CN104072373A - Preparation method of diethyl phthalate (DEP) - Google Patents
Preparation method of diethyl phthalate (DEP) Download PDFInfo
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- CN104072373A CN104072373A CN201310109697.1A CN201310109697A CN104072373A CN 104072373 A CN104072373 A CN 104072373A CN 201310109697 A CN201310109697 A CN 201310109697A CN 104072373 A CN104072373 A CN 104072373A
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- 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
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Abstract
The invention discloses a preparation method of diethyl phthalate (DEP). The preparation method comprises the following steps: adding the raw materials including phthalic anhydride and superfluous ethanol to a reaction kettle, adding concentrated sulfuric acid as a catalyst, controlling the temperature in the reaction kettle to be 0-150 DEG C, reacting for 16-20 hours, neutralizing the catalyst and unreacted phthalic anhydride with an alkaline solution after the reaction is completed, standing for layering and then carrying out washing with clear water for several times. After alcohol-containing wastewater is collected, alcohols are recovered with a recovery tower and are reused. A lower ester layer after layering is heated to recover alcohols at reduced pressure (ethanol is recovered by using a supergravity bed and is reused). After activated carbon is added for decoloration, the finished product of DEP is obtained through filter pressing by adopting a plate-and-frame filter press. The preparation method has the beneficial effects that the superfluous alcohol serves as a water-carrying agent, so that the esterification reaction is gradually carried through to the end, the technological process is simplified and the product quality is good; relative to a process of distillation in a rectifying tower, the preparation method has the advantages that the supergravity bed is used to recover ethanol in the process, so that the energy consumption is effectively reduced and the process has better environmental significance.
Description
Technical field
The present invention relates to organic compound preparation method field, specifically relate to a kind of preparation method of diethyl phthalate.
Background technology
Diethyl phthalate is that one has very strong solvent softening agent to various kinds of resin, and the softening agent, rubber, the Vinylite that are usually used in celluosic resin mix, and have good film-forming properties, tackiness and water-repellancy.At present, on market, the usage quantity of diethyl phthalate class softening agent is very large, but in process of production, the production method that traditional industrial production adopts, technique more complicated, reacts not thorough, has waste starting material, the shortcoming that production cost is high.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of diethyl phthalate is provided, to simplify technique, economize in raw materials, strengthen environmental protection, make the purity of product disposablely to reach requirement becomes possibility simultaneously.
For achieving the above object, the present invention is achieved through the following technical solutions:
A preparation method for diethyl phthalate, comprises the following steps:
(1), esterification step
In reactor, first drop into the ethanol of getting ready, the machine that then blows in is thrown phthalic anhydride, opens stirring simultaneously, in molfraction, and ethanol: phthalic anhydride=1.5: 1; Add the vitriol oil, its consumption by weight percentage, is 0.2%～1% of feed ethanol consumption, and the present invention is for esterification is carried through to the end gradually, therefore adopt excessive alcohol as band aqua; Stir afterwards, reactor temperature is controlled at 0～150 DEG C, reacts about 16-20 hour;
(2) in and operation
In reactor, add alkali lye, its concentration counts 4%～6% with massfraction, and its consumption by weight percentage, is 2%～4% of the intoxicated consumption of benzene feedstock; Now temperature is controlled at 60～90 DEG C, and stirring velocity is controlled at per minute 50～70 and turns, and neutralization finishes time control relieving haperacidity value=0.05mgKOH/g, and after neutralization, washing, underpressure distillation, obtains diethyl phthalate crude product;
(3), dealcoholysis operation
Dealcoholysis under vacuum, requires system vacuum to be greater than 620mmHg post, and temperature is controlled at 80～140 DEG C, and decompression dealcoholysis, to without till shunting, adds gac, and its consumption by weight percentage, is 0.2%～1% of feed ethanol and the intoxicated sum of benzene; Press filtration, obtains the qualified finished product of diethyl phthalate;
(4), ethanol recovery process
Waste water heating is constantly maintained to azeotropic state, make ethanol steam layering after condensation, upper strata ethanol is constantly isolated outside system, and in the continuous reflux tower of lower layer of water, continues distillation until distillate without ethanol, and described recovery adopts hypergravity bed to reclaim.
Wherein:
Above-mentioned method, the consumption of the reagent vitriol oil described in it, by weight percentage, is preferably 0.2%～0.5% of feed ethanol consumption.
