CN107827779A - Batch reactive distillation production cyanoacetate compound, malonate compound device and its production technology - Google Patents
Batch reactive distillation production cyanoacetate compound, malonate compound device and its production technology Download PDFInfo
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- CN107827779A CN107827779A CN201711032634.5A CN201711032634A CN107827779A CN 107827779 A CN107827779 A CN 107827779A CN 201711032634 A CN201711032634 A CN 201711032634A CN 107827779 A CN107827779 A CN 107827779A
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- esterification
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- -1 cyanoacetate compound Chemical class 0.000 title claims abstract description 53
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000000066 reactive distillation Methods 0.000 title claims abstract description 23
- 238000005516 engineering process Methods 0.000 title claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 201
- 230000032050 esterification Effects 0.000 claims abstract description 199
- 238000000605 extraction Methods 0.000 claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000012071 phase Substances 0.000 claims abstract description 47
- 238000010992 reflux Methods 0.000 claims abstract description 47
- 239000008346 aqueous phase Substances 0.000 claims abstract description 44
- 238000000895 extractive distillation Methods 0.000 claims abstract description 34
- 238000004581 coalescence Methods 0.000 claims abstract description 30
- 150000002148 esters Chemical class 0.000 claims abstract description 17
- 239000000284 extract Substances 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000009834 vaporization Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 238000007599 discharging Methods 0.000 description 8
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010533 azeotropic distillation Methods 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical compound CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- LXNHXLLTXMVWPM-UHFFFAOYSA-N pyridoxine Chemical compound CC1=NC=C(CO)C(CO)=C1O LXNHXLLTXMVWPM-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- UNEABORYRHUWBR-UHFFFAOYSA-N 2-cyanoacetic acid;ethanol Chemical compound CCO.OC(=O)CC#N UNEABORYRHUWBR-UHFFFAOYSA-N 0.000 description 1
- BZAARVXVDWLOFK-UHFFFAOYSA-N 4-methoxy-2,3-dimethylpyridine Chemical class COC1=CC=NC(C)=C1C BZAARVXVDWLOFK-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 238000007309 Fischer-Speier esterification reaction Methods 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- RSMCZIMSRVMJEB-UHFFFAOYSA-N [Cl].CCOC(C)=O Chemical compound [Cl].CCOC(C)=O RSMCZIMSRVMJEB-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VILAVOFMIJHSJA-UHFFFAOYSA-N dicarbon monoxide Chemical compound [C]=C=O VILAVOFMIJHSJA-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- ANGDWNBGPBMQHW-UHFFFAOYSA-N methyl cyanoacetate Chemical compound COC(=O)CC#N ANGDWNBGPBMQHW-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004334 oxygen containing inorganic group Chemical group 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- RADKZDMFGJYCBB-UHFFFAOYSA-N pyridoxal hydrochloride Natural products CC1=NC=C(CO)C(C=O)=C1O RADKZDMFGJYCBB-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011726 vitamin B6 Substances 0.000 description 1
- 235000019158 vitamin B6 Nutrition 0.000 description 1
- 229940011671 vitamin b6 Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- 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
- Y02P20/10—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of batch reactive distillation production cyanoacetate compound, malonate compound device and its production technology, connection esterification splitter at the top of reaction kettle of the esterification in device, it is esterified connection esterification tower bottom at the top of splitter, esterification tower bottom connection reaction kettle of the esterification top, at the top of esterification tower esterification reflux ratio distributor is connected through esterification condensator, it is esterified reflux ratio distributor connection coalescence phase-splitter, coalesce phase-splitter top connection esterification tower top, aqueous phase receiving tank connection coalescence phase-splitter bottom, oil phase receiving tank connection esterification reflux ratio distributor, extractive distillation column connects aqueous phase receiving tank, extract overhead condenser connection extracting rectifying top of tower, extract return tank of top of the tower connection extraction overhead condenser, extract at the top of return tank of top of the tower bottom connection reaction kettle of the esterification.The present invention improves the yield of thick ester, reduces energy resource consumption, and entrainer, extractant can reclaim use.
