CN102249913B - Preparation method of butyl acrylate - Google Patents
Preparation method of butyl acrylate Download PDFInfo
- Publication number
- CN102249913B CN102249913B CN 201110126789 CN201110126789A CN102249913B CN 102249913 B CN102249913 B CN 102249913B CN 201110126789 CN201110126789 CN 201110126789 CN 201110126789 A CN201110126789 A CN 201110126789A CN 102249913 B CN102249913 B CN 102249913B
- Authority
- CN
- China
- Prior art keywords
- tower
- conversion zone
- butyl acrylate
- acid
- butanols
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to a preparation method of butyl acrylate, which is characterized in that the synthesis of butyl acrylate is completed in a reaction rectifying tower, the separation of products and raw materials is completed through azeotropic rectification, and heavy components generated by the reaction in a stripping section and the tower are resolved into the raw materials and the products so as to finally obtain a butyl-acrylate-enriched organic phase having an acrylic acid content of 4ppm at the tower top.
Description
Technical field
The present invention relates to the preparation method of a kind of organic compound in the chemical industry field, specifically, relate to a kind of method for preparing butyl acrylate by reactive distillation.This method is complete butyl acrylate in a rectifying tower synthetic, complete separating of product and raw material by azeotropic distillation simultaneously, meanwhile will react the heavy component that generates and be decomposed into raw material and product in stripping section and tower reactor, finally obtaining acrylic acid content at tower top is the organic phase that is rich in butyl acrylate of 4ppm.
Background technology
Acrylic ester monomer is the starting monomer of the important synthetic polymer of a class.Butyl acrylate (AEB) is widely used in coating, sizing agent, weaving, papermaking, leather and the fields such as plastics, acrylic elastomer as synthon, modified additive.
In following statement, except special declaration, per-cent all refers to mass percent.
Butyl acrylate (AEB) can be obtained by the esterification of vinylformic acid (AA) and butanols (BuOH) usually, but the esterification of vinylformic acid (AA) and butanols (BuOH) is a reversible reaction, therefore have the problem of an equilibrium conversion, this depends on the equilibrium constant under reaction conditions.In order to improve equilibrium conversion, on technique, two kinds of methods of general employing are broken molecular balance at present: the one, remove the water (H that reaction generates
2O), usually adopt the way of distilling to reduce the concentration of water in liquid product, balance is moved to the direction that generates product, the product butyl acrylate is with the extraction of still liquid, as published patent US5945560.The 2nd, remove simultaneously water and the ester of generation, usually adopt the way of component distillation to reduce simultaneously the concentration of water and ester in reaction solution, balance is moved to the direction that generates product, complete simultaneously separating of butyl acrylate and vinylformic acid and heavy component.
US Patent No. 4280010 discloses a kind of continuous production method for preparing alkyl acrylate, this method is under reduced pressure carried out, adopting sulfuric acid or organic sulfonic acid is catalyzer, on the top of the first distillation zone of reaction zone, the azeotropic mixture of alkyl acrylate, water and unreacted alkyl alcohol is separated.
The disclosed method of European patent 0733617 is for adopting single reaction vessel to carry out continuous esterification, and the water that generates in reactor and alkyl ester are separated by reactor top rectifying tower as moisture azeotrope.
European patent 0779268 disclose a kind of in esterification reaction mixture the method for Propylene recovery acid butyl ester, by vinylformic acid knockout tower AA, BuOH, AEB, the H of autoreactor in the future
2The mixture of O separates, and tower top obtains being rich in the organic phase of AEB, and wherein AA content is higher, approximately 2000ppm.
Chinese patent ZL00809024.6 discloses a kind of method that relates to equilibrium-limited reaction, as esterification and alcoholysis reaction.Employing single reaction district and the acid separation column that comprises rectification zone and stripping zone, at single reaction district's cracking heavy ingredient, and the part of at least a ester products of vaporizing.
Above disclosed method all adopts single reactor to carry out esterification, common this reactive mode is to obtain high conversion need adopt the long residence time, cause need to be larger reactor volume, reason is in order to make the reaction product vaporization, temperature of reactor is higher, butanols and water, ester form azeotrope equally, have reduced the reaction zone butanol concentration, make the esterification Speed Reduction.In addition, do not have catalyzer in knockout tower, butanols can't react again, needs to use follow-up system to reclaim a large amount of unreacted pure Returning reactors, causes energy consumption to increase.In addition, for obtaining the organic phase of low acrylic acid concentration, above method all needs a vinylformic acid knockout tower to continue to separate.