Above-mentioned method, the consumption of gac described in it, by weight percentage, is preferably 0.3%～0.6% of feed ethanol and the intoxicated sum of benzene.
Above-mentioned method, described in it, in esterification operation, described reactor temperature is preferably controlled at 100～150 DEG C.
Above-mentioned method, in described in it and in operation, described alkali lye, its concentration is preferably 4.5～5.5% in massfraction, its consumption by weight percentage, be preferably 3% of the intoxicated consumption of benzene feedstock, described now temperature is preferably controlled at 70～75 DEG C, and described stirring velocity is preferably controlled at per minute 60 and turns.
The present invention has following significant progress and useful effect:
The present invention as band aqua, carries through to the end esterification with excessive alcohol gradually, has simplified technological process, and good product quality.With respect to the technique of rectifying tower distillation, this technique is used hypergravity bed to reclaim ethanol, effectively reduces energy consumption, has good environment protection significance; Make the purity of product disposablely to reach requirement simultaneously and become possibility.
Chemical reaction process of the present invention is as follows:
Esterification, point two steps are carried out
(1) generation of monoesters: during what phthalic anhydride was very fast in the time of 115 DEG C be dissolved in ethanol and the formation mono-ethyl phthalate that reacts to each other.The generation of (it is irreversible that this reaction does not need catalyzer to carry out smoothly and to react) (2) dibasic acid esters: monoesters, under the effect of catalyst sulfuric acid, generates dibasic acid esters and water with ethanol synthesis at 145～150 DEG C.This step reaction is reversible reaction, and carries out very slow (equilibrium constant K p=2～4).When the monoesters of equivalent and alcohol molecular balance, dibasic acid esters productive rate is 66%, must make alcohol excessive for improving dibasic acid esters productive rate, and the water generating except dereaction as far as possible.
Brief description of the drawings
Fig. 1 is the process flow sheet of a kind of diethyl phthalate of preparation.
Embodiment
In order to further illustrate technical scheme of the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these are described is in order to further illustrate the features and advantages of the present invention, instead of limiting to the claimed invention.
The ethanol that the present embodiment is used and the purity of phthalic anhydride are all=99%.
A preparation method for diethyl phthalate, comprises the following steps:
One, esterification step
1, proportioning raw materials
Phthalic anhydride ethanol sulfuric acid activated carbon reclaims alcohol
a、1600kg 2400kg 9kg 5kg /
b、1600kg 1700kg 9kg 5kg 875kg
2, get the raw materials ready, monitoring device, starts
A, the ethanol that first input is got ready, the machine that then blows in is thrown phthalic anhydride, opens stirring simultaneously, then throws gac, and sulfuric acid, finally builds hand hole plate.
B, temperature reaction: first open the water coolant of condenser, open water knockout blow-off valve, to get rid of at any time non-condensable gases in system.Then open chuck, the logical steam of coil pipe admission valve slowly heats up, and first controls vapour at 2kg/cm2.In the time that liquid temperature rises to more than 110 DEG C, (heat up and approximately need 20 minutes) comes to life.In the situation that not rushing material, esterification is carried out under this boiling state, in 94 DEG C of left and right of gas phase temperature, ethanol-water azeotropic thing carries out condenser through esterification column, after quantizer layering, ethanol flows into esterification column top, carries out after mass exchange with the azeotrope of vaporization, at the bottom of tower bottom flow enters esterifying kettle, again participate in esterification.Water after layering flows into water knockout, in the time that liquid temperature reaches 125 DEG C, open return valve, due to constantly dehydration in esterification reaction process, after certain hour, the water yield that steams thing reduces gradually, and liquidus temperature rises gradually, in the time that liquid temperature reaches 145～150 DEG C, reacting balance, water outlet is very few, reacts and within four hours, starts to get one time every 30 minutes sample, titration esterifying liquid acidity.Below acidity reaches 2mgKOH/g time, react complete.Stop steam heating and close return valve, open chuck water coolant, in the time that liquid temperature is down to 80 DEG C of left and right, in notice, carry out dnockout with operation.
C, esterification key points for operation: heat up steadily, can not fill material.
Two, in and operation
1, batching: take about 48kg soda ash and add 1500L to join alkali groove, be then warmed up to 50～60 DEG C, now concentration of lye approximately 3～4%, surveys proportion in 1.03 left and right.