Description
Technical field
The invention belongs to the synthesis technique of continuous production processes, more particularly to produce cyanogen second for a kind of batch reactive distillation
Acid esters compound, malonate compound device and the device using rectifying production cyanoacetate compound, malonate compound enter
Row rectifying production cyanoacetate compound, the technique of malonate compound.
Background technology
Ethyl cyanoacetate is a kind of important chemical intermediate, for synthesizing ester, amide-type, acids, nitrile compounds.
Japan is mainly used as the intermediate of cyanoacrylate Instant cement, for the bonding of auto parts, household electrical appliance assembly, separately
It is additionally operable to the fields such as vitamin B6, synthetic dyestuffs outside.5- can be made with methoxy ethylacetoacetone and ammoniacal liquor cyclization in ethyl cyanoacetate
Cyano group -6- hydroxyl -4- methoxyl methyl -2- picolines.3- amino -5- aminomethyls -4- can be obtained through nitrification, chlorination, catalytic hydrogenation
Methoxyl methyl -2- picolines.Further diazotising, hydrolysis, into salt can obtain micro-element B6.
Esterification, it is a kind of organic chemical reactionses, is reaction of the alcohol with carboxylic acid or oxygen-containing inorganic acid generation ester and water.Carboxylic
Acid is reversible with the esterification of alcohol, and General reactions are extremely slow, therefore the conventional concentrated sulfuric acid makees catalyst.Esterification belongs to
Reversible reaction, generally reaction is carried out not thorough, according to reaction equilibrium theory, to improve the yield of ester, it is necessary to from production
A kind of method that thing isolates composition or makes reactant one of which composition excessive carries out reaction positive direction.Traditional esterification skill
Art is to use acid and the alcohol heating reflux reaction under sour (being often the concentrated sulfuric acid) catalysis.This reaction is also referred to as Fischer esterification.
The effect of the concentrated sulfuric acid is catalyst and water absorbing agent, and it can protonate the carbonyl of carboxylic acid, strengthen the electrophilicity of carbonyl carbon, make anti-
Speed is answered to accelerate；The water byproduct of dereaction can also be removed, improves the yield of ester.
The content of the invention
It is an object of the invention to overcome above-mentioned shortcoming, there is provided a kind of to react rectifying thorough, that the reaction time is short
Produce cyanoacetate compound, malonate compound device.
The technical scheme is that：
A kind of batch reactive distillation production cyanoacetate compound, malonate compound device, including reaction kettle of the esterification, esterification
Splitter, esterification tower, esterification reflux ratio distributor, coalescence phase-splitter, aqueous phase receiving tank, oil phase receiving tank；Esterification
Connection esterification splitter at the top of kettle, esterification splitter top connection esterification tower bottom, the connection esterification of esterification tower bottom
Reactor top, esterification tower top connect esterification reflux ratio distributor through esterification condensator, and esterification reflux ratio distributor connects
Connect esterification tower top, esterification reflux ratio distributor connection coalescence phase-splitter, coalescence phase-splitter top connection esterification tower
Top, aqueous phase receiving tank connection coalescence phase-splitter bottom, oil phase receiving tank, which connects, is esterified reflux ratio distributor, under oil phase receiving tank
End is connected at the top of reaction kettle of the esterification.
As preferable technical scheme, described device further comprises extractive distillation column, extraction overhead condenser, extraction tower
Return tank is pushed up, the extractive distillation column connects the aqueous phase receiving tank, the extraction overhead condenser connection extracting rectifying tower top
Portion, the extraction return tank of top of the tower connection extraction overhead condenser, the extraction return tank of top of the tower bottom connection reaction kettle of the esterification
Top, extractive distillation column top.
As preferable technical scheme, it is connected at the top of described reaction kettle of the esterification with being esterified the bottom of splitter, esterification point
Connected from the top of post and the middle and lower part of esterification tower, the bottom of esterification tower and the top of reaction kettle of the esterification connect.