Chinese patent ZL98122474.1 discloses a kind of method for preparing alkyl acrylate.This method is the synthesizing propylene acid alkyl ester in an esterification, hydrolysis reactor, simultaneously process impurity is hydrolyzed to raw material, and in reactor separate raw materials and product, this esterification, hydrolysis reactor are stirred reactors, a rectifying tower is arranged at its top.This reactor substantially still exists single reaction zone and disengaging zone, and therefore the same with aforementioned patent, speed of reaction is on the low side, and reactor volume is larger.
Summary of the invention
The present invention is intended to overcome the above-mentioned deficiency that discloses all patented methods, and a kind of method for preparing butyl acrylate by reactive distillation is provided.Specifically, it is complete butyl acrylate in a rectifying tower synthetic, complete separating of product and raw material by azeotropic distillation simultaneously, and the heavy component that will generate in reacting in stripping section and tower reactor simultaneously is decomposed into raw material and product, and finally obtaining acrylic acid content at tower top is the organic phase that is rich in butyl acrylate of 4ppm.
That is to say, the inventive method is characterised in that: described reactive distillation Tower System comprises rectifying section, conversion zone, stripping section; Vinylformic acid and butanols carry out esterification at conversion zone, and the butyl acrylate and the water that generate are simultaneously separated from liquid-phase reaction system by azeotropic distillation; Reactant vinylformic acid is from first plate charging of conversion zone, butanols is from the charging of conversion zone bottommost, the live catalyst that replenishes adds from first block of plate of conversion zone, and stopper adds at first plate spray of rectifying section, and overhead condensation water, organic phase are partly refluxed to respectively tower top; The heavy constituent that conversion zone generates: propylene dimer acid, tripropylene sour with and with esterification products and the Michael addition adducts of butanols, be vinylformic acid, butanols and butyl acrylate by catalytic decomposition in stripping section and tower reactor; Tower bottoms partly is circulated to first block of plate of conversion zone, to reclaim catalyzer and stopper, make conversion zone keep certain catalyst concn, rest part still liquid enters thin-film evaporator, and the butanols of recovery, vinylformic acid, butyl acrylate and part heavy component enter conversion zone.
According to above-mentioned, the reactive distillation Tower System that the inventive method is used comprises: the rectifying section of rectifying tower, conversion zone, stripping section, phlegma phase separation tank, thin-film evaporator, overhead condenser and tower reactor reboiler; Fresh AA is sent into first block of plate of conversion zone by pipeline top, fresh BuOH sends into plate of conversion zone bottommost by pipeline, and additional live catalyst solution is sent into first block of plate of conversion zone by pipeline, and stopper adds first block of plate of tower top through pipeline; React in AA and the BuOH liquid layer on the conversion zone column plate, the AEB and the H that generate simultaneously
2O, BuOH distill out liquid phase under the effect of azeotropic; The top gaseous phase mixture, is isolated the organic phase that is rich in AEB and contains a small amount of organic water through layering in phase splitter after condenser condenses by pipeline; The part water is back to tower top by pipeline, and as the component that forms binary, ternary azeotropic system, all the other waters are delivered to follow-up system by pipeline and reclaimed BuOH and AEB; Organic phase is passed through the pipeline partial reflux to tower top, thereby effectively reduces the AA concentration of rectifying section, and all the other organic phases are sent into follow-up system by pipeline and reclaimed BuOH and the AEB that purifies; BuOH, AEB that follow-up system reclaims are sent into the bottom of conversion zone by pipeline; Tower bottoms returns to tower reactor through pipeline by reboiler, and the rectified heat load is provided; The part tower bottoms directly returns to first block of plate of conversion zone through pipeline, reclaims wherein catalyzer and stopper, makes the catalyzer in conversion zone column plate liquid layer maintain finite concentration; All the other tower bottomss enter thin-film evaporator through pipeline, reclaim BuOH, AA, AEB and part heavy component, and the material of recovery returns to conversion zone through pipeline; The thin-film evaporator bottom discharge enters follow-up system through pipeline and further processes, usually as waste material.
The invention is characterized in by a reaction fractionating tower, complete simultaneously esterification, heavy component and be decomposed into separating of the reaction of product and raw material and product and raw material, and obtain substantially not contain the organic phase that is rich in AEB of AA at tower top, namely having completed by a reaction fractionating tower needs the function completed by a plurality of devices such as single reaction district, vinylformic acid knockout tower, hydrolyzer, crackers in the prior art, make technique more compact integrated.
