CN101367724A - Method and apparatus for synthesis of isopropyl acetate - Google Patents
Method and apparatus for synthesis of isopropyl acetate Download PDFInfo
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- CN101367724A CN101367724A CNA2008101400561A CN200810140056A CN101367724A CN 101367724 A CN101367724 A CN 101367724A CN A2008101400561 A CNA2008101400561 A CN A2008101400561A CN 200810140056 A CN200810140056 A CN 200810140056A CN 101367724 A CN101367724 A CN 101367724A
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Abstract
The present invention relates to a technical method of synthesizing isopropyl acetate with a reaction-rectification bulkhead column, and a device thereof. The reactive distillation bulkhead column is characterized in that a bulkhead is arranged in the vertical direction in a conventional rectification column, the right-side bottom of the bulkhead is sealed, and the whole column is divided into five regions. Raw materials, namely, isopropyl alcohol and acetic acid are added into the column from the upper space of the column reactor; the isopropyl alcohol and the acetic acid perform esterification reaction in the reaction zone or in the lower part of the column reactor to prepare the isopropyl acetate with the influence of a catalyst acidic cation exchange resin; after the gas phase at the top of the column is condensed and separated, the water phase is discharged out of the system, and the ester phase are driven into the top of the column as a back flow; the product isopropyl acetate of high purity can be acquired at the bottom of the side stripping section; and no materials are discharged at the bottom of the column. The advantages of the bulkhead and the reaction distillation are fully developed in the present invention, the esterification reaction and the product purification can be realized in one tower, and the equipment investment and energy consumption can be effectively reduced.
Description
Technical field
The present invention relates to a kind of reactive distillation process method and device thereof, specifically be meant a kind of novel process method and device thereof that utilizes reactive distillation next door tower synthesis of acetic acid isopropyl ester, synthetic, the product of isopropyl acetate can be separated and purify to be incorporated in the tower and finish.
Background technology
Isopropyl acetate is a kind of important Organic Chemicals and organic solvent, have good alkali resistance, hydrophobicity, isopropyl acetate has than present widely used ethyl acetate and the more superior performance of n-butyl acetate, its solubility property is better than ethyl acetate, and its volatile performance is better than n-butyl acetate.Therefore can substitute ethyl acetate, n-butyl acetate, be applied to industries such as medicine, coating, printing ink, tackiness agent.The technology of present industrial production isopropyl acetate has the acid alcohol esterification process, Virahol and ethyl acetate ester-interchange method (CN1785955A), and acetate and propylene direct esterification method (CN 1260203C) etc., and wherein widespread use is the acid alcohol esterification process.
Traditional acid alcohol esterification process production technique is: adopt acetate and Virahol to do the raw material esterification and produce isopropyl acetate, this method is made catalyzer with the vitriol oil or highly acidic resin, in reactor, react, obtain near the equilibrated reaction mixture, there are a series of by products to generate simultaneously, with the mixture rectifying in distillation tower that obtains thus, distill out the mixture that approaches Virahol, isopropyl acetate and water ternary heterogeneous azeotrope.Then the organic phase of the ternary heterogeneous azeotrope that obtains is thus carried out fractionation by distillation.The main drawback of this technology is to form complicated azeotrope between water, Virahol and the isopropyl acetate etc., be difficult for further being refined into the high purity isopropyl acetate, all bring certain difficulty for the refining of product and raw material recovery, and the aftertreatment of reactant will be through neutralization, washing to remove sulfuric acid, and there are problems such as equipment corrosion is serious, side reaction is many, product separation is difficult, production cost is high, wastewater treatment trouble in this technology.
The appearance of reaction rectification technique has successfully solved this problem.The reactive distillation synthesis technique organically is coupled reaction process and rectification and purification process, reactant acetate and Virahol are in reaction, reaction product isopropyl acetate and water in time leave reaction zone, reactant acetate and the concentration of Virahol in reaction zone have been improved, thereby the carrying out that has suppressed reversed reaction, so reactive distillation can effectively improve the transformation efficiency of speed of reaction and acetate.Patent CN1194957C discloses the method for a kind of reactive distillation coproduction ethyl acetate and isopropyl acetate, esterification takes place with Fischer-Tropsch process alcohol mixture and acetate and generates ethyl acetate and isopropyl acetate in this method under the effect of acid catalyst, mixture with ethyl acetate and isopropyl acetate shifts out reaction tower as overhead product then, this overhead product obtains containing the organic phase and the water of ester mixture after the condensation phase-splitting, reclaim ethyl acetate and isopropyl acetate through a series of rectifyinges from organic phase then.
