CN109369400A - A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate - Google Patents
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate Download PDFInfo
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- CN109369400A CN109369400A CN201811194264.XA CN201811194264A CN109369400A CN 109369400 A CN109369400 A CN 109369400A CN 201811194264 A CN201811194264 A CN 201811194264A CN 109369400 A CN109369400 A CN 109369400A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
- C07C68/065—Preparation of esters of carbonic or haloformic acids from organic carbonates from alkylene carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/128—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by alcoholysis
- 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
- 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
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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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
- C07C68/08—Purification; Separation; Stabilisation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, it is related to a kind of production technology of industrial chemicals, the present invention passes through simple rectifying, liquid of top of the tower obtains high-purity diethyl carbonate solution by atmospheric distillation, and a large amount of ethylene glycol, minute quantity diethyl carbonate and a small amount of ethylene carbonate can be obtained by decompression separation in tower bottoms, ethyl alcohol and ethylene carbonate are directly as feedstock circulation to the first reactive distillation column.One is started using ethylene carbonate and ethyl alcohol as the process route of Material synthesis ethylene carbonate.It realizes and ethylene carbonate and ethyl alcohol is directly catalyzed in catalytic rectifying tower simple separation technology with multi-functional compound basic matterial.The production technology of the one-step synthesis diethyl carbonate, synthesis path is short, and process flow is simple, selectivity of product and high income, and relatively current technique can significantly more efficient production diethyl carbonate.
Description
Technical field
A kind of industrial chemicals production technology is related to the production that a kind of solid base catalyst is directly catalyzed high-purity diethyl carbonate
Technique.
Background technique
Contain alkoxy and carbonyl in diethyl carbonate (Diethyl Carbonate, vehicle economy C) molecule, chemically
Matter is active, can react with a variety of alcohol, phenol, amine and ester etc., is the solvent of a kind of important organic synthesis intermediate and function admirable,
It is widely used in the industries such as medicine, pesticide and fiber, in addition, DEC or a kind of excellent gasoline additive, there is good market
Prospect.
Diethyl carbonate is in terms of solvent, for also serving as surfactant in the fixed paint of cathode for electron tube；In pesticide side
Face is used for pyrethroid；As the solvent of plasticizer or directly make plasticizer in plastic processing and use；Capacitor batteries,
It is used as on Lithium Battery Industry and prepares electrolyte；As the basic ingredients of cortisone ointment, synthetic intermediate benzene bar in terms of medicine
Than appropriate etc., there is the extensive prospect of marketing.
Consulting literatures are it is found that diethyl carbonate is mainly the following synthetic method at present:
(1) phosgenation
It is to be reacted to obtain carbonic acid diethyl vinegar with phosgene and dehydrated alcohol that phosgenation, which prepares diethyl carbonate,.Reaction equation is as follows:
COCl2 + C2H5OH→C2H5OCOCl +HCl..................................(1)
C2H5OCOCl + C2H5OH→C2H5OCOOC2H5 +HCl.............................(2)
Commercial operations process is as follows: phosgene led in people's dehydrated alcohol, phosgene first generates ethyl chloroformate with ethanol synthesis, and
Release hydrogen chloride gas.Ethyl chloroformate generates diethyl carbonate with ethanol synthesis again and further releases hydrogen chloride gas
Body.The molar ratio of phosgene usage and ethanol consumption is 1.05:1 to 1.1:01, and reaction temperature is 70-90 DEG C, is returned after having led to phosgene
2 hours are flowed, the hydrogen chloride for reacting generation can by-product hydrochloric acid through cooling absorb.125-128 DEG C of reaction product rectifying collection evaporates
Dividing is product, and the purity of industrial carbonic acid diethylester is up to 99% or more.
Phosgenation prepares diethyl carbonate and needs more alcohol, and the reaction time is longer, and reaction temperature is also relatively high, and
Reaction generates the strong hydrogen chloride of corrosivity, it is desirable that consersion unit must be corrosion-resistant, this will cause equipment investment to increase, to mention
High production cost.
(2) oxidation of ethanol carbonylation method
Oxidation of ethanol carbonylation method is with carbon monoxide, oxygen and the direct synthesizing diethyl carbonate of ethyl alcohol.Reaction equation is as follows:
2 C2H5OH+1/2O2+CO→ C2H5OCOOC2H5+H2O................................(3)
Reaction will carry out under the action of catalyst, general to be loaded in active carbon, A with precious metal salts such as handles2O3、SiO2It is upper to be used as catalysis
Agent, catalyst system can be homogeneous, be also possible to heterogeneous.(9.8-19.6) × 10 is divided in CO4Pa reaction temperature 60-
It at 150 DEG C, adjusts in reaction system outside gas component to explosion limit, ethyl alcohol, carbon monoxide and oxygen are at a high speed and Gao Xuan
The reaction of selecting property generates diethyl carbonate.
This law has the characteristics that raw material cheap and easy to get, small toxicity, simple process, at low cost, so having certain development
Future has vapor phase method and two kinds of liquid phase method at present.But this method makees catalyst using precious metal, and dosage is more, because
And cost is too high.