High boiling point reactant A A is from conversion zone top charging, lower boiling BuOH is from the conversion zone underfeed, guaranteed that like this AA that BuOH in the liquid phase of conversion zone bottom maintains in the liquid phase on higher concentration, conversion zone top maintains higher concentration, on whole conversion zone column plate, two kinds of reactants all maintain high density relatively thereby make, and the azeotrope of product formation simultaneously removes from system, and molecular balance is moved right faster.It is pointed out that according to present existing technology, pure and mild acid enters in the single reaction vessel of similar tower reactor, under same operation pressure, its temperature is higher than temperature in the middle part of tower, so the relative concentration of BuOH is lower, thereby speed of response is lower, often causes reactor volume larger, and cost is higher.
The reaction fractionating tower stage number of using in the present invention is 20～100, and wherein the conversion zone stage number is 5～35, and the rectifying section stage number is 10～50, and the stripping section stage number is 5～15.Conversion zone stage number and catalyst concn, conversion zone temperature are relevant.Catalyst concn is higher, the conversion zone temperature is higher, and esterification speed is faster, and the required reaction times is shorter, and namely required column plate total liquid inventory is less, and required conversion zone stage number is fewer.But catalyst concn, when the conversion zone temperature is high, side reaction occurs easily, reduce the AEB yield.Preferred 6～20 of conversion zone stage number, the liquid-phase catalysis agent concentration is preferred 4～15%, preferred 80～100 ℃ of conversion zone temperature.The transformation efficiency of AA is 90～99%, preferred 95～99%.For keeping AA that higher transformation efficiency and selectivity are arranged, in each burst charging, total mol ratio of BuOH and AA is 1: 1～1.7: 1, preferred 1.2～1.5.In existing single esterifier Technology, decompose therein for guaranteeing heavy component, temperature of reaction is generally higher, high temperature and, under sour environment, the side reaction that dehydration generates dibutyl ether (DBE) easily occurs in BuOH, has increased pure consumption.
Reaction fractionating tower adopts decompression operation, preferred operations pressure 20～70kPaA.Compare with atmospheric operation, can reduce the service temperature of tower reactor when guaranteeing that conversion zone is temperature required, reduce the tendency that polymkeric substance produces, extend the driving cycle, also can reduce simultaneously the consumption of stopper.
Obtaining substantially not contain the organic phase that is rich in AEB of AA from tower top, is by AEB and H
2O, BuOH form the azeotrope realization, and in this system, the composition of azeotrope is as shown in table 1.According to table 1, the water yield of reacting generation can not satisfy the ratio of two yuan of AEB, ternary azeotrope, therefore reach certain azeotropic ratio by water, organic phase reflux amount, the AEB that generates is all taken out of from tower top, thereby make thin-film evaporator bottom discharge substantially not contain the heavy component of AEB.The control of the low AA content at tower top place realizes at rectifying section by a certain amount of organic phase reflux.In addition, organic phase consists of BuOH and AEB, the organic phase that is back in tower need to form two yuan, ternary azeotrope again with the water backflow, just can steam tower top, otherwise the AEB, the BuOH that reflux will fall into tower reactor in a large number, therefore, the aqueous-phase reflux amount not only will satisfy the azeotropic proportioning that reaction generates AEB, also will satisfy simultaneously the azeotropic proportioning of backflow organic phase.If but the water backflow is excessive, also without benefit, at first can increase energy consumption to operation, in addition, to fix at pressure one, therefore the boiling point of water can increase the temperature of rectifying section higher than the boiling point of azeotrope, and tower top AA content is increased greatly.Preferred organic phase reflux ratio is 1: 1～15: 1, and preferred aqueous-phase reflux ratio is 2: 1～30: 1.In organic phase, AA content is no more than 8ppm, preferably is no more than 4ppm, the organic phase that does not substantially contain AA can cancel AA in follow-up system in and operation, otherwise need add alkali neutralization, washing etc., can increase wastewater flow rate, alkali consumption and AA unit consumption etc.
Table 1 azeotrope forms and boiling point
From the stripping section to the tower reactor, the heavy component that reaction generates, as sour in the acid of: propylene dimer, tripropylene with and with esterification products and the Michael addition adducts of butanols, concentration in liquid phase is more and more higher, and AEB, AA concentration in liquid phase reduces gradually, under the effect of catalyzer, the reactions such as heavy component is hydrolyzed, cracking are decomposed into AA, AEB, BuOH etc.For keeping certain decomposition rate, in tower bottoms, the concentration of heavy component is at least greater than 50%, and preferred 55～70%, the tower reactor temperature is 100～130 ℃, preferred 105～125 ℃.Temperature is too low, and the heavy component rate of decomposition is inadequate, and temperature is too high, and the side reactions such as polymerization, carbonization easily occur.
