CN104761452B - A kind of purification process of butyl acrylate coarse product - Google Patents
A kind of purification process of butyl acrylate coarse product Download PDFInfo
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- CN104761452B CN104761452B CN201510170921.7A CN201510170921A CN104761452B CN 104761452 B CN104761452 B CN 104761452B CN 201510170921 A CN201510170921 A CN 201510170921A CN 104761452 B CN104761452 B CN 104761452B
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- butyl acrylate
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention discloses a kind of purification process of butyl acrylate coarse product, extractant is made with water, butyl acrylate coarse product is subjected to continuous countercurrent extraction, raffinate organic phase containing butyl acrylate coarse product is sufficiently mixed carry out neutralization reaction with liquid caustic soda in static mixer, discharge the salt separated out, impurity, light component and heavy constituent are removed again, finally give the butyl acrylate of purity more than 99.6%.The purifying process of the present invention is simple, butyl acrylate purity is high, yield is up to more than 98.5%, compared with traditional handicraft, averagely produce the liquid caustic soda that one ton of butyl acrylate product saves 20%, influence of the washing link to purification system will be neutralized simultaneously and is reduced to minimum, and there is significant practicality and economic benefit, be easy to large-scale industrial production.
Description
Technical field
The invention belongs to butyl acrylate production field, and in particular to a kind of purification process of butyl acrylate coarse product.
Background technology
Principal monomer of the esters of acrylic acid as products such as polymer emulsion, adhesive, pressure sensitive adhesive, water-absorbing resins,
Favor is enjoyed in Chemical market.Butyl acrylate (BA) is most important kind in esters of acrylic acid, existing consecutive production work
In skill, direct esterification legal system butyl acrylate is international main production process, its technical process are at this stage：Raw material
Acrylic acid and n-butanol carry out esterification in two tandem reactors, using organic acid as catalyst, and take side to react
The method of side dehydration, so that reversible esterification equilibrium reaction is carried out to butyl ester generation direction as far as possible.The acrylic acid of reactor discharge
Butyl ester crude product enters extraction tower, scrubbing tower, removes catalyst, unnecessary acrylic acid in material, and alkali wash water reclaims into alcohol
Tower, reclaim n-butanol；Material sequentially enters alcohol topping tower, ester purifying column after washing, removes the n-butanol, water and heavy component of residual
Afterwards, butyl acrylate product is obtained.
Chinese patent CN102173990A discloses a kind of preparation method of butyl acrylate, and this method includes three steps
Suddenly：Esterification, neutralization reaction, rectification and purification, in neutralization reaction step directly by reactant of esterification mass concentration be 7~
8% sodium hydroxide lye catalyst neutralisation p-methyl benzenesulfonic acid, alkali lye dosage is adjusted, pH7.0 is neutralized to, after precipitation by aqueous phase
Separation, the good semi-finished product of neutralisation treatment are obtained, then semi-finished product input refining kettle is subjected to rectification and purification, it is 99.5% to obtain purity
Butyl acrylate.This method is directly all neutralized catalyst p-methyl benzenesulfonic acid with alkali lye, is not only wasted a large amount of organic acids and is urged
Agent, it is seted to add production cost, and a large amount of sodium hydroxide lyes of consuming from recycling, produce a large amount of waste water, no
Beneficial to environmental protection.
Chinese patent CN102344366A discloses a kind of two kinds of solvent side entry feed liquid-liquid extraction extraction butyl acrylate
Method, using polynary alcohol and water as extractant, by the butyl acrylate containing butanol, butyl ether, butoxy butyl acrylate and water
Material continuous countercurrent extraction in extraction tower, raffinate obtain the higher butyl acrylate of purity；Extraction phase separates through rectifying, point
Recycled respectively from rear polyalcohol and water.The weak point of this method essentially consists in：Select polynary alcohol and water to make extractant, extract
The isolated polyalcohol of phase rectifying is taken, technique is cumbersome, and extraction process uses a large amount of organic solvents, expensive, is not easy to big
Technical scale metaplasia is produced.
