When progress, extraction and separation are carried out to product without solvent, enormously simplify the process flow of conventional methyl ethyl carbonate Lipase absobed, simultaneously
Multicomponent can be made disposably to separate, and separation purity is high, and dimethyl carbonate is recycled.
The method that the present invention produces methyl ethyl carbonate has following additional technical characteristic：
This method used catalyst is a kind of solid base catalyst.Catalyst performance stabilised, it is existing there is no inactivating using 5000h
As usage amount is the 0.3%~5% of the total mass of raw material.The method used catalyst of separating dimethyl carbonate and methanol
For a kind of solid acid catalyst prepared by coprecipitation method.Deactivation phenomenom is not present using 5000h in the catalyst performance stabilised,
Usage amount is the 0.3%~5% of the total mass of raw material.
The partition of heretofore described reactor and rectifying column is arranged to make the cross-sectional area of 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 is 1~
30 pieces, the number of plates of public stripping section is 1~30 piece.
Main reaction rectifying column, vacuum rectification tower are plate column, packed tower or board-like-filler mixing column in the present invention.
Additional aspect and advantage of the invention will be set forth in part in the description, and will partially become from the following description
Obviously, or practice through the invention is recognized.
Embodiment 1
Use dimethyl carbonate and ethyl alcohol molar ratio for 1.2:1 is used as raw material, through transesterification Catalysts of Preparing Methyl Ethyl Carbonate, during this
Continuous separating dimethyl carbonate and methanol, isolated dimethyl carbonate return in main reaction rectifying column and continue to participate in transesterification
Reaction cycle utilizes.
Reactive distillation column used catalyst is solid base catalyst, and dosage is the 3% of total mass of raw material sum, fore-running section and side
The ratio between cross-sectional area of line segment is 1：1.
Operating condition is as follows：
Main reaction rectifying column：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 0.1-1 MPa；60 DEG C of tower top temperature；The column bottom temperature of public stripping section
160℃；180 DEG C of the column bottom temperature of side line section.
The vacuum rectification tower of separating dimethyl carbonate and water：Tower diameter 3000mm；Tower height 40000mm；Public rectifying section, fore-running
Section, side line section, the number of plates of public stripping section are respectively 10,20,30,15；Tower pressure interior force 0.1-1.0MPa；Tower top temperature 90
DEG C, 95 DEG C of the column bottom temperature of public stripping section；120 DEG C of the column bottom temperature of side line section.
The vacuum rectification tower of separating dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate：Tower diameter 3000mm；Tower height
40000mm；Public rectifying section, fore-running section, side line section, the number of plates of public stripping section are respectively 10,20,30,15；Tower pressure interior force
0.1-1.0MPa；90 DEG C of tower top temperature, 120 DEG C of the column bottom temperature of public stripping section；130 DEG C of the column bottom temperature of side line section.
Embodiment 2
In fixed bed reactors, influence of the differential responses temperature to methanol conversion is probed into.Solid acid is packed into fixed bed
50 g of catalyst, air speed are 2 h-1, it is as shown in the table for reaction temperature, and stablizes 500 h, and sampling carries out chromatography meter after stablizing
It calculates, methanol conversion is as shown in table 1.
1 differential responses temperature of table compares the influence of methanol conversion variation
As can be seen from Table 1, as the raising methanol conversion of reaction temperature gradually rises, but after temperature is higher than 100 DEG C,
Methanol is converted close to complete.
Embodiment 3
In fixed bed reactors, influence of the differential responses air speed to methanol conversion is probed into.Solid acid is packed into fixed bed
50 g of catalyst, temperature are 100 DEG C, and it is as shown in the table for reaction velocity, and stablizes 500 h, and sampling carries out chromatography meter after stablizing
It calculates, methanol conversion is as shown in table 2.
The influence that the different air speeds of table 2 change methanol conversion
From table 2 it can be seen that when material quality air speed is lower than 2.0 h-1When, methanol conversion is close to 100%, when air speed is greater than 2h-1When, methanol conversion is begun to decline.