The tower reactor liquid effluent enters thin-film evaporator, and because tower bottoms is mainly the by product that reaction generates, the flow of this burst logistics is very little.Material high-temperature zone residence time in thin-film evaporator is very short, polymerization and the carbonization of heavy component have been avoided, therefore thin-film evaporator can operate at higher temperature, with further decomposition heavy component, and wherein a small amount of BuOH, AA, AEB are recovered to rectifying tower, make in thin-film evaporator bottom discharge waste material substantially not contain raw material and product.The service temperature of thin-film evaporator is 140～160 ℃, preferred 150～160 ℃.
Catalyzer described in the present invention is selected from sulfuric acid, Phenylsulfonic acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid, naphthene sulfonic acid or C
1-C
10A kind of in alkylsulphonic acid.Live catalyst replenishes at first block of plate of conversion zone and adds, and solvent can be water, butanols or vinylformic acid, and the concentration of solution and magnitude of recruitment are discharged catalytic amount according to the thin-film evaporator bottom and determined, principle is that to keep in reaction system catalyst concn certain.The tower bottoms major part loops back conversion zone top, to reclaim catalyzer and the stopper of tower reactor high-content, keeps catalyzer preferred concentration 4～15% in the reaction liquid phase.
Can adopt stopper to suppress the formation of the polymkeric substance of AA, AEB and derivative thereof.Stopper is added by the tower top spray, it is 0.01～0.9% of raw material total mass that stopper adds quality, and stopper wherein is selected from one or more in Resorcinol, benzoquinones, thiodiphenylamine, copper dibutyldithiocarbamate, neutralized verdigris, nitroxyl free radical piperidine alcohols, tetramethyl piperidine nitrogen oxygen free radical tris phosphite.
(as described in US5945560) compares with prior art, and the present invention removes water and the ester of generation simultaneously by reactive distillation, reduces the concentration of two kinds of products in reaction solution, makes speed of response faster; Complete simultaneously separating of ester and acid and heavy component, greatly simplified the separating technology of follow-up system.
The present invention concentrates on the acquisition of esterification, heavy component hydrolysis, cracking, low AA concentration AEB simultaneously in a reaction fractionating tower and completes.Esterification is carried out at conversion zone, BuOH, AA are respectively from bottom, the top charging of conversion zone, make that on whole conversion zone column plate, two kinds of reactants all maintain high density relatively, compare the middle alkyd of prior art (described in US4280010, EP0733617, EP077268, ZL00809024.6) and enter simultaneously single reaction vessel, speed of response is faster; The present invention reacts the heavy component of generation, from the stripping section to the tower reactor, concentration in liquid phase raises gradually, and AEB, AA, BuOH concentration in liquid phase reduces gradually, the reactions such as under the effect of catalyzer, heavy component is hydrolyzed, cracking, be decomposed into raw material and product, everything is compared with prior art (ZL98122474.1), has simplified technique, has saved the equipment such as cracker, hydrolyzer; By rectifying section and suitable aqueous-phase reflux, organic phase reflux, make tower top obtain AA concentration less than the oil phase that is rich in AEB of 4ppm, this compares with prior art (EP077268, ZL00809024.6, ZL98122474.1), need not to separate AA with the vinylformic acid knockout tower again, and in oil phase, the concentration of AA is lower, technique is more compact integrated, has saved equipment investment and energy consumption.
Description of drawings
Fig. 1 is the brief schematic diagram of technical process of the reactive distillation Tower System that adopts of the inventive method.
number in the figure is: 1-reaction fractionating tower rectifying section, 2-reaction fractionating tower conversion zone, 3-reaction fractionating tower stripping section, 4-phlegma phase separation tank, the 5-thin-film evaporator, 6-fresh makeup catalyst pipeline, 7-vinylformic acid feeding line, 8-butanols feeding line, 9-top gaseous phase pipeline, 10-water discharging pipeline, 11-organic phase discharging pipeline, 12-aqueous-phase reflux pipeline, 13-organic phase reflux pipeline, 14-tower reactor reboiler circulation line, 15-tower bottoms circulation line, 16-thin-film evaporator feeding line, 17-thin-film evaporator gas phase is returned the tower pipeline, 18-heavy component outfall pipeline, the 19-follow-up system reclaims BuOH, the AEB pipeline, 20-stopper feeding line, the 21-overhead condenser, 22-tower reactor reboiler.
Embodiment
Below by an embodiment, this explanation is further described in detail, but the present invention is in no way limited to this embodiment.Per-cents all in embodiment are mass percent.