(3) ester-interchange method
1, dimethyl carbonate and ethyl alcohol ester-interchange method
Dimethyl carbonate and ethyl alcohol carry out the reaction of transesterification synthesizing diethyl carbonate and are divided into two steps: through ethyl alcohol and dimethyl carbonate
First step ester exchange reaction generates intermediate methyl ethyl carbonate (Methyl Ethyl Carbonate, abbreviation MEC), carbonic acid
Methyl ethyl ester continues to generate final product diethyl carbonate with ethyl alcohol transesterification, and reaction equation is as follows:
CH3OCOOCH3 +CH3CH2OH→ CH3OCOOCH2CH3 +CH3OH......................(4)
CH3OCOOCH2CH3 +CH3CH2OH→ CH3CH2OCOOCH2CH3 +CH3OH................(5)
This method uses poisonous material dimethyl carbonate, will not generate pollution, and reaction condition is mild, can be in normal pressure
Lower reaction, reaction temperature is no more than 80 DEG C, to the of less demanding of equipment, so being industrially easily achieved.The reaction is flat
Row series connection reversible reaction, will have selectivity, if not taking any special measure, dimethyl carbonate is can not
It can be fully converted into diethyl carbonate, will have and greatly be converted to methyl ethyl carbonate, thus waste raw material and energy consumption,
Engineering measure appropriate can be taken to solve the problems, such as by reactive distillation above-mentioned.
2, propene carbonate and ethyl alcohol ester-interchange method
The method that diethyl carbonate is produced in propene carbonate and ethyl alcohol transesterification is started by raw material of propylene oxide, epoxy third
Alkane and carbon dioxide reaction generate propene carbonate, and propene carbonate carries out ester exchange reaction with ethyl alcohol again and generates propylene glycol and carbon
Diethyl phthalate.Its reaction equation is as follows:
The essential raw material of propene carbonate and ethyl alcohol ester-interchange method synthesizing diethyl carbonate is carbon dioxide and ethyl alcohol, propylene oxide
It is a kind of carrier in the process, while is converted to propylene glycol.Since propylene glycol is mainly to be produced with propylene oxide hydrolysis, because
The essence of this this process is carbon dioxide and (being in thermodynamic principles cannot be direct for the process of ethyl alcohol synthesizing diethyl carbonate
Carry out) with the coupling of propylene oxide hydrolysis propylene glycol process.But since second step reaction is a reversible reaction, and
The chemical equilibrium constant of reaction is smaller, when realizing product separation, back reaction speed can be made to accelerate because of the reduction of concentration of alcohol, thus
Reduce product yield.
3, ethylene carbonate and ethyl alcohol ester-interchange method
Ethylene carbonate and ethyl alcohol ester exchange reaction prepare the method and propene carbonate and ethyl alcohol transesterification system of diethyl carbonate
The method for taking diethyl carbonate is similar, and only raw material changes, and this method is using ethylene oxide as starting material, ethylene oxide and two
Carbon dioxide reaction generates ethylene carbonate, and ethylene carbonate carries out ester exchange reaction with ethyl alcohol again and generates ethylene glycol and carbonic acid diethyl
Ester.The equation of reaction is as follows:
The process of ethylene carbonate and ethyl alcohol transesterification synthesizing diethyl carbonate is equally faced with conversion ratio and the choosing of reversible reaction
The problem of selecting property problem, there are also product separation.
Zhao Xianping and Xiao Wende is using sodium ethoxide as homogeneous catalyst, ethylene carbonate and ethyl alcohol transesterification carbonate synthesis two
The process of ethyl ester while coproduction ethylene glycol.Catalyst concn, alcohol ester have been investigated than influence of the factors to reaction such as, temperature, has been obtained
Convenient process conditions: catalyst quality score is 0.3~0.9%, and alcohol ester ratio is 8~11, and reaction temperature is 30~50 DEG C.
But homogeneous catalyst dissolubility in alcohol is little, excessively high concentration will cause the precipitating of catalyst, fouling, or even meeting and carbon
Acid esters, which reacts, to be generated the very poor carbonate of dissolubility and reduces the conversion ratio of ethylene carbonate, and the waste of raw material is caused, because
That there are stability is poor for this catalyst, is difficult to the shortcomings that recycling and reusing.
There is the report of numerous studies ester exchange reaction in the country, as dimethyl carbonate and ethyl alcohol transesterification prepare carbonic acid diethyl
Ester, but dimethyl carbonate is the parallel reversible reaction contacted with ethyl alcohol ester exchange reaction, there are serious selective problems, carbon
Dimethyl phthalate is greatly converted to methyl ethyl carbonate, to waste raw material and energy.Coproduction simultaneously is existing market
The upper methanol that supply exceed demand, it is economically competitiveless.And with ethylene carbonate (or propene carbonate) and ethyl alcohol transesterification
The report for preparing diethyl carbonate is seldom.