The above is only several embodiments of the application, not does any type of limitation 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, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (9)
1. by the method for separating dimethyl carbonate and methanol continuous in lithium electricity methyl ethyl carbonate production process, which is characterized in that institute
The obtained dimethyl carbonate of method for stating one step separating dimethyl carbonate of method and methanol, reenters reaction as reactant
System participates in ester exchange reaction；Using dimethyl carbonate and ethyl alcohol as raw material, synthesized in next step in solid base catalyst existence condition
Methyl ethyl carbonate, under solid acid catalyst existence condition, continuous separating dimethyl carbonate and methanol；
Reaction equation is as follows：
CH3OCOOCH3 + CH3CH2OH→CH3OCOOCH2CH3 + CH3OH...............................
(1)；
First rectifying column produces light component dimethyl carbonate and methanol passes through the fixed bed bed of solid acid catalyst, carbonic acid diformazan
Any reaction does not occur for ester, and methanol occurs dehydration and generates dimethyl ether（DME）And water, acidic catalyst are completely insoluble in raw material
And any pollutant, dimethyl ether is not present in product, reaction process（DME）It is gas phase in room temperature, is a kind of green combustion of high heating value
Material, easily separates with liquid phase dimethyl carbonate and water phase；Liquid phase dimethyl carbonate and water not azeotropic, are isolated by rectification under vacuum
Dimethyl carbonate reenters reaction system as reactant；Separating dimethyl carbonate and methanol reactive mode are fixed bed company
Continuous reactor.
2. according to claim 1 by separating dimethyl carbonate continuous in lithium electricity methyl ethyl carbonate production process and methanol
Method, which is characterized in that the solid acid catalyst is prepared as follows by the precipitation method：
1）It is mixed with a certain proportion of silica and deionized water to obtain mixed liquor first；
2）It takes the aluminum nitrate of carrier quality 0.1-50% to be dissolved in the deionized water of certain volume, is made into certain density aluminum nitrate
Solution, while certain density sodium carbonate alkaline solution is prepared, the mixed liquor that will be prepared stirs evenly, then certain
Bath temperature and intense agitation under, into mixed liquor simultaneously aluminum nitrate solution and sodium carbonate alkaline solution is added dropwise, be added dropwise
Solution pH value is controlled in the process；
3）After aluminum nitrate solution is added dropwise, will be coprecipitated after suspension continue stir certain time, then aging at room temperature；
4）The solution that aging is finished filters, and the precipitating then washed with the deionized water of certain volume is until cleaning solution PH
It is 7；
5）Washing dry certain time at 110-120 DEG C to the catalyst precursor after neutrality；
6）Catalyst precursor after drying is roasted at 550-650 DEG C to 3-5 h in Muffle furnace, obtains solid acid catalysis
Agent.
3. according to claim 1 by separating dimethyl carbonate continuous in lithium electricity methyl ethyl carbonate production process and methanol
Method, which is characterized in that the coprecipitated alkaline solution, the additional amount of alkaline solution will at least flood all carriers, to carry
10-20 times or more of body volume, preferably 15 times, it is 8-14 that solution PH value is controlled when coprecipitated, and preferably PH is 9；
Above-mentioned coprecipitation method bath temperature is -99 DEG C of room temperature, preferably 70 DEG C；Aging temperature is -80 DEG C of room temperature, ageing time 1
- 20 days, preferably 60 DEG C, ageing time 5 days hour；Catalyst detergent medium is preferably water, but is also not necessarily limited to water, and liquid medium is
2-10 times or more of catalyst volume, preferably 2-5 times, washing times are depending on washing efflux pH；
Catalyst drying temperature is -150 DEG C of room temperature, and the time is -10 days 1 hour, preferably 120 DEG C, 3-5 days dry；Maturing temperature
It is 150-800 DEG C, the time is 1-50 hours, preferably 500-700 DEG C, the time 30 hours.