2, operation: alkali lye is squeezed into elevated dosing vessel by beating alkali pump, in and in still material to control 70 ± 2 DEG C (winter is high 2 DEG C) and then open stirring, open half-turn alkali lye valve simultaneously and add alkali neutralization, adding the alkali lye time is controlled at 20 minutes, after adding alkali, stir 10 minutes, stop stirring after static 45 minutes, put waste lye, sample by middle control simultaneously, control acid number=0.05mgKOH/g.
Neutralization reaction control condition:
(1) concentration of lye and alkali lye consumption
Alkali concn is advisable with 4% (1.03,25 DEG C of proportions) left and right, and alkali consumption thinks that 3% of phthalic anhydride amount is advisable.
(2) neutral temperature
Theoretically, acid, alkali neutralization and temperature of reaction relation is little, but because temperature is lower, viscosity is large, adverse effect, and also not stratified, cause emulsification, be advisable for 70～75 DEG C.
(3) stir
Stirring velocity is 60 revs/min.
(4) esterification terminal acidity
If esterification terminal exceedes 2mgKOH/g, illustrate that esterification carries out not exclusively, have the existence of monoesters, now neutralization, not only need to increase the consumption of alkali, and monoesters is water-soluble with alkaline reaction generation sodium salt, and the water of layering is dropped down.
(5) concentration of ester
If the difference of specific gravity of the concentration of ester large (illustrating containing alcohol few) thick ester and alkali lye is little, very easily there is emulsion, cause layering difficulty, under normal circumstances, the proportion of thick ester should be in 0.95 left and right
Three, dealcoholysis operation
1, the preparation work before driving, dry dealcoholize column, open chuck and coil pipe steam valve open system vacuum, the water coolant of open cold condenser, put the acidity alkali lye of being with in clean neutral ester storage tank, when the first preheater temperature reaches 80 DEG C, when the second preheater temperature reaches 120 DEG C, in tower 135 DEG C, at the bottom of tower, get final product charging 140 DEG C time.Require system vacuum to be greater than 620mmHg post.
2, key points for operation:
A, reach 80 DEG C when the first preheater temperature, the second preheater temperature reaches 120 DEG C, tower top temperature reaches 135 DEG C, in tower, reach 135～140 DEG C, at the bottom of tower, 140～145 DEG C time, get final product charging, feed rate is controlled at 1200～1600L/hr, open live steam simultaneously, and be controlled at 450～500mmHg, in continuously feeding process, will pay special attention to water, electricity, vapour and tower reactor temperature.
B, tank switching in time when distilling thick ester tank and filling, first close the vacuum valve connecing on distillation ester tank, then open the vacuum valve on slack tank, after vacustat, open the material valve on slack tank, shut the former material valve on tank that is subject to, then by the emptying valve open completely distilling on thick ester tank, material is squeezed into press filtration basin.
C, stop, wash tower: before washing tower, material in tower should be put only, be closed discharge valve, add water and liquid caustic soda from preheater rinse mouth, tower be filled to (tank can be found out by decaptitating).Then the logical steam of chuck, Ta Neitong live steam, boils tower and within 2～3 hours, stops vapour and will wash tower and emit, then rinses to clean with tap water.
D, temporary stoppage, because cutting off the water, the reason such as power failure is while causing temporary stoppage, should close immediately feed valve and live steam, jacket steam valve, keeping system vacuum, wait recover normal after charging again.
E, dealcoholysis charging should keep continuously feeding as far as possible, and start-stop does not stop, in order to avoid affect quality product and consumption.
Four, three wastes processing
1. in waste water, reclaim ethanol operation:
Ethanol solubleness in water is 8% left and right, in waste lye, account for 4% left and right, utilize ethanol and water to form, 93 DEG C of azeotropic points, account for 57.5% at azeotrope composition ethanol, and water accounts for 42.5% time, so waste water heating is constantly maintained to azeotropic state, make ethanol steam layering after condensation, upper strata ethanol is constantly isolated outside system, and in the continuous reflux tower of lower layer of water, continues distillation until distillate without ethanol.
2. the recycling in middle layer:
In ester and rear all mixed and title middle layers of being difficult to layering of ester water that finds that there is in the time of point water, water is contained in middle layer, monoester sodium salt and ester, must not directly enter in ditch, should give independent collection, regularly focus on: in before processing, middle layer being sucked and in still, hold over night, point sub-cloud water liquid, whether sampling and measuring acid number reaches below 0.05mgKOH/g, as higherly in acid number should add soda ash, salt mixed solution neutralizes it, and give manipulation by neutralization operation requirement, after branch vibration layer, carry out dealcoholysis, press filtration, i.e. ester finished product.Regenerant in vacuum buffer tank, should leave that to do independent recycling for subsequent use concentratedly.