Summary of the invention
The purpose of the present invention is to provide the production works that a kind of solid base catalyst is directly catalyzed high-purity diethyl carbonate
Skill,.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, and the production technology reaction equation is such as
Shown in lower:
The reaction is one step high selection of raw material by ethylene carbonate (EC) and ethyl alcohol (EtOH) using multifunctional solid alkali as catalyst
Property obtains diethyl carbonate (DEC) and ethylene glycol (EG), and basic catalyst is completely insoluble in raw material and product, and reaction process is not deposited
In any pollutant, ethylene glycol (EG) is a kind of bulk chemical, and high-purity diethyl carbonate (DEC) is obtained in reaction process；
Its specific embodiment, comprising: the ethylene carbonate and ethyl alcohol of raw material liquid are preheated by the preheated tank V-1 of metering pump P-1
Afterwards, ethyl alcohol is by vapour form, the two enters the first reactive distillation column of T1, tower together after the preheated tank V-2 preheating of metering pump P-2
Kettle has a large amount of ethyl alcohol, and tower reactor does not have ethyl alcohol residue, and ethyl alcohol is to be fed in the form of high-temperature gas from first rectifying column bottom；Material carbon
Vinyl acetate and alcohol mixture are fed in the first reactive distillation column middle and upper part, are released catalyst bed after being subdivided cloth device and are filled out
The bed of material, catalyst bed and packing layer can be to mix and fill out, and be also possible to one layer of catalyst, one layer of filler；In the first reactive distillation
In tower, as catalytic distillation corresponsively carries out, product diethyl carbonate and excess ethyl alcohol are separated from tower top；Unreacted carbonic acid second
Enester and the glycol product downlink in rectifying column, contact, a small amount of ethylene carbonate and excess with a large amount of tower bottom hot ethanol steam
Ethyl alcohol sufficiently reacts, and ethylene carbonate is consumed almost fully reacting significantly, and the first obtained mixture includes that minute quantity is not anti-
The ethylene carbonate answered, a small amount of product diethyl carbonate and a large amount of ethylene glycol；First reactive distillation column top of tower comes out light
Group is divided into ethyl alcohol and diethyl carbonate, after the condensation of E-1 condenser, is directly entered T2 rectifying column, tower reactor is heavy constituent carbonic acid two
Ethyl ester, tower top is light component ethyl alcohol and little water, after molecular sieve adsorbing and dewatering, as raw material reuse；First reaction essence
Evaporate the heavy constituent that tower reactor bottom comes out are as follows: the unreacted ethylene carbonate of minute quantity, a small amount of product diethyl carbonate and a large amount of second
Glycol；By T3 vacuum rectification tower rectification under vacuum, part diethyl carbonate is steamed from tower top, tower reactor obtains heavy constituent minute quantity
Unreacted ethylene carbonate and a large amount of ethylene glycol；Heavy constituent in T3 tower reactor is directly entered T4 vacuum rectification tower, and tower top obtains
The ethylene glycol fine work of high-purity, tower reactor obtain ethylene carbonate directly as feedstock circulation to the first reactive distillation column.
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, and the catalyst is one
The multi-functional compound basic matterial of kind, catalyst carrier are the molecular sieve with meso-hole structure, load one or more metallic elements
As active component, usage amount is the 0.3%~5% of total mass of raw material.
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, the oxide spinel second
Enester and ethyl alcohol beat liquid feedstock with metering pump P-1 pump, preheating can V1 and V2 temperature is 40-70 with molar ratio 1:1-20:1
℃。
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, the production technology,
Its device includes: the first reactive distillation column of T1, has spaced apart from top to bottom urge among first reactive distillation column of T1
Agent import, oxide spinel vinyl acetate and ethyl alcohol import, ethyl alcohol import, the tower top of the first reactive distillation column of T1 have T2 normal pressure essence
The first connected discharge port of tower tower body is evaporated, the tower bottom of the first reactive distillation column of T1 has one and is connected with T3 vacuum rectification tower tower body
The second discharge port, and the tower body of the first reactive distillation column of T1 have first charging aperture and second charging aperture；T2 atmospheric distillation tower,
T2 atmospheric distillation tower tower body has the third feed inlet being connected with first discharge port, and T2 atmospheric distillation column overhead has third
The tower bottom of discharge port and T2 atmospheric distillation tower has the 4th discharge port；T3 vacuum rectification tower, T3 rectification under vacuum tower body have and the
Connected the 4th feed inlet of two discharge ports, the top of tower of vacuum rectification tower have the tower of the 5th discharge port and vacuum rectification tower
Bottom has the 6th discharge port；T4 vacuum rectification tower, T4 rectification under vacuum tower body have one the 5th to be connected with the 6th discharge port
The top of tower of feed inlet, vacuum rectification tower has the 8th discharge port with the tower bottom of the 7th discharge port and vacuum rectification tower.
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, the first reaction essence
It evaporates in tower T1, oxide spinel vinyl acetate and ethyl alcohol react under the effect of the catalyst, obtain the first mixture；First reaction
The light component of the top of the distillation column；Predominantly diethyl carbonate and ethyl alcohol are directly entered the separation of T2 normal pressure through condenser E-1 condensation,
T2 tower bottom heavy constituent diethyl carbonate is separated, the heavy constituent of the first reactive distillation column tower bottom；Predominantly a small amount of carbonic acid diethyl
Ester, a small amount of ethylene carbonate and ethylene glycol are directly entered T3 decompression separation, the light component carbon of T3 tower top through condenser E-2 condensation
Diethyl phthalate is separated, the heavy constituent of T3 tower bottom, and predominantly a small amount of ethylene carbonate and ethylene glycol are condensed through condenser E-6
It is directly entered T4 decompression separation, the light component ethylene glycol of T4 tower top is separated；Last T2 tower top obtains straight alcohol and T4 tower bottom
Obtained pure ethylene carbonate returns to T1 and continues rectification process.