As preferable technical scheme, the esterification condensator includes esterification first-stage condenser and esterification secondary condenser,
The top of esterification tower is connected with esterification first-stage condenser, and esterification first-stage condenser is connected with esterification secondary condenser, is esterified
The top of secondary condenser is connected with blow-down pipe or vacuum lines, is esterified bottom and the esterification backflow score of secondary condenser
The top connection of orchestration；The extraction pipeline of the esterification reflux ratio distributor connects with coalescence phase-splitter bottom feed line and oil phase
Connected at the top of closed cans, the overhead reflux pipeline of the reflux pipeline and esterification tower that are esterified reflux ratio distributor connects；It is described poly-
The overhead reflux pipeline of the top oil phase extraction pipeline and esterification tower of tying phase-splitter connects, and coalesces the bottom aqueous phase of phase-splitter
Extraction pipeline is connected with the top of aqueous phase receiving tank.
As preferable technical scheme, the oil phase receiving tank, aqueous phase receiving tank are connected with emptying house steward, oil phase receiving tank
Bottom be connected with the feeding line of reaction kettle of the esterification entrainer, the middle and lower part of the bottom of aqueous phase receiving tank and extractive distillation column connects
Connect, the middle and upper part connection of extractant feed pipeline and extractive distillation column.
As preferable technical scheme, the bottom of the extractive distillation column is connected with extraction tower reboiler bottom, extraction tower
The top of reboiler and the bottom of extractive distillation column connect, and the top of extractive distillation column is connected extraction tower with extraction overhead condenser
Top condenser overhead is connected with extraction tower top trap, is connected at the top of extraction tower top trap with blow-down pipe, extraction tower top is cold
Condenser bottom is connected with extracting the top of return tank of top of the tower, extracts bottom and the extractive distillation column overhead reflux pipe of return tank of top of the tower
Line, the connection of reaction kettle of the esterification entrainer feeding line, the bottom of extractive distillation column is connected with extractant recycle section.
The present invention also provides a kind of device using rectifying production cyanoacetate compound, malonate compound and carries out essence
Evaporate production cyanoacetate compound, the technique of malonate compound.
The technical scheme is that：
The technique that rectifying is carried out using batch reactive distillation production cyanoacetate compound, malonate compound device, including
Step：
1) quantitative cyanoacetic acid alcoholic solution, entrainer, alcohol solution are added into reaction kettle of the esterification, then determines catalyst
Amount is added in reaction kettle of the esterification；
2) in the presence of catalyst, with alcohols esterification generation water occurs in reaction kettle of the esterification for raw material cyanoacetic acid,
Water enters esterification splitter with entrainer in the form of azeotropic, then rises to esterification tower tower top, overhead vapours is through esterification
First-stage condenser, esterification secondary condenser condensation, then through being esterified reflux ratio distributor control, all extraction to coalescence phase-splitter,
After coalescing phase-splitter split-phase, aqueous phase is collected in aqueous phase receiving tank, and oil phase high-position backflow to esterification tower tower top is used as back
Stream, continuously takes water caused by esterification out of；
3) esterification is completed, and stops adopting material to coalescence phase-splitter, that opens oil phase receiving tank adopts material mouth, by being esterified back
Stream controls rate of withdrawal than distributor, and the alcohols remained in reaction kettle of the esterification, entrainer are all produced, can be according to actual feelings
Condition, system is vacuumized, the most light component in reactor is produced；
4) the thick ester in reaction kettle of the esterification is delivered to after thick ester cooler cools and produced；
5) the entrainer alcoholic solution in oil phase receiving tank is back to reaction kettle of the esterification by oil phase transfering material pump and then carried out down
Batch of esterification；
6) water conveying in aqueous phase receiving tank to the middle and lower part of extractive distillation column is fed, and falls into the liquid phase of tower reactor through extraction
The heating vaporization of tower reboiler, gas phase is after extractant extracts, and through extracting overhead condenser, extraction tower top trap condenses latter portion
Be allocated as being back to extracting rectifying column overhead for backflow, realize the Mass and heat transfer of tower top, another part be delivered to reaction kettle of the esterification after
The continuous esterification for carrying out next kettle；
7) extractant feed is delivered to extractant recovery tower and extracted in the middle and upper part of extraction tower, the material of extraction tower tower reactor
After taking agent to reclaim, extraction tower recycling is back to.
As preferable technical scheme, described reaction kettle of the esterification uses the technique of batch reactive distillation, using entrainer,
Take water caused by esterification out of, esterification is carried out to positive reaction direction, improve reaction speed and efficiency.