4. according to claim 1 by separating dimethyl carbonate continuous in lithium electricity methyl ethyl carbonate production process and methanol
Method, which is characterized in that the separating dimethyl carbonate and methanol reactive mode are fixed bed continuous reactor, dimethyl carbonate
With ethyl alcohol with molar ratio 1.2:1 into reactive distillation column, and the dimethyl carbonate and methanol that top of tower comes out beat liquid into reaction with pump
Device, in above-mentioned solid acid catalyst existence condition, isolated dimethyl carbonate, air speed are 0.1-100 h in next step-1, reaction
Under conditions of 50-250 DEG C of temperature, catalyst is solid acid catalyst, and catalyst amount is the 0.1-3wt% of material quality, carbonic acid
Dimethyl ester mass fraction is not less than 90%；
During fixed bed reactors separating dimethyl carbonate and methanol, optimum condition is air speed 0.5-5 h-1, reaction temperature
60-120 DEG C of degree.
5. according to claim 4 by separating dimethyl carbonate continuous in lithium electricity methyl ethyl carbonate production process and methanol
Method, which is characterized in that the process flow of continuous separating dimethyl carbonate and methanol in the methyl ethyl carbonate ester production process, it is former
The dimethyl carbonate and ethyl alcohol of feed liquid state are pumped into main reaction rectifying column by metering pump, raw material in main reaction rectifying column with solid base
Catalyst member, which contacts with each other, to react, and in reactive distillation column, dimethyl carbonate is sufficiently reacted with ethyl alcohol, first obtained
Mixture includes methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate and methanol；The light component that reactive distillation column top of tower comes out
For dimethyl carbonate and methanol, the two is pumped into reactor by metering pump, is contacted with each other and is reacted with solid acid catalyst, anti-
It answers in device, methanol dehydration generates dimethyl ether and water, and the dimethyl carbonate and water that reactor comes out are pumped into decompression essence by metering pump again
Tower is evaporated, in vacuum rectification tower, the light component that top of tower comes out is only dimethyl carbonate, obtains high-purity after condenser condenses
Dimethyl carbonate fine work；The recombination that main reaction rectifying tower reactor bottom comes out is divided into：Methyl ethyl carbonate, diethyl carbonate and a small amount of carbonic acid
Dimethyl ester is pumped into vacuum rectification tower via metering pump, and in vacuum rectification tower, the light component that top of tower comes out is only carbonic acid diformazan
Ester, obtains high-purity ethyl methyl carbonate fine work after condenser condenses, and the recombination that tower reactor comes out is divided into dimethyl carbonate and carbonic acid
Diethylester；The isolated high purity carbon dimethyl phthalate of two parts returns in main reaction rectifying column that continue to participate in transesterification anti-
It answers, dimethyl carbonate is recycled.
6. according to claim 1 by separating dimethyl carbonate continuous in lithium electricity methyl ethyl carbonate production process and methanol
Method, which is characterized in that its usage amount of the catalyst is the 0.3%~5% of total mass of raw material.
7. according to claim 1 by separating dimethyl carbonate continuous in lithium electricity methyl ethyl carbonate production process and methanol
Method, which is characterized in that the partition of the reactor and rectifying column is arranged to make the cross-sectional area of the fore-running section and the side
The ratio between cross-sectional area of line segment is 1:1-3:1.
8. according to claim 7 by separating dimethyl carbonate continuous in lithium electricity methyl ethyl carbonate production process and methanol
Method, which 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
The number of plates of rectifying section is 1~30 piece, and the number of plates of public stripping section is 1~30 piece.
9. according to claim 7 by separating dimethyl carbonate continuous in lithium electricity methyl ethyl carbonate production process and methanol
Method, which is characterized in that main reaction rectifying column, vacuum rectification tower are plate column, packed tower or board-like-filler in the reactor
Mixing column.
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| CN107473968A (en) * | 2017-07-20 | 2017-12-15 | 沈阳化工大学 | A kind of method of ester-interchange method methyl ethyl carbonate |
| CN108191605A (en) * | 2017-12-20 | 2018-06-22 | 沈阳化工大学 | The technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol |
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| CN108191605A (en) * | 2017-12-20 | 2018-06-22 | 沈阳化工大学 | The technique of one-step synthesis methyl ethyl carbonate co-production ethylene glycol |
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| CN114634415B (en) * | 2022-04-22 | 2024-03-22 | 天津凯美特化工科技有限公司 | Method for separating azeotrope of dimethyl carbonate and methanol by diethyl carbonate reaction and producing methyl ethyl carbonate |
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