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, and the T1 first reacts
The tower pressure interior force of rectifying column is 0.01MPa~5MPa, and tower top temperature is 110 DEG C~130 DEG C, and column bottom temperature is 180 DEG C~200
℃；The tower pressure interior force of T2 atmospheric distillation tower is 0.1MPa~0.5MPa, and 78 DEG C~85 DEG C of tower top temperature, column bottom temperature is 110 DEG C
~140 DEG C；The tower pressure interior force of vacuum rectification tower T3 is the MPa of 0.1 MPa~0.5, and tower top temperature is 90 DEG C~120 DEG C, tower bottom temperature
Degree is 160 DEG C~200 DEG C；The tower pressure interior force of vacuum rectification tower T4 be the MPa of 0.1 MPa~0.5, tower top temperature be 165 DEG C~
185 DEG C, column bottom temperature is 180 DEG C~200 DEG C；When diethyl carbonate content reaches 60% or more, T1 the first reactive distillation tower top
To T2 atmospheric distillation tower feed liquor.
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, and the T1 first reacts
Rectifying column, T2 atmospheric distillation tower, T3 vacuum rectification tower, T4 vacuum rectification tower are plate column, packed tower or board-like-filler mixing
Tower.
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, the reaction of described device
The partition of device and rectifying column is arranged to make the ratio between cross-sectional area of the cross-sectional area of the fore-running section and the side line section for 1:1-
3:1。
A kind of solid base catalyst is directly catalyzed the production technology of high-purity diethyl carbonate, the tower of the fore-running section
Plate number 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 stripping section
The number of plates is 1~30 piece.
The advantages and effects of the present invention are:
The present invention starts one using ethylene carbonate and ethyl alcohol as the process route of Material synthesis ethylene carbonate.It realizes with more function
The compound basic matterial of energy is directly catalyzed ethylene carbonate and ethyl alcohol in catalytic rectifying tower simple separation technology.By simple rectifying,
Liquid of top of the tower obtains high-purity diethyl carbonate solution by atmospheric distillation, and a large amount of second two can be obtained by decompression separation in tower bottoms
Alcohol, minute quantity diethyl carbonate and a small amount of ethylene carbonate, ethyl alcohol and ethylene carbonate are directly as feedstock circulation to first anti-
Answer rectifying column.The production technology of the one-step synthesis diethyl carbonate, synthesis path is short, and process flow is simple, selectivity of product and
High income, relatively current technique can significantly more efficient production diethyl carbonates.
Detailed description of the invention
Fig. 1 is the catalyzed by solid base rectification process figure that the high-purity diethyl carbonate of lithium electricity produces；
Fig. 2 is 13X molecular sieve de-watering apparatus figure.
Specific embodiment
The following describes the present invention in detail with reference to examples.
The present invention is a kind of to prepare the lithium battery solid of high-purity diethyl carbonate by ethylene carbonate and ethyl alcohol transesterification
Catalytic rectification process, reaction equation are as follows:
The reaction is one step high selection of raw material by ethylene carbonate (EC) and ethyl alcohol (EtOH) using multifunctional solid alkali as catalyst
Property obtains diethyl carbonate (DEC) and ethylene glycol (EG), and basic catalyst is completely insoluble in raw material and product, and reaction process is not deposited
In any pollutant, ethylene glycol (EG) is a kind of bulk chemical, has a vast market application prospect；It can be obtained in reaction process
To high-purity diethyl carbonate (DEC).
Protection is prepared the production catalyzed by solid base rectification process of diethyl carbonate, packet by ethylene carbonate and ethyl alcohol transesterification
It includes:
The ethylene carbonate and ethyl alcohol of certain mol proportion react in pre-reactor reach balance after, into normal pressure catalytic distillation
Tower, tower bottom are passed through excessive heat alcohol vapour, and overhead product is diethyl carbonate and excess ethyl alcohol；Tower kettle product is that minute quantity is not anti-
The ethylene carbonate answered, a small amount of product diethyl carbonate and a large amount of ethylene glycol.
For first reactive distillation tower overhead through vacuum rectification tower, tower top isolates the ethyl alcohol with a small amount of water, and tower bottom is to produce
Product diethyl carbonate.
After first reactive distillation column tower reactor recombinates lease making rectification under vacuum, tower top obtains diethyl carbonate, and tower reactor is containing few
Measure the ethylene glycol of ethylene carbonate.
The ethylene glycol of the ethylene carbonate containing minute quantity directly obtains polyester grade ethylene glycol, resultant product after rectification under vacuum
Directly as feedstock circulation to first rectifying column.
After hydrous ethanol passes through molecular sieve adsorbing and dewatering, as raw material reuse.