As preferable technical scheme, the addition of alcohol solution is more than esterification aequum in described step 1),
Because esterification belongs to reversible reaction, generally reaction is carried out not thorough, according to reaction equilibrium theory, to improve ester
Yield with a kind of method isolated composition from product or make reactant one of which composition excessive, it is necessary to make reaction to positive direction
Carry out.And the comparision of production of cyanoacetic acid it is cumbersome, it is necessary to input amount it is bigger, so in order to ensure that reaction can be to just
The Direction of Reaction is carried out, it is necessary to add excessive alcohol solution, is greatly improved the conversion ratio of cyanoacetic acid, is reduced the damage of cyanoacetic acid
Lose, increase the yield of ester.
As preferable technical scheme, the esterification is that normal pressure is carried out when being esterified and carrying out, after esterification is complete
Need, by the remaining entrainer in reactor, alcohols removing, to ensure the temperature of reactor, vacuumizing to be carried out to system.
Cyanoacetic acid charging mixes charging, the mainly cyanoacetic acid used in esterification with alcohol solution in the present invention
In it is not aqueous, and cyanoacetic acid is solid at normal temperatures, and to prevent cyanoacetic acid from blocking pipeline, a certain amount of nothing is added into cyanoacetic acid
Water alcohol solution is dissolved, and reaction kettle of the esterification is entered in the form of cyanoacetic acid alcoholic solution.Reaction kettle of the esterification is provided with agitating device, addition
Agitating device can be well mixed the material in reactor, increase the reaction speed and reaction efficiency of esterification, improve yield.
Connection esterification splitter at the top of reaction kettle of the esterification, is taken out of the steam in reactor by splitter in the present invention
Acidic catalyst is separated, and reduces corrosion of the steam to rectifying column.Reflux ratio distributor connection coalescence phase-splitter is esterified, is passed through
Oil phase and aqueous phase are completely separated by coalescence phase-splitter, reduce the input amount of entrainer, reduce energy consumption.It is esterified workshop section's connection extraction
Workshop section is taken, recovery is esterified the entrainer alcohol solution in workshop section's aqueous phase, extraction workshop section connection extractant recycle section, recovery extraction
Extractant in aqueous extractant waste liquid caused by workshop section.The process of the esterification reaction rectification of the present invention improves thick ester
Yield, energy resource consumption is reduced, while the entrainer of addition, extractant is reclaimed reuse, reduce entrainer, extraction
Take the consumption of agent.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, without having to pay creative labor, may be used also
To obtain other accompanying drawings according to these accompanying drawings.
Fig. 1 is the process schematic diagram of invention.
In figure：1- catalyst, 2- cyanoacetic acids ethanol solution, 3- absolute ethyl alcohols, 4- entrainers, 5- reaction kettle of the esterification, 6- esters
Change splitter, 7- esterification towers, 8- are esterified first-stage condenser, 9- is esterified secondary condenser, 10- is esterified reflux ratio distributor,
11- coalescences phase-splitter, 12- aqueous phases receiving tank, 13- oil phases receiving tank, 14- esterifying kettles discharging pump, the thick ester coolers of 15-, 16- oil
Phase transfering material pump, 17- aqueous phases discharging pump, 18- extractive distillation columns, 19- extraction towers reboiler, 20- extractions overhead condenser, 21- extractions
Take tower top trap, 22- extractions return tank of top of the tower, 23- extraction tower tops reflux pump, 24- extraction tower reactor extraction pumps.