But still there is certain defective in above-mentioned reaction rectification technique: the reactive distillation cat head obtains the complicated binary or the mixture of ternary azeotrope, need follow-up a series of rectifying tower further to separate and just can obtain highly purified isopropyl acetate product with extraction tower, and the air-teturning mixed phenomenon of intermediate component in the conventional polynary rectifying can occur, thermodynamic(al) efficiency is lower.This causes energy consumption and facility investment higher, is unfavorable for increasing economic efficiency.
And utilize reactive distillation next door tower technology effectively to address the above problem.Reactive distillation next door tower is that reactive distillation processes is applied in the tower of next door, is the integrated chemical production technical of a kind of height.In the tower of reactive distillation next door, the isopropyl acetate product is extracted out by side line, in a tower, finish tasks such as esterification, isopropyl acetate purification simultaneously, a rectifying tower and a condenser have been saved, and reactive distillation next door tower can effectively be avoided the back-mixing effect of intermediate component in the conventional polynary rectifying, and the thermodynamic(al) efficiency of process is higher, thereby cut down the consumption of energy and facility investment, increase economic efficiency.
Summary of the invention
The present invention relates to a kind of reactive distillation next door tower that utilizes and realize isopropyl acetate synthetic and product isolating height coupled processing method and device thereof.
Device of the present invention is made of reactive distillation next door tower, phase splitter, condenser, reboiler and auxiliary facility.Reactive distillation next door tower is that a vertical next door is set in a common rectifying tower inside, and the next door extends to the bottom of tower, its right side closed bottom from the top of tower.The combination of column plate or filler or column plate and filler is housed in the tower of reactive distillation next door, this tower is divided into five zones: public rectifying section (I), rectifying section (II), conversion zone (III), tower still (IV) and side line stripping section (V), catalyzer is equipped with in conversion zone (III) and tower still (IV) bottom, catalyzer is an acidic cation-exchange resin, cat head is established phase splitter, zero discharge at the bottom of the tower.The next door is that off-centre or center are provided with, and the cross-sectional area of rectifying section (II) and side line stripping section (V) is than between 0.5:1～5:1.
Raw material Virahol and acetate are added in the tower by tower still (IV) upper space, with Virahol esterification generation isopropyl acetate take place under the effect of acidity of catalyst Zeo-karb at conversion zone (III) and tower still (IV) bottom acetate; Isopropyl acetate that generates and water and Virahol form binary and ternary azeotrope, after removing wherein acetate through the refinery distillation of rectifying section (II) and public rectifying section (I), obtain approaching the mixture flow of isopropyl acetate, water and Virahol heterogeneous azeotrope at cat head, this logistics is through being divided into water and ester phase in phase splitter after the condensation, water is discharged system, and ester is squeezed into cat head as backflow; The next door top, part liquid phase mixture flows to into rectifying section (II) and provides liquid-phase reflux for it, another part liquid phase mixture enters side line stripping section (V), after a small amount of Virahol and water are removed in its centrifugation, obtains highly purified isopropyl acetate product in its bottom.
Reactive distillation next door tower working pressure is 80～200kPa.The volume space velocity of acetic acid feed is 0.3～1.5h
-1, Virahol and acetic acid feed mol ratio are 1:1～1.1:1.The cat head service temperature is 70～100 ℃, and the phase splitter service temperature is 40～60 ℃, and reaction bed temperature is 100～135 ℃.The liquid phase mass rate that is flowed into rectifying section (II) by the top, next door is 2:3～4:1 with the liquid phase mass rate ratio that flows into side line stripping section (V).Isopropyl acetate quality product mark reaches more than 99% among the present invention, and acetate approaches whole conversions.
The present invention organically is combined in reaction process, product separation and purification in the tower and carries out simultaneously, and can directly obtain highly purified isopropyl acetate product, simplified the popular response distillation process, and improve reaction conversion ratio to greatest extent, reduced energy consumption and facility investment expense effectively.