3. the recovery of residual ester in gac:
The breeze swapping out, still contain higher ester in sheet frame filter frame plate, the loss of ester will be increased if do not reclaimed, raw material consumption is increased, therefore carry out centrifuge dripping, recovery by drop into (once drop into breeze and be no more than 20kg) in the filter cloth in stainless steel whizzer containing ester breeze, each operation about approximately 2 hours, reclaims in the residual ester friendship of gained and process in post.
Claims (6)
1. a preparation method for diethyl phthalate, its spy levy in: described preparation method comprises the following steps:
(1), esterification step
In reactor, first drop into the ethanol of getting ready, the machine that then blows in is thrown phthalic anhydride, opens stirring simultaneously, in molfraction, and ethanol: phthalic anhydride=1.5: 1; Add the vitriol oil, its consumption by weight percentage, is 0.2%～1% of feed ethanol consumption; Stir afterwards, reactor temperature is controlled at 0～150 DEG C, reacts about 16-20 hour;
(2) in and operation
In reactor, add alkali lye, its concentration counts 4%～6% with massfraction, and its consumption by weight percentage, is 2%～4% of the intoxicated consumption of benzene feedstock; Now temperature is controlled at 60～90 DEG C, and stirring velocity is controlled at per minute 50～70 and turns, and neutralization finishes time control relieving haperacidity value=0.05mgKOH/g, and after neutralization, washing, underpressure distillation, obtains diethyl phthalate crude product;
(3), dealcoholysis operation
Dealcoholysis under vacuum, requires system vacuum to be greater than 620mmHg post, and temperature is controlled at 80～140 DEG C, and decompression dealcoholysis, to without till shunting, adds gac, and its consumption by weight percentage, is 0.2%～1% of feed ethanol and the intoxicated sum of benzene; Press filtration, obtains the qualified finished product of diethyl phthalate;
(4), ethanol recovery process
Waste water heating is constantly maintained to azeotropic state, make ethanol steam layering after condensation, upper strata ethanol is constantly isolated outside system, and in the continuous reflux tower of lower layer of water, continues distillation until distillate without ethanol, and described recovery adopts hypergravity bed to reclaim.
2. method according to claim 1, is characterized in that: the consumption of the described reagent vitriol oil by weight percentage, is 0.2%～0.5% of feed ethanol consumption.
3. method according to claim 1, is characterized in that: the consumption of described gac by weight percentage, is 0.3%～0.6% of feed ethanol and the intoxicated sum of benzene.
4. method according to claim 1, is characterized in that: described esterification operation, reactor temperature is controlled at 100～150 DEG C.
5. according to the arbitrary described method of claim 1～4, it is characterized in that: in described and operation, described alkali lye, its concentration counts 4.5～5.5% with massfraction, its consumption by weight percentage, for 3% of the intoxicated consumption of benzene feedstock, described now temperature is controlled at 70～75 DEG C, and described stirring velocity is controlled at per minute 60 and turns.
6. method according to claim 5, is characterized in that: described feed ethanol is excessive.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310109697.1A CN104072373A (en) | 2013-03-29 | 2013-03-29 | Preparation method of diethyl phthalate (DEP) |
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| CN201310109697.1A CN104072373A (en) | 2013-03-29 | 2013-03-29 | Preparation method of diethyl phthalate (DEP) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712811A (en) * | 2016-04-08 | 2016-06-29 | 于迎春 | Zero-emission efficient synthetic ester production device and technology |
| CN108997114A (en) * | 2018-08-06 | 2018-12-14 | 河北驭驰橡塑科技有限公司 | A kind of production technology of tributyl trimellitate |
-
2013
- 2013-03-29 CN CN201310109697.1A patent/CN104072373A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712811A (en) * | 2016-04-08 | 2016-06-29 | 于迎春 | Zero-emission efficient synthetic ester production device and technology |
| CN105712811B (en) * | 2016-04-08 | 2018-05-01 | 于丽 | A kind of zero-emission efficiently synthesizes ester process units and production technology |
| CN108997114A (en) * | 2018-08-06 | 2018-12-14 | 河北驭驰橡塑科技有限公司 | A kind of production technology of tributyl trimellitate |
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Application publication date: 20141001 |