Embodiment
As shown in figure 1, a kind of intermittent esterification reaction rectification technique productions cyanoacetate compound, the technique of malonate compound
The cyanoacetate compound of method and device, the present apparatus and technique productions can be ethyl cyanoacetate, methyl cyanoacetate, malonate
Compound can be dimethyl malenate, diethyl malonate.The device includes reaction kettle of the esterification 5, esterification splitter 6, esterification essence
Evaporate tower 7, esterification reflux ratio distributor 10, coalescence phase-splitter 11, aqueous phase receiving tank 12, oil phase receiving tank 13；Reaction kettle of the esterification 5 pushes up
Portion's connection esterification splitter 6, top connection esterification tower 7 bottom of esterification splitter 6, the connection esterification of the bottom of esterification tower 7
The top of reactor 5, the top of esterification tower 7 connect esterification reflux ratio distributor 10, esterification reflux ratio distribution through esterification condensator
Device 10 connects the top of esterification tower 7, and the esterification connection coalescence phase-splitter 11 of reflux ratio distributor 10, coalescence phase-splitter 11 top connects
The top of esterification tower 7 is connect, the connection coalescence phase-splitter 11 of aqueous phase receiving tank 12 bottom, aqueous phase receiving tank 12 is through aqueous phase discharging pump 17
Subsequent processing is connected to, the connection esterification reflux ratio distributor 10 of oil phase receiving tank 13, the lower end of oil phase receiving tank 13 turns material through oil phase
Pump 16 is connected to the top of reaction kettle of the esterification 5.
In batch reactive distillation production cyanoacetate compound, one embodiment of malonate compound device, described device
Further comprise extractive distillation column 18, extraction overhead condenser 20, extraction return tank of top of the tower 22, the extractive distillation column 18 connects
The aqueous phase receiving tank 12, the extraction overhead condenser 20 connect the top of extractive distillation column 18, the extraction return tank of top of the tower
22 connection extraction overhead condensers 20, the top of extraction return tank of top of the tower 22 bottom connection reaction kettle of the esterification 5, extractive distillation column
18 tops.
In batch reactive distillation production cyanoacetate compound, one embodiment of malonate compound device, described ester
Change the top of reactor 5 to be connected with being esterified the bottom of splitter 6, be esterified the top of splitter 6 and connect with the middle and lower part of esterification tower 7
Connect, the bottom of esterification tower 7 is connected with the top of reaction kettle of the esterification 5.
In batch reactive distillation production cyanoacetate compound, one embodiment of malonate compound device, the esterification
Condenser includes esterification first-stage condenser 8 and esterification secondary condenser 9, top and the esterification first-stage condenser 8 of esterification tower 7
Connection, esterification first-stage condenser 8 are connected with esterification secondary condenser 9, top and the blow-down pipe of esterification secondary condenser 9 or are taken out
Vacuum pipeline is connected, and the bottom for being esterified secondary condenser 9 is connected with being esterified the top of reflux ratio distributor 10；The esterification backflow
Extraction pipeline than distributor 10 is connected with the coalescence bottom feed line of phase-splitter 11 and the top of oil phase receiving tank 13, esterification backflow
It is connected than the reflux pipeline of distributor 10 with the overhead reflux pipeline of esterification tower 7；The top oil of the coalescence phase-splitter 11
Mutually extraction pipeline is connected with the overhead reflux pipeline of esterification tower 7, the bottom aqueous phase extraction pipeline and water of coalescence phase-splitter 11
The top connection of the closed cans that connects 12.
In batch reactive distillation production cyanoacetate compound, one embodiment of malonate compound device, the oil phase
Receiving tank 13, aqueous phase receiving tank 12 are connected with emptying house steward, and the coalescence phase-splitter 11 is through U-shaped curved top blow-down pipe and emptying
House steward is connected, and the bottom of oil phase receiving tank 13 is connected with the feeding line of oil phase transfering material pump 16, the discharge nozzle of oil phase transfering material pump 16
Line is connected with the feeding line of the entrainer of reaction kettle of the esterification 5, the bottom of aqueous phase receiving tank 12 and the feeding line of aqueous phase discharging pump
Connection, the discharging pipeline of aqueous phase discharging pump are connected with the middle and lower part of extractive distillation column 18, extractant feed pipeline and extracting rectifying
The middle and upper part connection of tower 18.