The content of the invention
It is an object of the invention to provide a kind of purification process of butyl acrylate coarse product, avoid making using organic solvent
Extractant, reduce the dosage of liquid caustic soda, one time yield reaches more than 98.5%, obtained butyl acrylate purity up to 99.6% with
On, purifying process of the invention is simple, has significant practicality and economic benefit, and obtained product purity is high, is easy to advise greatly
Mould industrialized production.
In order to achieve the above object, technical scheme is as follows：
A kind of purification process of butyl acrylate coarse product, comprises the following steps：
1) extract：Extractant is made with water, the butyl acrylate coarse product that esterification is obtained carries out continuous with extractant
Counter-current extraction；Organic acid catalyst in butyl acrylate coarse product enters aqueous phase, and butyl acrylate and accessory substance enter raffinate
Organic phase, separation, raffinate organic phase is continuously into static mixer；
2) mix and neutralize：Liquid caustic soda is continuously sufficiently mixed, in progress continuously into static mixer with raffinate organic phase
And reaction, the organic acid substance in accessory substance is removed, obtains reactant mixture material, pH is 9~12；
3) wash, reclaim：Reactant mixture material in step 2) enters scrubbing tower, is washed, in reactant mixture material
Butyl acrylate and remove the accessory substance of organic acid substance and flowed out from scrubbing tower top, salt caused by neutralization reaction and be dissolved in
The impurity of water flows out from scrubbing tower bottom of towe, reclaims the organic principle in tower bottom liquid；
4) separate, purify：The accessory substance of butyl acrylate and removing organic acid substance removes therein light by distillation
Component and heavy constituent, obtain butyl acrylate product.
Preferably, the extractant described in step 1) is desalted water.
Further, in addition to recycling step 1) organic acid catalyst in aqueous phase, described organic acid catalyst is first sulphur
At least one of acid, p-methyl benzenesulfonic acid and benzene sulfonic acid.
Preferably, the alkali in the liquid caustic soda described in step 2) is sodium hydroxide or potassium hydroxide, mass fraction is 10~
50%.
Further, the addition of liquid caustic soda and the mass ratio of butyl acrylate coarse product are：0.008~0.018:1.
Also, in the step 2), after carrying out neutralization reaction, the salt of periodically discharge precipitation.
Preferably, by being evaporated under reduced pressure the light component and heavy constituent that remove in accessory substance in step 4).What the present invention obtained
Butyl acrylate purity >=99.6%.
In the present invention, butyl acrylate coarse product makes organic acid catalyst enter aqueous phase, it is reclaimed by extraction
Utilize, effectively saved catalyst so as to reduce production cost；Before again underway and reaction, make raffinate organic phase and liquid
Alkali is continuously mixed, and the acid in raffinate organic phase and liquid caustic soda is sufficiently contacted, and soda acid reacts in mixing, removes
Organic acid substance in accessory substance, be advantageous to improve neutralization reaction efficiency, react fully progress, avoid in existing process because
Undercompounding and the phenomenon for increasing liquid caustic soda dosage, complete due to reacting, the dosage of liquid caustic soda substantially reduces, and also greatly reduces miscellaneous
The generation of matter, so as to shorten washing link time, the influence for neutralizing washing link to purification system is reduced, is advantageous to obtain
The butyl acrylate product of high-purity.
The beneficial effects of the invention are as follows：
1. in the purification process of the present invention, during extraction, avoiding using substantial amounts of organic solvent, but extractant is made with water,
Organic acid catalyst is entered aqueous phase, it can be reclaimed, recycled into esterifier, effectively saved catalysis
Agent and the use of organic solvent, reduce production cost.
Before 2. the present invention carries out neutralization reaction, raffinate organic phase is entered static mixer, on the one hand make raffinate organic phase
Carried out with liquid caustic soda in static mixer it is continuous, fast and efficiently mix, it will be apparent that reduce the dosage of liquid caustic soda, reduce production
Cost；On the other hand, by the sewage draining exit of static mixer device, it can periodically switch blender and clean out the salt of fouling,
It ensure that blender is efficiently run for a long time, save manpower and materials.
3. reduce the dosage of liquid caustic soda because the present invention neutralizes link, so as to reduce the generation of neutralized reaction product salt, again
The salt of periodically discharge fouling, the influence for neutralizing washing link to purification system is reduced, improves product purity；The present invention
Neutralization washing link time is shortened, production efficiency is improved, reduces production cost, while reduce the generation of waste water and drop
The low pollution to environment.
4. the present invention is simple and easy, process conditions are gentle and attended operation is simple, safe and reliable to operation, are adapted to extensive work
Industry metaplasia is produced.
Brief description of the drawings
Fig. 1 is the process chart of the embodiment of the present invention.
Embodiment
Technical scheme is described in further detail below in conjunction with specific embodiments and the drawings, but is not limited to this hair
It is bright.
A kind of purification process of 1 butyl acrylate coarse product of embodiment, its process chart is as shown in figure 1, specifically include
Following steps：
1) extract
Extractant is made with desalted water, butyl acrylate coarse product is entered into extraction tower C1 with average 10000kg/h flow
And continuous countercurrent extraction is carried out in extraction tower C1；Organic acid catalyst in butyl acrylate coarse product enters aqueous phase, with taking off
Salt solution counter current contacting, the organic acid catalyst in aqueous phase is reclaimed, the organic acid catalyst of recovery is from extraction tower C1 tower reactors
Send reactor back to；Butyl acrylate and accessory substance enter raffinate organic phase, are flowed out from extraction tower C1 tower tops, continuously enter static mixed
Clutch M1；
Accessory substance in described butyl acrylate coarse product includes：Organic acid catalyst, the acrylic acid not reacted completely,
Light component and heavy constituent, described light component include：N-butanol, butyl ether, butyl acetate, isobutyl propionate, isobutyl acrylate；
Heavy constituent includes：Benzaldehyde, furfural, isoamyl acrylate and butoxy butyl propionate.
2) mix and neutralize
30wt.% sodium hydroxide solution is continuously added in static mixer M1 with average 130kg/h flow, with extraction
Remaining organic phase is sufficiently mixed, and is carried out neutralization reaction, is periodically discharged the sodium salt of fouling, obtain reactant mixture material, pH value 10；
3) wash, reclaim
Reactant mixture material in step 2) enters scrubbing tower C2, washes away the impurity in mixture；In reactant mixture material
Butyl acrylate and accessory substance flow to submerged soil D1 from scrubbing tower C2 tower tops；Sodium salt caused by neutralization reaction and it is dissolved in the miscellaneous of water
Matter is flowed out as tower bottom liquid from scrubbing tower C2 bottom of towe, and alcohol therein and ester are reclaimed into alcohol recovery tower C3, and waste water is from alcohol recovery tower
C3 bottom of towe is discharged through pump P30, and the product of recovery enters submerged soil D2, and is sent into dehydrating tower by pump P31；
4) separate, purify
Scrubbing tower C2 tower tops are flow to submerged soil D1 butyl acrylate and accessory substance material is sequentially sent to follow-up alcohol and pulled out
Head tower C4, ester purifying column C5, light component and heavy constituent are removed respectively by being evaporated under reduced pressure, wherein, alcohol topping tower C4 passes through steam
It is 5KPaA that jet pump J1, which controls operating pressure, and it is 4KPaA that ester purifying column C5 controls operating pressure by steam jet pump J2.
Specifically, the material in submerged soil D1 squeezes into alcohol topping tower C4 by pump P21, by rectification under vacuum, by material
Light component steamed from alcohol topping tower C4 tower tops, and condensed by overhead condenser E1, condensate liquid is sent again after entering submerged soil D3
Reactor is returned to be recycled.Alcohol topping tower C4 tower bottoms is sent into ester purifying column C5 towers by pump P40, will by being evaporated under reduced pressure
Heavies removal in material, heavy constituent processing system is sent into from tower reactor through pump P50, butyl acrylate product is from ester purifying column C5
Tower top steams, and is condensed by condenser E2, and condensate liquid enters after submerged soil D4 is sent into products pot by pump P51, finally gives pure
Spend >=99.6% butyl acrylate product.
Organic acid catalyst in the present embodiment is one or both of methanesulfonic acid, p-methyl benzenesulfonic acid and benzene sulfonic acid.