Embodiment
Referring to Fig. 1, the figure shows the principle process sketch of the rectifying tower system that the inventive method mentions.1 is the rectifying section of rectifying tower, and 2 is conversion zone, and 3 is stripping section, and 4 is that phlegma phase separation tank, 5 is that thin-film evaporator, 21 is that overhead condenser, 22 is the tower reactor reboiler; Fresh AA is sent into first block of plate of conversion zone by pipeline 7, fresh BuOH sends into plate of conversion zone bottommost by pipeline 8, and additional live catalyst solution is sent into first block of plate of conversion zone by pipeline 6, and stopper adds first block of plate of tower top through pipeline 20; React in AA and the BuOH liquid layer on the column plate of conversion zone, the AEB and the H that generate simultaneously
2O, BuOH distill out liquid phase under the effect of azeotropic; The top gaseous phase mixture is by pipeline 9, and layering in phase splitter 4 after condenser 21 condensations is isolated the organic phase that is rich in AEB and contains a small amount of organic water; The part water is back to tower top by pipeline 12, and as the component that forms binary, ternary azeotropic system, all the other waters are delivered to follow-up system by pipeline 10 and reclaimed BuOH and AEB; Organic phase to tower top, reduces the AA concentration of rectifying section by pipeline 13 partial reflux effectively, and all the other organic phases are sent into follow-up system by pipeline 11 and reclaimed BuOH and the AEB that purifies; BuOH, AEB that follow-up system reclaims are sent into the bottom of conversion zone by pipeline 19; Tower bottoms returns to tower reactor through pipeline 14 by reboiler 22, and the rectified heat load is provided; The part tower bottoms directly returns to first block of plate of conversion zone through pipeline 15, reclaims wherein catalyzer and stopper, makes the catalyzer in conversion zone column plate liquid layer maintain finite concentration; All the other tower bottomss enter thin-film evaporator 5 through pipeline 16, reclaim BuOH, AA, AEB and part heavy component, and the material of recovery returns to conversion zone through pipeline 17; Thin-film evaporator 5 bottom discharges enter follow-up system through pipeline 18 and further process, usually as waste material.
Reaction fractionating tower is the band downtake sieve-tray tower of a diameter 100mm in this example, and wherein the conversion zone stage number is 15, and the rectifying section stage number is 30, and the stripping section stage number is 10, and full tower adopts the manufacturing of 316L stainless steel.Tower top is the condenser of two series connection, and first is the normal temperature water-cooled, and second is that-2 ℃ of refrigerated waters are cooling, and the second condenser gaseous phase outlet connects sliding vane rotary vacuum pump.The glass quantizer of a 2000ml is connected with the condenser downtake, and quantizer water, organic phase outlet divide respectively two-way, and one the tunnel returns tower top as refluxing through peristaltic pump, and one the tunnel enters respectively water, organic phase storage tank through under meter.Tower reactor is equipped with electrically heated cover and temperature control system, and tower reactor circulation and discharging are controlled by a frequency conversion toothed gear pump.The 500ml glass evaporators is with stirring scratch board, and with the material transmitting system, gas phase is returned to column plate of conversion zone foot by a frequency conversion toothed gear pump in the bottom.
The Bu0H of 1950g/h flow is sent into the bottom column plate of conversion zone by pipeline 8, and the fresh AA of 1740g/h flow sends into a conversion zone topmost plate with the 150g/h flow velocity by pipeline 7 with the AA solution that contains p-methyl benzenesulfonic acid 10% concentration.The aqueous solution of the nitroxyl free radical piperidine alcohols (ZJ-701) of 2.5% concentration adds tower top with the 40g/h flow velocity by pipeline 20.The recovery alcohol that consists of 75%Bu0H, 25%AEB is sent into the 10th block of plate of conversion zone with the 510g/h flow velocity by pipeline 19.Tower top pressure is set 25kPaA.The aqueous-phase reflux amount is set 3200g/h, and the organic phase reflux amount is set 1950g/h.110 ℃ of tower reactor Temperature Settings, the tower reactor internal circulating load is set as 14500g/h.Evaporator temperature is set 150 ℃, and bottom discharge is set as 150g/h.
Per hour to tower top organic phase and the sampling analysis of still liquid, to determine that whole system reaches stable state, begin timing after stablizing and weigh.Tower top organic phase discharging 3830g/h, wherein AEB content 88.5%, BuOH content 10%, AA content 4ppm; Tower top water discharging 460g/h, wherein BuOH content 1.3%, AEB content 0.4%; AA content 4ppm; Base of evaporator discharging 100g/h, wherein catalyst content 15%, AA content 18.7%, AEB content 5%, BuOH content 4.3%, all the other are water, heavy component.
Use the method, the reaction conversion ratio of AA is 99%, and take AA as benchmark, the reaction yield of AEB is 98%, and tower top organic phase AA content is 4ppm.