In batch reactive distillation production cyanoacetate compound, one embodiment of malonate compound device, the extraction
The bottom of rectifying column 18 is connected with the bottom of extraction tower reboiler 19, under the top of extraction tower reboiler 19 and extractive distillation column 18
Portion connects, and the top of extractive distillation column 18 is connected the top of extraction overhead condenser 20 and extraction tower top with extraction overhead condenser 20
Trap 21 is connected, and the top of extraction tower top trap 21 is connected with blow-down pipe, extracts the bottom of overhead condenser 20 and extraction tower
The top connection of return tank 22 is pushed up, the bottom for extracting return tank of top of the tower 22 is connected with extracting the feeding line of tower top reflux pump 23,
Extract the outlet line and the overhead reflux pipeline of extractive distillation column 18, the entrainer feed pipe of reaction kettle of the esterification 5 of tower top reflux pump 23
Line is connected, and the bottom of extractive distillation column 18 is connected with the extraction tower reactor extraction import of pump 24, extraction tower reactor extraction pump 24 and extractant
Recycle section connects.
Quantitative cyanoacetic acid ethanol solution 2, the hexamethylene of entrainer 4, absolute ethyl alcohol 3 are added into reaction kettle of the esterification 5, then
Catalyst 1 is added in reaction kettle of the esterification 5.The stirring of reaction kettle of the esterification is opened, while is passed through into reaction kettle of the esterification chuck
Steam, when reaction kettle of the esterification is raised to reaction temperature, esterification generation water, water, hexamethylene, second takes place with ethanol in cyanoacetic acid
Alcohol enters esterification splitter 6 in the form of ternary azeotropic, then rises to the tower top of esterification tower 7, overhead vapours is through esterification one
Level condenser 8, esterification secondary condenser 9 are condensed, then controlled through being esterified reflux ratio distributor 10, all extraction to coalescence phase-splitter
11, after coalescing phase-splitter split-phase, aqueous phase is collected in aqueous phase receiving tank 12, and oil phase high-position backflow to esterification tower tower top is made
For backflow, continuously water caused by esterification is taken out of.After the completion of esterification, stop adopting material to coalescence phase-splitter,
That opens oil phase receiving tank 13 adopts material mouth, and rate of withdrawal is controlled by being esterified reflux ratio distributor 10, will be residual in reaction kettle of the esterification
Ethanol, the hexamethylene stayed all produces, and in order to control the temperature in reactor, reduces the progress of side reaction, system is vacuumized,
Most light component in reactor is produced.Thick ester in reaction kettle of the esterification is delivered to slightly by esterifying kettle discharging pump 14
Ester cooler 15 produces after cooling.Hexamethylene, ethanol solution in oil phase receiving tank 13 are returned by oil phase transfering material pump 16
The esterification of next group is then carried out to reaction kettle of the esterification.And the aqueous phase in aqueous phase receiving tank is conveyed by aqueous phase discharging pump 17
Fed to the middle and lower part of extractive distillation column 18, the liquid phase for falling into tower reactor heats vaporization through extraction tower reboiler 19, and steam is through extraction
After agent extraction, then through extracting overhead condenser 20, the condensation collection of extraction tower top trap 21 in return tank of top of the tower 22 is extracted, extraction
The material in return tank of top of the tower 22 is taken to be conveyed through extracting tower top reflux pump 23, a part is back to extractive distillation column 18 as backflow
Tower top, realize the Mass and heat transfer of tower top.Another part is delivered to the esterification that reaction kettle of the esterification continues next kettle.Extraction
Agent is fed in the middle and upper part of extraction tower.The material of extraction tower tower reactor produces to extractant recovery tower through extracting tower reactor extraction pump 24
After the recovery of row extractant, extraction tower recycling is back to.The top of extraction tower top trap 21 is provided with drain, for prevent not by
The gas of condensation releases pollution environment, is vented after emptying end gas can be absorbed with fluid-tight using fluid-tight absorption plant.
Concrete example is analyzed, and the device is applied to most esterification：
1mol cyanoacetic acids react generation nearly 1mol water, the water of generation with excessive ethanol in the presence of the concentrated sulfuric acid and led to
The extraction of entrainer hexamethylene azeotropic distillation is crossed, the oil phase that tower top azeotropic is taken out of is back to tower top, takes the water of generation out of repeatedly, take out of
Aqueous phase be recovered to water-free alkanol by extracting rectifying and return to then carry out esterification, and generate nearly 1mol cyanogen
Ethyl acetate produces with the complete cyanoacetic acid of unreacted, the catalyst concentrated sulfuric acid from tower reactor.