After the ethylene carbonate and ethyl alcohol of raw material liquid are by the preheated tank V-1 preheating of metering pump P-1, ethyl alcohol is by metering pump P-
After 2 preheated tank V-2 preheatings in vapour form, the two enters the first reactive distillation column of T1 together, and tower reactor has a large amount of ethyl alcohol (tower reactors
There is no ethyl alcohol residue, and ethyl alcohol is to feed in the form of high-temperature gas from first rectifying column bottom).Oxide spinel vinyl acetate and ethyl alcohol are mixed
It closes object to feed in the first reactive distillation column middle and upper part, releases catalyst bed and packing layer (catalyst bed after being subdivided cloth device
It can be to mix with packing layer and fill out, be also possible to one layer of catalyst, one layer of filler).In the first reactive distillation column, with catalysis essence
It evaporates and corresponsively carries out, product diethyl carbonate and excess ethyl alcohol are separated from tower top；Unreacted ethylene carbonate and product second two
Alcohol downlink in rectifying column is contacted with a large amount of tower bottom hot ethanol steam, and a small amount of ethylene carbonate is sufficiently reacted with excess ethyl alcohol, carbon
Vinyl acetate is consumed almost fully reacting significantly, and the first obtained mixture includes the unreacted ethylene carbonate of minute quantity,
A small amount of product diethyl carbonate and a large amount of ethylene glycol.The light component that first reactive distillation column top of tower comes out is ethyl alcohol and carbonic acid
Diethylester is directly entered T2 rectifying column after the condensation of E-1 condenser, and tower reactor is heavy constituent diethyl carbonate, and tower top is light component
Ethyl alcohol and little water, after molecular sieve adsorbing and dewatering, as raw material reuse.The recombination that first reactive distillation column bottom comes out
It is divided into: the unreacted ethylene carbonate of minute quantity, a small amount of product diethyl carbonate and a large amount of ethylene glycol.Pass through T3 rectification under vacuum
Tower rectification under vacuum steams part diethyl carbonate from tower top, and tower reactor obtains the unreacted ethylene carbonate of heavy constituent minute quantity
With a large amount of ethylene glycol.Heavy constituent in T3 tower reactor is directly entered T4 vacuum rectification tower, and tower top obtains the ethylene glycol fine work of high-purity,
Tower reactor obtains ethylene carbonate directly as feedstock circulation to the first reactive distillation column.
For the present invention by the technique of ethylene carbonate and ethyl alcohol transesterification preparation production diethyl carbonate, Fig. 1 is reaction raw materials
Ethylene carbonate and ethyl alcohol enter the first reactive distillation column of T1, and ethylene carbonate and ethanol synthesis are abundant, finally obtained product
It is diethyl carbonate and ethylene glycol.When the synthesis technology reactive distillation carries out, extraction and separation are carried out to product without solvent, significantly
The process flow of conventional diethyl carbonate synthesis is simplified, while multicomponent can be made disposably to separate, separation purity is high.
The present invention is had by ethylene carbonate with the production technology that ethyl alcohol transesterification prepares diethyl carbonate following additional
Technical characteristic:
Catalyst used in the technique is a kind of multi-functional compound basic matterial, and catalyst carrier is the molecule with meso-hole structure
Sieve, loads one or more metallic elements as active component.Deactivation phenomenom is not present using 5000h in catalyst performance stabilised,
Its usage amount is the 0.3%~5% of the total mass of raw material.
The ethylene carbonate and ethyl alcohol beat liquid feedstock, preheating can V1 with metering pump P-1 pump with molar ratio 1:1-20:1
It is 40-70 DEG C with V2 temperature.
The present invention is prepared the device of diethyl carbonate by ethylene carbonate and ethyl alcohol transesterification, comprising: T1 first reacts essence
Tower is evaporated, there is from top to bottom spaced apart catalyst inlet, oxide spinel vinyl acetate among first reactive distillation column of T1
With ethyl alcohol import, ethyl alcohol import, the tower top of first reactive distillation column of T1 has first that T2 atmospheric distillation tower tower body is connected
The tower bottom of discharge port, first reactive distillation column of T1 has second discharge port being connected with T3 vacuum rectification tower tower body,
And the tower body of first reactive distillation column of T1 has first charging aperture and second charging aperture；T2 atmospheric distillation tower, the T2 are normal
Pressure rectifying column tower body has the third feed inlet being connected with first discharge port, and the T2 atmospheric distillation column overhead has third
The tower bottom of discharge port and the T2 atmospheric distillation tower has the 4th discharge port；T3 vacuum rectification tower, the T3 rectification under vacuum tower body
With the 4th feed inlet being connected with second discharge port, the top of tower of the vacuum rectification tower has the 5th discharge port
And the tower bottom of the vacuum rectification tower has the 6th discharge port；T4 vacuum rectification tower, the T4 rectification under vacuum tower body have with
Connected the 5th feed inlet of 6th discharge port, the top of tower of the vacuum rectification tower have the 7th discharge port and described
The tower bottom of vacuum rectification tower has the 8th discharge port.
An example according to the present invention, in the first reactive distillation column T1, oxide spinel vinyl acetate and ethyl alcohol are being catalyzed
It reacts under the action of agent, obtains the first mixture；Light component (the predominantly diethyl carbonate of first reactive distillation column overhead
With ethyl alcohol) it is directly entered T2 normal pressure through condenser E-1 condensation and separates, T2 tower bottom heavy constituent diethyl carbonate is separated.First
The heavy constituent (predominantly a small amount of diethyl carbonate, a small amount of ethylene carbonate and ethylene glycol) of reactive distillation column tower bottom is through condenser E-
2 condensations are directly entered T3 decompression separation, and the light component diethyl carbonate of T3 tower top is separated, and the heavy constituent of T3 tower bottom is (main
For a small amount of ethylene carbonate and ethylene glycol) through condenser E-6 condensation be directly entered T4 decompression separation, the light component second two of T4 tower top
Alcohol is separated.The pure ethylene carbonate that last T2 tower top obtains straight alcohol and T4 tower bottom obtains returns to T1 and continues rectification process.