Description of drawings
Fig. 1, isopropyl acetate synthetic reactive distillation next door tower schematic flow sheet
Among the figure: 1 reactive distillation next door tower; 2 next doors; 3 condensers; 4 phase splitters; 5,6 reboilers; 7 catalyzer; The public rectifying section of I; The II rectifying section; The III conversion zone; IV tower still; V side line stripping section
Specific embodiments
The present invention is described in further detail below in conjunction with accompanying drawing:
As shown in Figure 1, device of the present invention mainly is made of reactive distillation next door tower (1), condenser (3), phase splitter (4), reboiler (5,6) and other utility appliance.Reactive distillation next door tower (1) is that a vertical next door (2) is set in a common rectifying tower inside, next door (2) extends to the bottom of tower from the top of tower, its right side closed bottom, next door (2) is that off-centre or center are provided with, rectifying section (II) is 0.5:1～5:1 with the cross-sectional area ratio of side line stripping section (V), column plate or filler or the combination of the two are housed in the reactive distillation next door tower (1), catalyzer (7) is equipped with in conversion zone (III) and tower still (IV) bottom, catalyzer (7) is an acidic cation-exchange resin, cat head is established phase splitter (4), zero discharge at the bottom of the tower.
Reactive distillation next door tower working pressure is 80～200kPa.Raw acetic acid is 0.3～1.5h according to volume space velocity
-1Virahol is that the flow of 1:1～1.1:1 is added in the tower by tower still (IV) upper space according to Virahol and acetate mol ratio, in conversion zone (III) and tower still (IV) bottom, esterification takes place and generates isopropyl acetate in acetate and Virahol under the effect of catalyzer (7) acidic cation-exchange resin, beds (7) temperature is 100～135 ℃.Isopropyl acetate that generates and water and Virahol form binary and ternary azeotrope, remove the mixture flow that obtains approaching isopropyl acetate, water and Virahol heterogeneous azeotrope behind wherein the acetate at cat head through the refinery distillation of rectifying section (II) and public rectifying section (I), this logistics is divided into water and ester phase in phase splitter (4) after condenser (3) condensation, water is discharged system, and ester is squeezed into cat head as backflow, the cat head service temperature is 70～100 ℃, and the phase splitter service temperature is 40～60 ℃.Top, next door (2) liquid phase flows into rectifying section (II) and side line stripping section (V) by a certain percentage respectively, wherein, the liquid phase mass rate that flows into rectifying section (II) is 2:3～4:1 with the liquid phase mass rate ratio that flows into side line stripping section (V), the logistics that flows into side line stripping section (V) obtains highly purified isopropyl acetate product in its bottom after a small amount of Virahol and water are removed in its centrifugation.Be respectively equipped with reboiler (5,6) at the bottom of side line stripping section (V) bottom and the tower and provide heat for reactive distillation next door tower.
The present invention can illustrate by following example:
Example 1: reactive distillation next door tower is tower diameter 2400mm, the packing tower of high 19000mm, zone (I)～zone (III) and zone (V) packed height are respectively 2000mm, 4000mm, 5500mm, 4000mm, and rectifying section (II) is 3.3:1 with the cross-sectional area ratio of side line stripping section (V).Working pressure is 100kPa, and the cat head service temperature is 77 ℃, and the phase splitter service temperature is 50 ℃.Catalyzer is equipped with in conversion zone (III) and tower still (IV) bottom, and catalyzer is a Purolite CT179 acidic cation-exchange resin, and reaction bed temperature is 110～112 ℃.The volume space velocity of acetic acid feed is 0.86h
-1, Virahol and acetic acid feed mol ratio are 1.04:1.The liquid phase mass rate that is flowed into rectifying section (II) by top, next door (2) is 7:3 with the liquid phase mass rate ratio that flows into side line stripping section (V).Each logistics quality flow and quality are formed as shown in table 1.Gained acetate transformation efficiency is 99.83%.
Table 1 example 1 each logistics quality flow and quality are formed
Example 2: reactive distillation next door tower is tower diameter 2400mm, the packing tower of high 19000mm, zone (I)～zone (III) and zone (V) packed height are respectively 2000mm, 4000mm, 5500mm, 4000mm, and rectifying section (II) is 2.1:1 with the cross-sectional area ratio of side line stripping section (V).Working pressure is 150kPa, and the cat head service temperature is 88 ℃, and the phase splitter service temperature is 50 ℃.Catalyzer is equipped with in conversion zone (III) and tower still (IV) bottom, and catalyzer is Amberlyst 15 acidic cation-exchange resins, and reaction bed temperature is 122～124 ℃.The volume space velocity of acetic acid feed is 0.86h
-1, Virahol and acetic acid feed mol ratio are 1.04:1.The liquid phase mass rate that is flowed into rectifying section (II) by top, next door (2) is 3:2 with the liquid phase mass rate ratio that flows into side line stripping section (V).Each logistics quality flow and quality are formed as shown in table 2.Gained acetate transformation efficiency is 99.78%.