Claims (3)
1. method for preparing butyl acrylate, its process comprises: complete the synthetic of butyl acrylate in a rectifying tower, complete separating of product and raw material by azeotropic distillation simultaneously, meanwhile will react the heavy component that generates and be decomposed into raw material and product in stripping section and tower reactor, finally obtaining acrylic acid content at tower top is the organic phase that is rich in butyl acrylate of 4ppm; The method is characterized in that:
Described rectifying tower comprises rectifying section, conversion zone, stripping section; Vinylformic acid and butanols carry out esterification at conversion zone, and the butyl acrylate and the water that generate are simultaneously separated from liquid-phase reaction system by azeotropic distillation; Reactant vinylformic acid is from first plate charging of conversion zone, butanols is from the charging of conversion zone bottommost, the live catalyst that replenishes adds from first block of plate of conversion zone, and stopper adds at first plate spray of rectifying section, and overhead condensation water, organic phase are partly refluxed to respectively tower top; The heavy constituent that conversion zone generates: propylene dimer acid, tripropylene sour with and with esterification products and the Michael addition adducts of butanols, be vinylformic acid, butanols and butyl acrylate by catalytic decomposition in stripping section and tower reactor; Tower bottoms partly is circulated to first block of plate of conversion zone, to reclaim catalyzer and stopper, make conversion zone keep certain catalyst concn, rest part still liquid enters thin-film evaporator, and the butanols of recovery, vinylformic acid, butyl acrylate and part heavy component enter conversion zone; Wherein rectifying is to carry out in stage number is the rectifying tower of 20～100, the conversion zone stage number is 5～35, the rectifying section stage number is 10～50, and the stripping section stage number is 5～15, and the column plate type is selected from macroporous plate, the sieve plate with downtake, valve tray or bubble cap plate; Butyl acrylate be separating of vinylformic acid and heavy component to realize by the azeotropic distillation that forms with water, butanols in rectifying tower, the aqueous-phase reflux ratio is 0.5: 1～40: 1, the organic phase reflux ratio is 1: 1～40: 1; Described azeotropic distillation carries out under 5～101kPaA; The temperature of described conversion zone is 70～110 ℃; The butanols and the acrylic acid mol ratio that enter reaction fractionating tower are 1: 1～1.7: 1.
2. the method for preparing butyl acrylate according to claim 1, it is characterized in that: in tower reactor, the mass concentration of catalyzer is 2～20%, and catalyzer is selected from sulfuric acid, Phenylsulfonic acid, p-methyl benzenesulfonic acid, xylene monosulfonic acid, naphthene sulfonic acid or C
1-C
10A kind of in alkylsulphonic acid.
3. the method for preparing butyl acrylate according to claim 1, it is characterized in that: in mass, the add-on of stopper is 0.01～0.9% of reaction raw materials total mass, and stopper is selected from one or more in Resorcinol, benzoquinones, thiodiphenylamine, copper dibutyldithiocarbamate, neutralized verdigris, nitroxyl free radical piperidine alcohols, tetramethyl piperidine nitrogen oxygen free radical tris phosphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110126789 CN102249913B (en) | 2011-05-17 | 2011-05-17 | Preparation method of butyl acrylate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110126789 CN102249913B (en) | 2011-05-17 | 2011-05-17 | Preparation method of butyl acrylate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102249913A CN102249913A (en) | 2011-11-23 |
| CN102249913B true CN102249913B (en) | 2013-11-06 |
Family
ID=44977528
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110126789 Active CN102249913B (en) | 2011-05-17 | 2011-05-17 | Preparation method of butyl acrylate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102249913B (en) |
Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675098A (en) * | 2012-05-29 | 2012-09-19 | 江门谦信化工发展有限公司 | New process for continuous production of butyl acrylate |