1mol monoxones react generation nearly 1mol water, the water of generation with excessive ethanol in the presence of the concentrated sulfuric acid and led to
The extraction of entrainer hexamethylene azeotropic distillation is crossed, the oil phase that tower top azeotropic is taken out of is back to tower top, takes the water of generation out of repeatedly, take out of
Aqueous phase be recovered to water-free alkanol by extracting rectifying and return to then carry out esterification, and generate nearly 1mol chlorine
Ethyl acetate produces with the complete monoxone of unreacted, the catalyst concentrated sulfuric acid from tower reactor.
1mol butyric acid reacts generation nearly 1mol water, the water of generation with excessive ethanol in the presence of the concentrated sulfuric acid and passed through
Entrainer hexamethylene azeotropic distillation produces, and the oil phase that tower top azeotropic is taken out of is back to tower top, takes the water of generation out of repeatedly, take out of
Aqueous phase is recovered to water-free alkanol by extracting rectifying and returns to then carry out esterification, and generates nearly 1mol butyric acid
Ethyl ester produces with the complete butyric acid of unreacted, the catalyst concentrated sulfuric acid from tower reactor.
General principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the simply explanation described in above-described embodiment and specification is originally
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (10)
1. batch reactive distillation production cyanoacetate compound, malonate compound device, it is characterised in that：Described device includes ester
Change reactor, esterification splitter, esterification tower, esterification reflux ratio distributor, coalescence phase-splitter, aqueous phase receiving tank, oil phase to connect
Closed cans；Connection esterification splitter at the top of reaction kettle of the esterification, esterification splitter top connection esterification tower bottom, esterification tower
Bottom connection reaction kettle of the esterification top, esterification tower top connect esterification reflux ratio distributor through esterification condensator, are esterified back
Stream is than distributor connection esterification tower top, and esterification reflux ratio distributor connection coalescence phase-splitter, coalescence phase-splitter top connects
Esterification tower top, aqueous phase receiving tank connection coalescence phase-splitter bottom are connect, the connection of oil phase receiving tank is esterified reflux ratio distributor,
Oil phase receiving tank lower end is connected at the top of reaction kettle of the esterification.
2. batch reactive distillation production cyanoacetate compound as claimed in claim 1, malonate compound device, its feature exist
In：Described device further comprises extractive distillation column, extraction overhead condenser, extraction return tank of top of the tower, the extractive distillation column
The aqueous phase receiving tank, the extraction overhead condenser connection extracting rectifying top of tower are connected, the extraction return tank of top of the tower connects
Connect extraction overhead condenser, the extraction return tank of top of the tower bottom connection reaction kettle of the esterification top, extractive distillation column top.
3. batch reactive distillation production cyanoacetate compound as claimed in claim 1, malonate compound device, its feature exist
In：It is connected, is esterified in the top and esterification tower of splitter with being esterified the bottom of splitter at the top of the reaction kettle of the esterification
Bottom connects, and the bottom of esterification tower and the top of reaction kettle of the esterification connect.
4. batch reactive distillation production cyanoacetate compound as claimed in claim 1, malonate compound device, its feature exist
In：The esterification condensator includes esterification first-stage condenser and esterification secondary condenser, top and the esterification one of esterification tower
Level condenser connection, esterification first-stage condenser are connected with esterification secondary condenser, are esterified top and the blow-down pipe of secondary condenser
Line or vacuum lines connection, the bottom for being esterified secondary condenser are connected with being esterified the top of reflux ratio distributor；The esterification
The extraction pipeline of reflux ratio distributor is esterified reflux ratio with being connected at the top of coalescence phase-splitter bottom feed line and oil phase receiving tank
The reflux pipeline of distributor and the overhead reflux pipeline of esterification tower connect；The top oil phase extraction pipe of the coalescence phase-splitter
The overhead reflux pipeline of line and esterification tower connects, and coalesces bottom aqueous phase extraction pipeline and the top of aqueous phase receiving tank of phase-splitter
Portion connects.