Table 2 example 2 each logistics quality flow and quality are formed
Example 3: reactive distillation next door tower is tower diameter 2600mm, the tray column of high 2400mm, and zone (I)～zone (III) and zone (V) stage number are respectively 8,14,20,14, and rectifying section (II) is 1.4:1 with the cross-sectional area ratio of side line stripping section (V).Working pressure is 130kPa, and the cat head service temperature is 83 ℃, and the phase splitter service temperature is 50 ℃.Catalyzer is equipped with in conversion zone (III) and tower still (IV) bottom, and catalyzer is a Purolite CT179 acidic cation-exchange resin, and reaction bed temperature is 117～119 ℃.The volume space velocity of acetic acid feed is 0.86h
-1, Virahol and acetic acid feed mol ratio are 1.04:1.The liquid phase mass rate that is flowed into rectifying section (II) by top, next door (2) is 1:1 with the liquid phase mass rate ratio that flows into side line stripping section (V).Each logistics quality flow and quality are formed as shown in table 3.Gained acetate transformation efficiency is 99.66%.
Table 3 example 3 each logistics quality flow and quality are formed
Example 4: reactive distillation next door tower is tower diameter 2600mm, the filler column plate combined column of high 22000mm, column plate is equipped with in zone (I), zone (II), zone (V), stage number is respectively 8,14,14, filler is equipped with in zone (III), packed height is 5500mm, and rectifying section (II) is 1.9:1 with the cross-sectional area ratio of side line stripping section (V).Working pressure is 120kPa, and the cat head service temperature is 82 ℃, and the phase splitter service temperature is 50 ℃.Catalyzer is equipped with in conversion zone (III) and tower still (IV) bottom, and catalyzer is Amberlyst 15 acidic cation-exchange resins, and reaction bed temperature is 115～121 ℃.The volume space velocity of acetic acid feed is 0.86h
-1, Virahol and acetic acid feed mol ratio are 1.04:1.The liquid phase mass rate that is flowed into rectifying section (II) by top, next door (2) is 3:2 with the liquid phase mass rate ratio that flows into side line stripping section (V).Each logistics quality flow and quality are formed as shown in table 4.Gained acetate transformation efficiency is 99.91%.
Table 4 example 4 each logistics quality flow and quality are formed
Claims (8)
1. the synthesizer of an isopropyl acetate comprises reactive distillation next door tower, phase splitter, condenser, reboiler and other auxiliary facilitys.A vertical next door is established in tower inside, reactive distillation next door, and the next door extends to the bottom of tower, its right side closed bottom from the top of tower.Reactive distillation next door tower is divided into five zones: public rectifying section (I), rectifying section (II), conversion zone (III), tower still (IV) and side line stripping section (V).
2. synthesizing isopropyl acetate method is characterized in that isopropyl acetate is synthetic and obtain separating and purify in the reactive distillation next door tower described in claim 1, and this process is made up of following steps:
A) raw material Virahol and acetate are added in the tower by tower still (IV) upper space, esterification takes place under conversion zone (III) and tower still (IV) bottom acetate and the effect of Virahol at catalyzer generate isopropyl acetate, zero discharge at the bottom of the tower.
B) isopropyl acetate of Sheng Chenging and water and Virahol form binary and ternary azeotrope, remove the mixture flow that obtains approaching isopropyl acetate, water and Virahol heterogeneous azeotrope behind wherein the acetate at cat head through the refinery distillation of rectifying section (II) and public rectifying section (I).
C) non-homogeneous mixture that obtains of cat head is through being divided into water and ester phase in phase splitter after the condensation, and water is discharged system, and ester is squeezed into cat head as backflow.
D) next door top, a part of liquid phase mixture flow to into rectifying section (II) to it provides liquid-phase reflux, and another part enters side line stripping section (V), after a small amount of Virahol and water are removed in its centrifugation, obtain highly purified isopropyl acetate product in its bottom.
3. as claim 1,2 described device and processing methodes, it is characterized in that catalyst filling in conversion zone (III) and tower still (IV) bottom, described catalyzer is an acidic cation-exchange resin.
4. device as claimed in claim 1 is characterized in that the next door is that off-centre or center are provided with, and the cross-sectional area of rectifying section (II) and side line stripping section (V) is than between 0.5:1～5:1.
5. device as claimed in claim 1 is characterized in that being equipped with in the tower of reactive distillation next door the combination of column plate or filler or column plate and filler.
6. processing method as claimed in claim 2, it is characterized in that top, next door liquid phase flows into rectifying section (II) and side line stripping section (V) by a certain percentage respectively, the liquid phase mass rate that enters rectifying section (II) is 2:3～4:1 with the liquid phase mass rate ratio that enters side line stripping section (V).
7. processing method as claimed in claim 2, the volume space velocity that it is characterized in that acetic acid feed is 0.3～1.5h
-1, Virahol and acetic acid feed mol ratio are 1:1～1.1:1.
8. processing method as claimed in claim 2 is characterized in that reactive distillation next door tower working pressure is 80～200kPa, and the cat head service temperature is 70～100 ℃, and the phase splitter service temperature is 40～60 ℃, and reaction bed temperature is 100～135 ℃.
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| CN2008101400561A CN101367724B (en) | 2008-09-18 | 2008-09-18 | Method and apparatus for synthesis of isopropyl acetate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103214367A (en) * | 2013-05-09 | 2013-07-24 | 江苏瑞佳化学有限公司 | Continuous production device and method for isopropyl acetate |
| CN103254067A (en) * | 2013-04-28 | 2013-08-21 | 江门谦信化工发展有限公司 | Esterification production method of isopropyl acetate |
| CN103265429A (en) * | 2013-05-24 | 2013-08-28 | 青岛理工大学 | Process method for synthesizing methyl acetate |
| CN104529763A (en) * | 2014-11-07 | 2015-04-22 | 济南大学 | Process and device for synthesizing ethyl formate with reactive distillation dividing wall column |
| CN108516934A (en) * | 2018-05-18 | 2018-09-11 | 烟台大学 | A kind of production technology of next door reactive distillation production cyclohexyl formate |
| CN109608319A (en) * | 2018-12-23 | 2019-04-12 | 中国科学院山西煤炭化学研究所 | A kind of technique of higher ketone, water and carbon dioxide mixture separation |
| CN109776284A (en) * | 2017-11-15 | 2019-05-21 | 江苏鼎烨药业有限公司 | A kind of preparation method of 2- methoxyl group propylene |
| CN109776287A (en) * | 2017-11-15 | 2019-05-21 | 江苏鼎烨药业有限公司 | A kind of preparation method of acetone dimethyl acetal |
| CN114797147A (en) * | 2022-05-16 | 2022-07-29 | 湖南中创化工股份有限公司 | Method and device for recovering tail gas of isopropyl acetate refining tower |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1446791A (en) * | 2002-03-27 | 2003-10-08 | 上海化工研究院 | Method and equipments for preparing isopropyl acetate by esterification in continuous process |
| US7371912B2 (en) * | 2005-06-15 | 2008-05-13 | Uop Llc | Process for making xylene isomer using a deheptanizer with a side draw recycle |
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2008
- 2008-09-18 CN CN2008101400561A patent/CN101367724B/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254067A (en) * | 2013-04-28 | 2013-08-21 | 江门谦信化工发展有限公司 | Esterification production method of isopropyl acetate |
| CN103214367A (en) * | 2013-05-09 | 2013-07-24 | 江苏瑞佳化学有限公司 | Continuous production device and method for isopropyl acetate |
| CN103214367B (en) * | 2013-05-09 | 2015-06-10 | 江苏瑞佳化学有限公司 | Continuous production device and method for isopropyl acetate |
| CN103265429A (en) * | 2013-05-24 | 2013-08-28 | 青岛理工大学 | Process method for synthesizing methyl acetate |
| CN104529763A (en) * | 2014-11-07 | 2015-04-22 | 济南大学 | Process and device for synthesizing ethyl formate with reactive distillation dividing wall column |
| CN109776284A (en) * | 2017-11-15 | 2019-05-21 | 江苏鼎烨药业有限公司 | A kind of preparation method of 2- methoxyl group propylene |
| CN109776287A (en) * | 2017-11-15 | 2019-05-21 | 江苏鼎烨药业有限公司 | A kind of preparation method of acetone dimethyl acetal |
| CN108516934A (en) * | 2018-05-18 | 2018-09-11 | 烟台大学 | A kind of production technology of next door reactive distillation production cyclohexyl formate |
| CN108516934B (en) * | 2018-05-18 | 2021-02-19 | 烟台大学 | Production process for producing cyclohexyl formate through bulkhead reaction rectification |
| CN109608319A (en) * | 2018-12-23 | 2019-04-12 | 中国科学院山西煤炭化学研究所 | A kind of technique of higher ketone, water and carbon dioxide mixture separation |
| CN114797147A (en) * | 2022-05-16 | 2022-07-29 | 湖南中创化工股份有限公司 | Method and device for recovering tail gas of isopropyl acetate refining tower |
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| CN101367724B (en) | 2012-07-18 |
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