| CN102850155B (en) * | 2012-09-24 | 2015-07-08 | 上海和创化学股份有限公司 | Preparation method of methacrylate products |
| CN103193640A (en) * | 2013-04-09 | 2013-07-10 | 富阳经略化工技术有限公司 | Reactive distillation method for producing methyl methacrylate |
| CN103739485B (en) * | 2013-10-29 | 2015-07-22 | 河北美邦工程科技有限公司 | Production method of cyclohexyl acetate and used reaction rectifying tower |
| CN104529759A (en) * | 2014-11-28 | 2015-04-22 | 江门谦信化工发展有限公司 | Energy-saving and environmental-protection butyl acrylate production method |
| CN104502520B (en) * | 2014-12-03 | 2016-06-22 | 江门谦信化工发展有限公司 | The assay method of p-methyl benzenesulfonic acid content in a kind of butyl acrylate reactor |
| CN104557538B (en) * | 2014-12-04 | 2016-08-24 | 江门谦信化工发展有限公司 | In a kind of tower, reactive distillation produces the industrialized preparing process of butyl acrylate |
| CN104557537B (en) * | 2014-12-04 | 2016-06-08 | 江门谦信化工发展有限公司 | In a kind of tower, reactive distillation produces the method for butyl acrylate |
| CN106673955B (en) * | 2015-11-05 | 2019-08-06 | 中国石油化工股份有限公司大连石油化工研究院 | A method of preparing isopropanol |
| CN106673963B (en) * | 2015-11-05 | 2019-09-10 | 中国石油化工股份有限公司大连石油化工研究院 | A method of preparing sec-butyl alcohol |
| CN105801408B (en) * | 2016-05-13 | 2019-07-16 | 中建安装集团有限公司 | A kind of reaction and rectification device producing high purity acrylic acid N-butyl and method |
| CN106278882A (en) * | 2016-07-29 | 2017-01-04 | 江门谦信化工发展有限公司 | A kind of butyl acrylate production system neutralized without alkali and production method thereof |
| BR112020002983B1 (en) * | 2017-08-17 | 2023-03-21 | Basf Se | PROCESS FOR CONTINUOUSLY PREPARING A BUTYL ACRYLATE |
| CN109277070A (en) * | 2018-10-31 | 2019-01-29 | 江苏国胶化学科技有限公司 | The production technology and its device of different monooctyl ester acrylic acid |
| CN109678756B (en) * | 2018-12-25 | 2021-09-17 | 上海交通大学 | Reaction device and method for producing adiponitrile |
| CN109776312A (en) * | 2019-03-20 | 2019-05-21 | 衡阳师范学院 | A kind of preparation method of acryloxy propionic ester type compound |
| 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 |
| CN110935188B (en) * | 2019-12-18 | 2021-10-22 | 万华化学集团股份有限公司 | Continuous rectification separation method and device for hydroxyethyl (meth) acrylate crude product |
| CN111099998A (en) * | 2019-12-30 | 2020-05-05 | 东营海德新材料有限公司 | Esterification production process and production system of butyl acrylate |
| CN111018712B (en) * | 2019-12-30 | 2022-04-19 | 上海华谊新材料有限公司 | Method for producing (meth) acrylic esters |
| CN112663078A (en) * | 2020-11-03 | 2021-04-16 | 重庆大学 | Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile |
| CN112844482B (en) * | 2021-01-14 | 2022-04-22 | 万华化学集团股份有限公司 | Acid-base dual-function heterogeneous catalyst with core-shell structure, preparation method thereof and method for cracking and recycling butyl acrylate heavy component |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2552987A1 (en) * | 1975-11-26 | 1977-06-02 | Hoechst Ag | PROCESS FOR THE CONTINUOUS MANUFACTURING OF AETHER-FREE ACRYLIC ACID ALKYLESTER |
| GB1535489A (en) * | 1976-08-10 | 1978-12-13 | Japan Synthetic Rubber Co Ltd | Process for producing methacrylic acid esters |
| US5360926A (en) * | 1992-10-22 | 1994-11-01 | Sumitomo Chemical Company, Limited | Process for producing methyl methacrylate |
| CN1150142A (en) * | 1995-09-28 | 1997-05-21 | 巴斯福股份公司 | Continuous preparation of alkyl esters of (meth) acrylic acid and apparatus for this purpose |
| CN1161322A (en) * | 1995-12-15 | 1997-10-08 | 罗姆和哈斯公司 | Process for producing butyl acrylate |
| CN1204640A (en) * | 1997-07-04 | 1999-01-13 | Basf公司 | Preparation of esters |
| CN1363545A (en) * | 2000-12-15 | 2002-08-14 | 金属技术股份有限公司 | Preparation of acrylate or methacrylate |
| CN1616399A (en) * | 2004-09-27 | 2005-05-18 | 广西民族学院 | Method and apparatus for continuously preparing ethyl acetate by single tower |
| CN101328119A (en) * | 2008-06-20 | 2008-12-24 | 中国石油大学(华东) | Synthetic process method of methyl acetate and apparatus thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0495958A (en) * | 1990-08-08 | 1992-03-27 | Seiko Epson Corp | Cleaning device for glass mask |
| JP3551620B2 (en) * | 1996-04-30 | 2004-08-11 | 東亞合成株式会社 | Method for producing (meth) acrylate and apparatus for producing the same |