5. batch reactive distillation production cyanoacetate compound as claimed in claim 1, malonate compound device, its feature exist
In：The oil phase receiving tank, aqueous phase receiving tank are connected with emptying house steward, bottom and the reaction kettle of the esterification entrainer of oil phase receiving tank
Feeding line connection, the middle and lower part of the bottom of aqueous phase receiving tank and extractive distillation column connects, extractant feed pipeline and extraction
The middle and upper part connection of rectifying column.
6. batch reactive distillation production cyanoacetate compound as claimed in claim 1, malonate compound device, its feature exist
In：The bottom of the extractive distillation column is connected with extraction tower reboiler bottom, the top of extraction tower reboiler and extractive distillation column
Bottom connection, the top of extractive distillation column be connected with extraction overhead condenser to be extracted tower top condenser overhead and is caught with extracting tower top
Storage connects, and is connected at the top of extraction tower top trap with blow-down pipe, extraction overhead condenser bottom and extraction return tank of top of the tower
Top connection, extract the bottom of return tank of top of the tower and fed with extractive distillation column overhead reflux pipeline, reaction kettle of the esterification entrainer
Pipeline is connected, and the bottom of extractive distillation column is connected with extractant recycle section.
7. utilize batch reactive distillation production cyanoacetate compound, malonate compound as described in any one of claim 1 to 6
The technique that device carries out rectifying, it is characterised in that the industry comprises the following steps：
1) quantitative cyanoacetic acid alcoholic solution, entrainer, alcohol solution are added into reaction kettle of the esterification, then quantifies catalyst
It is added in reaction kettle of the esterification；
2) in the presence of catalyst, esterification generation water occurs in reaction kettle of the esterification for raw material cyanoacetic acid and alcohols, water and
Entrainer enters esterification splitter in the form of azeotropic, then rises to esterification tower tower top, overhead vapours is through being esterified one-level
Condenser, esterification secondary condenser condensation, then through being esterified reflux ratio distributor control, all extraction is to coalescence phase-splitter, through poly-
After tying phase-splitter split-phase, aqueous phase is collected in aqueous phase receiving tank, and oil phase high-position backflow to esterification tower tower top is as flowing back, even
It is continuous constantly to take water caused by esterification out of；
3) esterification is completed, and stops adopting material to coalescence phase-splitter, that opens oil phase receiving tank adopts material mouth, by being esterified reflux ratio
Distributor control rate of withdrawal, by the alcohols remained in reaction kettle of the esterification, entrainer all produce, can according to actual conditions,
System is vacuumized, the most light component in reactor is produced；
4) the thick ester in reaction kettle of the esterification is delivered to after thick ester cooler cools and produced；
5) the entrainer alcoholic solution in oil phase receiving tank is back to reaction kettle of the esterification by oil phase transfering material pump and then carries out next group
Esterification；
6) water conveying in aqueous phase receiving tank to the middle and lower part of extractive distillation column is fed, and falls into the liquid phase of tower reactor through extraction tower again
Device heating vaporization is boiled, gas phase is after extractant extracts, and through extracting overhead condenser, extraction tower top trap condensation rear portion is made
Extracting rectifying column overhead is back to for backflow, the liquid of backflow carries out heat transfer and mass transfer with the gas risen, formed
Stable thermograde and concentration gradient, another part are delivered to the esterification that reaction kettle of the esterification continues next kettle；
7) extractant feed is delivered to extractant recovery tower and carries out extractant in the middle and upper part of extraction tower, the material of extraction tower tower reactor
After recovery, extraction tower recycling is back to.
8. batch reactive distillation production technology as claimed in claim 7, it is characterised in that：Between described reaction kettle of the esterification uses
Have a rest the technique of reactive distillation, using entrainer, take water caused by esterification out of, esterification is carried out to positive reaction direction.
9. batch reactive distillation life technique as claimed in claim 7, it is characterised in that：Alcohol solution in described step 1)
Addition is more than esterification aequum, and the catalyst used in described esterification is acidic catalyst.
10. batch reactive distillation production technology as claimed in claim 7, it is characterised in that：The esterification be esterified into
It is that normal pressure is carried out during row.
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| CN201711032634.5A CN107827779B (en) | 2017-10-30 | 2017-10-30 | Device for producing cyanoacetic acid ester and malonic acid ester by batch reaction rectification and production process thereof |
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