The tower pressure interior force of first reactive distillation column of T1 is 0.01MPa~5MPa, and tower top temperature is 110 DEG C~130 DEG C,
Column bottom temperature is 180 DEG C~200 DEG C；The tower pressure interior force of the T2 atmospheric distillation tower is 0.1MPa~0.5MPa, tower top temperature 78
DEG C~85 DEG C, column bottom temperature is 110 DEG C~140 DEG C；The tower pressure interior force of the vacuum rectification tower T3 is the MPa of 0.1 MPa~0.5,
Tower top temperature is 90 DEG C~120 DEG C, and column bottom temperature is 160 DEG C~200 DEG C；The tower pressure interior force of the vacuum rectification tower T4 is 0.1
The MPa of MPa~0.5, tower top temperature are 165 DEG C~185 DEG C, and column bottom temperature is 180 DEG C~200 DEG C；When diethyl carbonate content reaches
When to 60% or more, T1 the first reactive distillation tower top is to T2 atmospheric distillation tower feed liquor.
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.
The first reactive distillation column of T1, T2 atmospheric distillation tower, T3 vacuum rectification tower, T4 vacuum rectification tower are board-like in the present invention
Tower, packed tower or board-like-filler mixing column.
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
Using ethylene carbonate and excessive ethyl alcohol as raw material, reaction production diethyl carbonate and ethylene glycol the mass ratio of the material are
1:1, the ethyl alcohol steamed recycle.
Catalyst is alkaline composite material 15%BaO-5%MgO-3%La2O3/ Cs-meso-EMT, fore-running section and side line section
The ratio between cross-sectional area is 1:1.
T1 and T2 tower operating condition is as follows:
First reactive distillation column T1: tower diameter 1000mm；Tower height 19000mm；Public rectifying section, fore-running section, side line section, public stripping
The number of plates of section is respectively 10,20,30,15；Tower pressure interior force 0.5MPa；130 DEG C of tower top temperature；The column bottom temperature of public stripping section
190℃；170 DEG C of the column bottom temperature of side line section.
Atmospheric distillation tower T2: 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, 65 DEG C of tower top temperature, 120 DEG C of the column bottom temperature of public stripping section.
In the first reactive distillation column T1, oxide spinel vinyl acetate and ethyl alcohol are in 15%BaO-5%MgO-3%La2O3/Cs-
It sufficiently reacts under the action of meso-EMT spheric catalyst, the first obtained mixture includes diethyl carbonate, unreacted
Complete ethyl alcohol and ethylene glycol.The light component (predominantly diethyl carbonate and ethyl alcohol) of first reactive distillation column overhead is through condenser E-
1 condensation is directly entered T2 and carries out normal pressure separation, and T2 tower bottom heavy constituent diethyl carbonate is separated.
Embodiment 2
T3 and T4 tower operating condition is as follows:
Vacuum rectification tower T3: tower diameter 3000mm；Tower height 40000mm；Public rectifying section, fore-running section, side line section, public stripping section
The number of plates is respectively 10,20,30,15；0.1 MPa of tower pressure interior force；90 DEG C of tower top temperature, the column bottom temperature 160 of public stripping section
℃；120 DEG C of the column bottom temperature of side line section.
Vacuum rectification tower T4: 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；0.1 MPa of tower pressure interior force；165 DEG C of tower top temperature, the tower bottom temperature of public stripping section
180 DEG C of degree；150 DEG C of the column bottom temperature of side line section.
In the first reactive distillation column T1, oxide spinel vinyl acetate and ethyl alcohol are in 15%BaO-5%MgO-3%La2O3/Cs-
It reacts under the action of meso-EMT spheric catalyst, the first obtained mixture includes that diethyl carbonate, unreacted are complete
Ethyl alcohol and ethylene glycol.Heavy constituent (predominantly a small amount of dimethyl carbonate, a small amount of ethylene carbonate and the second two of first mixture tower bottom
Alcohol) T3 is directly entered through condenser E-2 condensation carries out decompression separation, the light component diethyl carbonate of T3 tower top separated, T3
The a small amount of ethylene carbonate of the heavy constituent of tower bottom and glycol condenser E-6 condensation are directly entered T4 and are depressurized, T4 tower top it is light
Component ethylene glycol is separated, and the heavy constituent ethylene carbonate of T4 tower bottom comes back to T1 as raw material and continues rectification process.
Embodiment 3
T2 atmospheric distillation column overhead obtains 95% ethyl alcohol and is removed water to obtain 99.99% ethyl alcohol by 13X molecular sieve de-watering apparatus
It comes back to T1 tower reactor and continues rectification process.
95% ethyl alcohol, which squeezes into molecular sieve de-watering apparatus with certain speed, can be obtained 99.99% ethyl alcohol, is extracted and is divided with vacuum pump
The sub a large amount of water sieved above and a small amount of ethyl alcohol are pumped into vacuum rectification tower, and a large amount of water can be obtained in tower bottom, and tower top obtains 95% ethyl alcohol,
It is pumped into molecular sieve de-watering apparatus circular treatment again.
Molecular sieve de-watering apparatus figure is as shown in Figure 2:
The above is only several embodiments of the application, not does any type of limitation to the application, although the application with
Preferred embodiment discloses as above, however not to limit the application, any person skilled in the art is not departing from this
In the range of applying for technical solution, a little variation or modification are made using the technology contents of the disclosure above and is equal to equivalent reality
Case is applied, is belonged in technical proposal scope.
Claims (9)
1. the production technology that a kind of solid base catalyst is directly catalyzed high-purity diethyl carbonate, which is characterized in that the production work
Skill reaction equation is as follows:
The reaction is one step high selection of raw material by ethylene carbonate (EC) and ethyl alcohol (EtOH) using multifunctional solid alkali as catalyst
Property obtains diethyl carbonate (DEC) and ethylene glycol (EG), and basic catalyst is completely insoluble in raw material and product, and reaction process is not deposited
In any pollutant, ethylene glycol (EG) is a kind of bulk chemical, and high-purity diethyl carbonate (DEC) is obtained in reaction process；
Its specific embodiment, comprising: the ethylene carbonate and ethyl alcohol of raw material liquid are preheated by the preheated tank V-1 of metering pump P-1
Afterwards, ethyl alcohol is by vapour form, the two enters the first reactive distillation column of T1, tower together after the preheated tank V-2 preheating of metering pump P-2
Kettle has a large amount of ethyl alcohol, and tower reactor does not have ethyl alcohol residue, and ethyl alcohol is to be fed in the form of high-temperature gas from first rectifying column bottom；Material carbon
Vinyl acetate and alcohol mixture are fed in the first reactive distillation column middle and upper part, are released catalyst bed after being subdivided cloth device and are filled out
The bed of material, catalyst bed and packing layer can be to mix and fill out, and be also possible to one layer of catalyst, one layer of filler；In the first reactive distillation
In tower, as catalytic distillation corresponsively carries out, product diethyl carbonate and excess ethyl alcohol are separated from tower top；Unreacted carbonic acid second
Enester and the glycol product downlink in rectifying column, contact, a small amount of ethylene carbonate and excess with a large amount of tower bottom hot ethanol steam
Ethyl alcohol sufficiently reacts, and ethylene carbonate is consumed almost fully reacting significantly, and the first obtained mixture includes that minute quantity is not anti-
The ethylene carbonate answered, a small amount of product diethyl carbonate and a large amount of ethylene glycol；First reactive distillation column top of tower comes out light
Group is divided into ethyl alcohol and diethyl carbonate, after the condensation of E-1 condenser, is directly entered T2 rectifying column, tower reactor is heavy constituent carbonic acid two
Ethyl ester, tower top is light component ethyl alcohol and little water, after molecular sieve adsorbing and dewatering, as raw material reuse；First reaction essence
Evaporate the heavy constituent that tower reactor bottom comes out are as follows: the unreacted ethylene carbonate of minute quantity, a small amount of product diethyl carbonate and a large amount of second
Glycol；By T3 vacuum rectification tower rectification under vacuum, part diethyl carbonate is steamed from tower top, tower reactor obtains heavy constituent minute quantity
Unreacted ethylene carbonate and a large amount of ethylene glycol；Heavy constituent in T3 tower reactor is directly entered T4 vacuum rectification tower, and tower top obtains
The ethylene glycol fine work of high-purity, tower reactor obtain ethylene carbonate directly as feedstock circulation to the first reactive distillation column.
2. a kind of solid base catalyst according to claim 1 is directly catalyzed the production technology of high-purity diethyl carbonate,
It being characterized in that, the catalyst is a kind of multi-functional compound basic matterial, and catalyst carrier is the molecular sieve with meso-hole structure,
One or more metallic elements are loaded as active component, usage amount is the 0.3%~5% of total mass of raw material.
3. a kind of solid base catalyst according to claim 1 is directly catalyzed the production technology of high-purity diethyl carbonate,
It is characterized in that, the oxide spinel vinyl acetate and ethyl alcohol beat liquid feedstock with metering pump P-1 pump, in advance with molar ratio 1:1-20:1
Hot tank V1 and V2 temperature are 40-70 DEG C.
4. a kind of solid base catalyst according to claim 1 is directly catalyzed the production technology of high-purity diethyl carbonate,
It is characterized in that, the production technology, device includes: the first reactive distillation column of T1, tool among first reactive distillation column of T1
There are from top to bottom spaced apart catalyst inlet, oxide spinel vinyl acetate and ethyl alcohol import, ethyl alcohol import, T1 first reacts essence
The first discharge port that there is the tower top of tower T2 atmospheric distillation tower tower body to be connected is evaporated, the tower bottom of the first reactive distillation column of T1 has one
The second discharge port being connected with T3 vacuum rectification tower tower body, and the tower body of the first reactive distillation column of T1 has first charging aperture and the
Two feed inlets；T2 atmospheric distillation tower, T2 atmospheric distillation tower tower body have the third feed inlet being connected with first discharge port, T2
Atmospheric distillation column overhead has the 4th discharge port with the tower bottom of third discharge port and T2 atmospheric distillation tower；T3 vacuum rectification tower,
T3 rectification under vacuum tower body has the 4th feed inlet being connected with the second discharge port, and the top of tower of vacuum rectification tower has the 5th
Discharge port and the tower bottom of vacuum rectification tower have the 6th discharge port；T4 vacuum rectification tower, T4 rectification under vacuum tower body have and the
Connected the 5th feed inlet of six discharge ports, the top of tower of vacuum rectification tower have the tower of the 7th discharge port and vacuum rectification tower
Bottom has the 8th discharge port.
5. a kind of solid base catalyst according to claim 1 is directly catalyzed the production technology of high-purity diethyl carbonate,
It being characterized in that, in the first reactive distillation column T1, oxide spinel vinyl acetate and ethyl alcohol react under the effect of the catalyst,
Obtain the first mixture；The light component of first reactive distillation column overhead；Predominantly diethyl carbonate and ethyl alcohol, through condenser E-1
Condensation is directly entered the separation of T2 normal pressure, and T2 tower bottom heavy constituent diethyl carbonate is separated, the weight of the first reactive distillation column tower bottom
Component；Predominantly a small amount of diethyl carbonate, a small amount of ethylene carbonate and ethylene glycol are directly entered T3 through condenser E-2 condensation and subtract
Pressure separation, the light component diethyl carbonate of T3 tower top separated, the heavy constituent of T3 tower bottom, predominantly a small amount of ethylene carbonate and
Ethylene glycol is directly entered T4 decompression separation through condenser E-6 condensation, and the light component ethylene glycol of T4 tower top is separated；Last T2
The pure ethylene carbonate that tower top obtains straight alcohol and T4 tower bottom obtains returns to T1 and continues rectification process.
6. a kind of solid base catalyst according to claim 1 is directly catalyzed the production technology of high-purity diethyl carbonate,
It is characterized in that, the tower pressure interior force of first reactive distillation column of T1 is 0.01MPa~5MPa, and tower top temperature is 110 DEG C~130
DEG C, column bottom temperature is 180 DEG C~200 DEG C；The tower pressure interior force of T2 atmospheric distillation tower be 0.1MPa~0.5MPa, 78 DEG C of tower top temperature
~85 DEG C, column bottom temperature is 110 DEG C~140 DEG C；The tower pressure interior force of vacuum rectification tower T3 is the MPa of 0.1 MPa~0.5, tower top temperature
Degree is 90 DEG C~120 DEG C, and column bottom temperature is 160 DEG C~200 DEG C；The tower pressure interior force of vacuum rectification tower T4 is 0.1 MPa~0.5
MPa, tower top temperature are 165 DEG C~185 DEG C, and column bottom temperature is 180 DEG C~200 DEG C；When diethyl carbonate content reaches 60% or more
When, T1 the first reactive distillation tower top is to T2 atmospheric distillation tower feed liquor.
7. a kind of solid base catalyst according to claim 6 is directly catalyzed the production technology of high-purity diethyl carbonate,
Be characterized in that, first reactive distillation column of T1, T2 atmospheric distillation tower, T3 vacuum rectification tower, T4 vacuum rectification tower be plate column,
Packed tower or board-like-filler mixing column.
8. a kind of solid base catalyst according to claim 1 is directly catalyzed the production technology of high-purity diethyl carbonate,
It is characterized in that, the reactor of described device and the partition of rectifying column are arranged to make the cross-sectional area of the fore-running section and the side line
The ratio between cross-sectional area of section is 1:1-3:1.
9. a kind of solid base catalyst according to claim 8 is directly catalyzed the production technology of high-purity diethyl carbonate,
It is characterized in that, the number of plates of the 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
It is 1~30 piece, the number of plates of public stripping section is 1~30 piece.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113548967A (en) * | 2021-08-13 | 2021-10-26 | 中国科学院山西煤炭化学研究所 | Device and method for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification |
| CN114736122A (en) * | 2022-05-23 | 2022-07-12 | 天津科技大学 | Reaction circulation rectification process method for producing ethyl methyl carbonate and diethyl ester |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657717A (en) * | 2013-12-09 | 2014-03-26 | 南京工业大学 | Solid base catalyst for catalyzing ester exchange reaction and preparation method thereof |
-
2018
- 2018-10-15 CN CN201811194264.XA patent/CN109369400A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103657717A (en) * | 2013-12-09 | 2014-03-26 | 南京工业大学 | Solid base catalyst for catalyzing ester exchange reaction and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113548967A (en) * | 2021-08-13 | 2021-10-26 | 中国科学院山西煤炭化学研究所 | Device and method for producing high-purity dimethyl carbonate by heterogeneous catalytic reaction rectification |
| CN114736122A (en) * | 2022-05-23 | 2022-07-12 | 天津科技大学 | Reaction circulation rectification process method for producing ethyl methyl carbonate and diethyl ester |
| CN114736122B (en) * | 2022-05-23 | 2023-12-08 | 天津科技大学 | Reaction circulation rectification process method for producing methyl ethyl carbonate and diethyl ester |
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