The present invention enters scrubbing tower, alcohol plug after being sufficiently mixed butyl acrylate product and liquid caustic soda in static mixer
Tower, ester purifying column, purity is finally given up to more than 99.6% butyl acrylate, compared with traditional handicraft, averagely produces one ton
Butyl acrylate product saves 20% liquid caustic soda, while will neutralize influence of the washing link to purification system and be reduced to minimum,
With significant practicality and economic benefit, it is easy to large-scale industrial production.
By being illustrated in conjunction with the embodiments, the personnel of association area can provide the present invention according to the present invention completely
Method carry out suitably change or change with combining, to obtain technical scheme.It should be strongly noted that it is all this
A bit by carrying out similar change or change to technological process provided by the invention with combining, for a person skilled in the art
It is it will be apparent that being considered as in the spirit, scope and content of the present invention.
Claims (5)
1. a kind of purification process of butyl acrylate coarse product, it is characterised in that comprise the following steps：
1) extract
Extractant is made with water, the butyl acrylate coarse product that esterification is obtained carries out continuous countercurrent extraction with extractant；Third
Organic acid catalyst in olefin(e) acid butyl ester crude product enters aqueous phase, and butyl acrylate and accessory substance enter raffinate organic phase, separation,
Raffinate organic phase is continuously into static mixer；Reclaim the organic acid catalyst in aqueous phase；
Described organic acid catalyst is at least one of methanesulfonic acid, p-methyl benzenesulfonic acid and benzene sulfonic acid；
2) mix and neutralize
Liquid caustic soda is continuously sufficiently mixed with raffinate organic phase, neutralize instead continuously into the static mixer provided with sewage draining exit
Should, the organic acid substance in accessory substance is removed, obtains reactant mixture material, pH is 9~12；The addition and acrylic acid of liquid caustic soda
The mass ratio of butyl ester crude product is：0.008~0.018:1；Wherein, the mass fraction of alkali is 10~50% in liquid caustic soda；
3) wash, reclaim
Reactant mixture material in step 2) enters scrubbing tower, is washed, and butyl acrylate in reactant mixture material and removes
Go the accessory substance of organic acid substance to be flowed out from scrubbing tower top, salt caused by neutralization reaction and be dissolved in the impurity of water from scrubbing tower
Bottom of towe flows out, and reclaims the organic principle in tower bottom liquid；
4) separate, purify
The accessory substance of butyl acrylate and removing organic acid substance removes light component and heavy constituent therein, obtained by distillation
To butyl acrylate product, obtained butyl acrylate purity >=99.6%.
2. the purification process of butyl acrylate coarse product according to claim 1, it is characterised in that described in step 1)
Extractant is desalted water.
3. the purification process of butyl acrylate coarse product according to claim 1 or 2, it is characterised in that institute in step 2)
The liquid caustic soda stated is sodium hydroxide solution or potassium hydroxide solution.
4. the purification process of butyl acrylate coarse product according to claim 1, it is characterised in that in step 2), carry out
After neutralization reaction, the salt of precipitation is discharged.
5. the purification process of butyl acrylate coarse product according to claim 1, it is characterised in that by subtracting in step 4)
Light component and heavy constituent in pressure distillation removing accessory substance.
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| CN105218345B (en) * | 2015-09-08 | 2017-07-07 | 中国石油天然气股份有限公司 | Alkylation reaction device and method |
| CN109107221B (en) * | 2018-08-21 | 2024-11-19 | 金发科技股份有限公司 | A solid-liquid extraction purification device and purification method |
| CN109988066A (en) * | 2018-12-21 | 2019-07-09 | 江门谦信化工发展有限公司 | A kind of n-butyl acrylate industrialized producing technology reducing brine waste |
| CN110776417A (en) * | 2019-11-05 | 2020-02-11 | 常州仁晟生物能源科技有限公司 | Production method of isobutyl acrylate |
| CN110937997A (en) * | 2019-12-09 | 2020-03-31 | 东营海德新材料有限公司 | Production process for improving purity of butyl acrylate |
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| US5877345A (en) * | 1997-02-07 | 1999-03-02 | Rohm And Haas Company | Process for producing butyl acrylate |
| CN101239909B (en) * | 2008-03-17 | 2011-01-12 | 上海华谊丙烯酸有限公司 | Method for preparing (methyl) acrylate and device used for the same |
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