| DE10257525A1 (en) * | 2002-12-10 | 2004-07-01 | Cognis Deutschland Gmbh & Co. Kg | Process for the production of linear or branched fatty acid esters by heterogeneously catalyzed reactive rectification with a pre-reactor |
-
2011
- 2011-05-17 CN CN 201110126789 patent/CN102249913B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2552987A1 (en) * | 1975-11-26 | 1977-06-02 | Hoechst Ag | PROCESS FOR THE CONTINUOUS MANUFACTURING OF AETHER-FREE ACRYLIC ACID ALKYLESTER |
| GB1535489A (en) * | 1976-08-10 | 1978-12-13 | Japan Synthetic Rubber Co Ltd | Process for producing methacrylic acid esters |
| US5360926A (en) * | 1992-10-22 | 1994-11-01 | Sumitomo Chemical Company, Limited | Process for producing methyl methacrylate |
| CN1150142A (en) * | 1995-09-28 | 1997-05-21 | 巴斯福股份公司 | Continuous preparation of alkyl esters of (meth) acrylic acid and apparatus for this purpose |
| CN1161322A (en) * | 1995-12-15 | 1997-10-08 | 罗姆和哈斯公司 | Process for producing butyl acrylate |
| CN1204640A (en) * | 1997-07-04 | 1999-01-13 | Basf公司 | Preparation of esters |
| CN1363545A (en) * | 2000-12-15 | 2002-08-14 | 金属技术股份有限公司 | Preparation of acrylate or methacrylate |
| CN1616399A (en) * | 2004-09-27 | 2005-05-18 | 广西民族学院 | Method and apparatus for continuously preparing ethyl acetate by single tower |
| CN101328119A (en) * | 2008-06-20 | 2008-12-24 | 中国石油大学(华东) | Synthetic process method of methyl acetate and apparatus thereof |
Non-Patent Citations (4)
| Title |
|---|
| 丁斌等.丙烯酸正丁酯生产新工艺研究.《东北师大学报自然科学版》.2002,第34卷(第3期),60-63. |
| 丙烯酸正丁酯生产新工艺研究;丁斌等;《东北师大学报自然科学版》;20020930;第34卷(第3期);第61页第16-26行，图1 * |
| 催化精馏合成丙烯酸正丁酯;杨梅等;《吉林化工学院学报》;20000315;第17卷(第1期);22-23 * |
| 杨梅等.催化精馏合成丙烯酸正丁酯.《吉林化工学院学报》.2000,第17卷(第1期),22-23. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102249913A (en) | 2011-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102249913B (en) | Preparation method of butyl acrylate | |
| EP4049748A1 (en) | Gas-liquid bubbling bed reactor, reaction system and method for synthesizing carbonate | |
| CN1084324C (en) | Continuous preparation of alkyl esters of (meth) acrylic acid and apparatus for this purpose | |
| CN104024210B (en) | The method of vinylformic acid 2-monooctyl ester is manufactured by direct esterification | |
| CN101195574A (en) | Integrated process and apparatus for preparing esters of methacrylic acid from acetone and hydrocyanic acid | |
| US20210331999A1 (en) | System and process for co-producing dimethyl carbonate and ethylene glycol | |
| CN103044257B (en) | Terylene waste material produces alcoholysis method and the apparatus system of dioctyl terephthalate | |
| CN101195576B (en) | Method and apparatus for preparing alkyl esters of methacrylic acid | |
| CN102206230B (en) | Method for preparing triethyl phosphate | |
| CN106588589A (en) | Purification method for polyoxymethylene dimethyl ether(PODE) | |
| CN103193640A (en) | Reactive distillation method for producing methyl methacrylate | |
| CN109678692A (en) | The preparation method of methacrylic acid | |
| CN106631699A (en) | Method for preparing sec-butyl alcohol | |
| CN113354540A (en) | Method for efficiently and continuously preparing methyl ethyl carbonate | |
| US8772534B2 (en) | Method of recovering (meth) acrylic acid ester | |
| RU2161150C2 (en) | Alkyl acrylate production process (versions) | |
| CN106588598A (en) | Polyformaldehyde dimethyl ether refinement method | |
| CN101357880A (en) | Technique and system for preparing dichloropropanol by autocatalysis reaction of glycerine and hydrogen chloride | |
| CN106588596A (en) | Method for purifying polyoxymethylene dimethyl ether | |
| CN106588597A (en) | Method for purifying polyoxyethene dimethyl ether | |
| CN102442893B (en) | Separation method of aldehyde condensation products | |
| CN102040479B (en) | System for preparing dichloropropanol by autocatalytic reaction of glycerol and hydrogen chloride | |
| CN103641797B (en) | Preparation method for N-acetyl morpholine | |
| KR0122429B1 (en) | Method and its new apparatus for producing unsaturated carboxylic acid esters | |
| CN113387978B (en) | Method for preparing diphenyl dimethoxysilane by continuous alcoholysis method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170213 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |