CN106316840A - Method for preparing and purifying tertbutyl propionate - Google Patents
Method for preparing and purifying tertbutyl propionate Download PDFInfo
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- CN106316840A CN106316840A CN201610702328.7A CN201610702328A CN106316840A CN 106316840 A CN106316840 A CN 106316840A CN 201610702328 A CN201610702328 A CN 201610702328A CN 106316840 A CN106316840 A CN 106316840A
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- propanoic acid
- isobutene
- butyl ester
- acid tert
- esterification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for preparing and purifying tertbutyl propionate. The method comprises the following steps of: continuously adding propionic acid and isobutylene-containing mixed gas raw materials into a catalyst filled esterifying tower according to the predefined proportion, controlling the predefined reaction pressure and temperature under the action of the catalyst, performing esterification reaction to obtain crude ester; delivering the obtained crude ester into a separating tower, leading propionic acid and isobutylene polymer and water to be azeotropic, controlling the gaseous phase reflux in the tower to be within the first temperature range, deacidifying and removing polymer of isobutylene, rectifying, collecting the rectification product between 115-125 DEG C, to obtain tertbutyl propionate. According to the method, the reaction is stable and safe, the purity of the product can achieve 99.5% or above, the sources of raw materials are sufficient, and the method is capable of realizing energy conservation and environmental protection, and is low in cost.
Description
Technical field
The invention belongs to organic solvent synthesis technical field, be specifically related to a kind of side prepared and purify propanoic acid tert-butyl ester
Method.
Background technology
Propanoic acid tert-butyl ester is a kind of colourless liquid, can mix with alcohol, ether, can be dissolved in propanoic acid, be practically insoluble in water, as nitre
The solvent of base cellulose, essence, spice, be celluloid, the natural and solvent of synthetic resin, can make lacquer solvent, also use
In essence manufacture.
The method of the current propionic acid synthesized tert-butyl ester mainly has propionyl chloride method: in equipped with agitator, Dropping funnel, reflux condensation mode
In the reaction bulb of device, add the tert-butyl alcohol 285g(1.15mol being dried), DMA 151.5g(159mL,
1.26mol), absolute ether 100mL.Backflow it is heated under stirring.Dropping propionyl chloride 110g(1.19mol), rate of addition controls
State is still maintained the reflux for removing thermal source.When adding the propionyl chloride of about 2/3, ammonium salt separates out and reacts and acutely carries out, available
Ice-water bath cools down.It is slowly added into remaining chloroacetic chloride again.Back flow reaction 1h is continued after adding.It is cooled to room temperature, adds 100mL water,
It is sufficiently stirred for so that solids is completely dissolved.Separate organic layer.Organic layer, with the sulfuric acid scrubbing of 10%, then uses saturated sodium bicarbonate
Solution washs, and anhydrous sodium sulfate is dried.Steam ether, fractional distillation, collect the fraction of 117.5～118.5 DEG C, obtain propanoic acid tert-butyl ester
(1) 92g, yield 62%., the most easily there is intramolecular dehydration, so closing in aforementioned manners in sterically hindered very big due to the tert-butyl alcohol
The reaction becoming propanoic acid tert-butyl ester requires higher, and productivity is relatively low, and side reaction is many, especially can not use the catalysis of water separation capability
Agent；Propanoic acid tert-butyl ester is produced by the acid catalysis propionyloxyization reaction of isobutene. with propanoic acid.This method and work above
Skill compares, and advantageous is at following two aspects: (1) uses alkene to do raw material, relatively can reduce production cost；(2) acid/
Alkene technique belongs to typical green chemical industry technique, and therefore acid/alkene method must be the main method producing propanoic acid tert-butyl ester.But it is this
Method is disadvantageous in that in course of reaction that Ta Neichang can occur the accumulation of (isobutene .) dimer and the situation of catalyst failure,
Result in pureed deposit and finally need parking to clean out tower, and the dimer of alkene adds the separation of propanoic acid tert-butyl ester
Purification difficult.
In order to the relevant issues of prior art being reduced or eliminated and by the high cost problem of purified isobutylene, it is desirable to than
The material that pure isobutene. is more easy to get is to produce propanoic acid tert-butyl ester.In recent years, document report is had can to pass through propanoic acid, propionic andydride and methyl
The mixture of tertbutyl ether (MTBE) or ethyl tert-butyl oxide (ETBE) is catalyzed at one big net type strong-acid ion exchange resin
Produce propanoic acid tert-butyl ester under agent effect, but the catalyst that this technique is used is the highest to the selectivity of propanoic acid tert-butyl ester.
By propanoic acid chlorine method synthesis thick ester, the method for purification usually wash with water after again with 10% potassium carbonate or carbonic acid
It is neutrality that sodium solution is washed till ester layer, and the ester layer anhydrous magnesium sulfate separated distills after drying, collects 117.5-118.5 DEG C
Fraction is product.The thick ester of other method synthesis usually carries out rectification.The propanoic acid tert-butyl ester obtained by these methods pure
Degree generally 99.0%.
Summary of the invention
It is an object of the invention to provide a kind of method prepared and purify propanoic acid tert-butyl ester, course of reaction is stable, safety, and third
Tert-butyl acrylate purity reaches more than 99.5%, and low cost.
A kind of method prepared and purify propanoic acid tert-butyl ester, comprises the steps: propanoic acid and the gaseous mixture containing isobutene.
Body raw material is continuously added to, equipped with in the esterification column of catalyst, under catalyst action, control predetermined reaction pressure according to preset blending ratio
Power and temperature, carry out esterification, obtains thick ester；Will obtain thick ester send into knockout tower, make propanoic acid, isobutene. polymer with
Water azeotropic, in control tower, gas phase refluxes in the first temperature range, carries out de-hydrocarbon, controls gas phase and refluxes in the second temperature range
In, carry out dealcoholysis, control gas phase and reflux in the 3rd temperature range, carry out deacidification and the polymer of removing isobutene., rectification, receive
Rectification product between collecting 115-125 DEG C, obtains propanoic acid tert-butyl ester.
Preferably, the predetermined mol ratio of described propanoic acid and isobutene. is 1:0.30-1:5.00, the Feed space velocities of propanoic acid
0.5-5.0h-1。
Preferably, described catalyst is strongly acidic ion-exchange resin catalyst, and catalyst amount is 30-90ml.
Preferably, described esterification reaction pressure is 0.5-2.0MPa, and reaction temperature is 30-110 DEG C.
Preferably, adding mass fraction in described propanoic acid is the water of 10-30%, the polymer of described water, propanoic acid and isobutene.
Form azeotropic material.
Preferably, adding mass fraction in described propanoic acid is the alcohol compound of 5-20%, to suppress the polymerization of isobutene..
Preferably, the described mixed gas feed containing isobutene. is pure isobutene., oil refining product C4 containing isobutene., described
The admixture of gas that oil refining product C4 is made up of containing four carbon atom petroleum cracking product.
Preferably, the first temperature of described de-hydrocarbon is 70-85 DEG C, and the second temperature of described dealcoholysis is 78-90 DEG C, described de-
3rd temperature of the polymer of acid and removing isobutene. is 90-110 DEG C.
Preferably, described esterification reaction process the first esterification column and two esterification columns of the second esterification column, described first
The thick ester of product of esterification column and the mixed gas feed containing isobutene. enter second esterification column and react.
Preferably, the Feed space velocities of the thick ester of described second esterification column of entrance is 1.0-2.0h-1, in second esterification column
Other reaction conditions and the first esterification column identical.
The present invention uses propanoic acid and the admixture of gas containing isobutene. to be raw material, anti-by esterification column continuous feed esterification
Should, to mention thick ester, utilize propanoic acid simultaneously, the method for the polymer azeotrope with water of isobutene. produces and refined product, overcomes biography
The problem of point water difficulty that the acid alcohol technique of system exists, the most also solves olefin(e) acid method production isobutene polymer product and separates tired
A difficult difficult problem, it is achieved that continuous esterification and separating-purifying, makes propanoic acid tert-butyl ester product content reach more than 99.5%.It addition, work as
When admixture of gas containing isobutene. uses oil refining product C4 to be raw material, raw material sources are convenient, in liberal supply, low cost, and energy
Turn waste into wealth, energy-conserving and environment-protective.
Detailed description of the invention
Below embodiments of the invention are elaborated: the present embodiment is carried out under premised on technical solution of the present invention
Implement, give embodiment and process in detail, but protection scope of the present invention is not limited to following embodiment.
The embodiment of the present invention provide a kind of method prepared and purifies propanoic acid tert-butyl ester, comprise the steps: by propanoic acid with
Mixed gas feed containing isobutene. is continuously added to equipped with in the esterification column of catalyst according to preset blending ratio, at catalyst action
Under, control predetermined reaction pressure and temperature, carry out esterification, obtain thick ester；The thick ester obtained is sent into knockout tower, makes third
Acid, the polymer azeotrope with water of isobutene., in control tower, gas phase refluxes in the first temperature range, carries out de-hydrocarbon, controls gas phase
Backflow, in the second temperature range, carries out dealcoholysis, controls gas phase and refluxes in the 3rd temperature range, carries out deacidification and removing isobutyl
The polymer of alkene, rectification, the rectification product between collecting 115-125 DEG C, obtain propanoic acid tert-butyl ester.
Preferably, the metering of described propanoic acid constant-flux pump is squeezed into, and esterification column and knockout tower use temperature controlling instruments to carry out temperature control
System.
Preferably, the predetermined mol ratio of described propanoic acid and isobutene. is 1:0.30-1:5.00, more preferably 1:1.5-1:
3；The Feed space velocities 0.5-5.0h of propanoic acid-1, more preferably 1.5-3.0 h-1；Described catalyst is strong-acid ion exchange resin
Catalyst, catalyst amount is 30-90ml, more preferably 45-60ml；Described esterification reaction pressure is 0.5-2.0MPa, more excellent
Elect 0.8-1.2MPa as；Reaction temperature is 30-110 DEG C, more preferably 45-80 DEG C；
Preferably, adding mass fraction in described propanoic acid is the water of 10-30%, water described in esterification reaction process, propanoic acid and isobutyl
The polymer of alkene forms azeotropic material, can be removed by water by forming azeotropic mixture, and the mass fraction of water is more preferably 15-25%；Institute
Stating interpolation mass fraction in propanoic acid is the alcohol compound of 5-20%, and to suppress the polymerization of isobutene., alcohol compound can be second
Alcohol, ethylene glycol etc., be not limited to this, and the mass fraction of alcohol compound is more preferably 10-15%.
Preferably, the described mixed gas feed containing isobutene. is pure isobutene., oil refining product C4 containing isobutene., described
The admixture of gas that oil refining product C4 is made up of containing four carbon atom petroleum cracking product, this reaction is preferably refined oil product C4 and is
Raw material, oil refining product C4 is more cheap for pure isobutene., is also easier to obtain, and using oil refining product C4 is that raw material is greatly lowered
Production cost.
Preferably, in knockout tower, the first temperature of described de-hydrocarbon is 70-85 DEG C, more preferably 75-80 DEG C；Described de-
Second temperature of alcohol is 78-90 DEG C, more preferably 80-88 DEG C；3rd temperature of the polymer of described deacidification and removing isobutene.
For 90-110 DEG C, more preferably 95-105 DEG C.
Preferably, described esterification reaction process the first esterification column and two esterification columns of the second esterification column, described first
The thick ester of product of esterification column and the mixed gas feed containing isobutene. enter second esterification column and react, described entrance
The Feed space velocities of the thick ester of second esterification column is 1.0-2.0h-1, more preferably 1.2-1.6 h-1；In second esterification column
Other reaction conditions and the first esterification column are identical.
Preparation and the method purifying propanoic acid tert-butyl ester, the productivity etc. of product is illustrated below by way of multiple embodiments.
Embodiment 1:
By propanoic acid with the oil refining product C4 feeding containing isobutene. equipped with in the esterification column of ion-exchange resin catalyst, wherein propanoic acid
Squeezing into constant-flux pump metering, catalyst uses strong acid ion exchange resin, and consumption is 45m1, uses temperature controlling instruments to carry out temperature
Control.Testing raw materials used for propanoic acid with containing the C4 of isobutene., the Feed space velocities of propanoic acid is 1.2h-1Send in esterification column, control
C4 exhaust flow containing isobutene. is 60m1/min, reaction pressure 0.8MPa, reaction temperature 60 DEG C, react within 6-7 hour, sample into
Row is analyzed, and obtains thick ester.Thick ester is sent into knockout tower, utilizes the method for the polymer azeotrope with water of propanoic acid, isobutene. to control top
Gas phase reflux temperature, de-hydrocarbon under the conditions of 70 DEG C, 78 DEG C of western dealcoholysis of condition, deacidification and the polymerization of isobutene. under the conditions of 90 DEG C
Thing, collects 115-125 DEG C of rectification product, obtains propanoic acid tert-butyl ester product, purity 99.5%.
Embodiment 2:
Testing raw materials used for propanoic acid, water and containing the C4 of isobutene., the Feed space velocities of propanoic acid is 2h-1, water and the mass ratio of propanoic acid
For 1:5, the C4 exhaust flow containing isobutene. is 60m1/min, and catalyst amount is 60ml, and reaction pressure is 1.0MPa, reaction temperature
Degree is 80 DEG C, and other conditions, with embodiment 1, obtain thick ester.Thick ester is sent into knockout tower, by utilize propanoic acid, isobutene. poly-
The method control top gaseous phase reflux temperature of compound azeotrope with water, DEG C de-hydrocarbon under the conditions of 75, dealcoholysis under the conditions of 85 DEG C,
Deacidification and the polymer of isobutene. under the conditions of 100 DEG C, rectification, collect 115-125 DEG C of rectification product, obtain propanoic acid tert-butyl ester and produce
Product, purity is 99.6%.
Embodiment 3:
Testing raw materials used for propanoic acid with containing the C4 of isobutene., the Feed space velocities of propanoic acid is 3h-1, C4 tail gas stream containing isobutene.
Amount is 60m1/min, and catalyst amount is 75ml, and reaction pressure is 1.2MPa, and reaction temperature is 65 DEG C, and other conditions are with implementing
Example 1, this reaction is carried out at esterification column 1.(propanoic acid tert-butyl ester is the propanoic acid tert-butyl ester crude product obtained by first esterification column
18.97%) continuously enter second esterification column, and supplement simultaneously containing isobutene. C4 there is esterification, control C4 tail gas stream
Amount 60ml/min, the Feed space velocities of thick ester is 1.5h-1, this reaction is carried out at esterification column two, and other conditions, with esterification column 1, obtain
Thick ester 2.Thick ester 2 is sent into knockout tower, utilizes the method for the polymer azeotrope with water of propanoic acid, isobutene. to control top gas and reflux mutually temperature
Degree, de-hydrocarbon under the conditions of 80 DEG C, dealcoholysis under the conditions of 90 DEG C, deacidification and the polymer of isobutene. under the conditions of 100 DEG C, rectification,
Collect 115-125 DEG C of rectification product, obtain propanoic acid tert-butyl ester product, purity 99.6%.
It should be noted that the invention is not limited in above-mentioned embodiment, according to the creative spirit of the present invention, this area
Technical staff can also make other changes, these changes done according to the creative spirit of the present invention, all should be included in this
Bright claimed within the scope of.
Claims (10)
1. the method prepared and purify propanoic acid tert-butyl ester, it is characterised in that comprise the steps: by propanoic acid with containing isobutene.
Mixed gas feed be continuously added to equipped with in the esterification column of catalyst according to preset blending ratio, under catalyst action, control pre-
Determine reaction pressure and temperature, carry out esterification, obtain thick ester；The thick ester that will obtain sends into knockout tower, makes propanoic acid, isobutene.
Polymer azeotrope with water, in control tower, gas phase refluxes in the first temperature range, carries out de-hydrocarbon, controls gas phase backflow in the second temperature
In the range of degree, carry out dealcoholysis, control gas phase and reflux in the 3rd temperature range, carry out deacidification and the polymer of removing isobutene.,
Rectification, the rectification product between collecting 115-125 DEG C, obtain propanoic acid tert-butyl ester.
2. preparation as claimed in claim 1 and the method for purification propanoic acid tert-butyl ester, it is characterised in that described propanoic acid and isobutene.
Predetermined mol ratio be 1:0.30-1:5.00, the Feed space velocities 0.5-5.0h of propanoic acid-1。
3. preparation as claimed in claim 1 and the method for purification propanoic acid tert-butyl ester, it is characterised in that described catalyst is strong acid
Property ion-exchange resin catalyst, catalyst amount is 30-90ml.
4. preparation as claimed in claim 1 and the method for purification propanoic acid tert-butyl ester, it is characterised in that described esterification reaction pressure
For 0.5-2.0MPa, reaction temperature is 30-110 DEG C.
5. preparation as claimed in claim 1 and the method for purification propanoic acid tert-butyl ester, it is characterised in that add matter in described propanoic acid
Amount mark is the water of 10-30%, and the polymer of described water, propanoic acid and isobutene. forms azeotropic material.
6. preparation as claimed in claim 1 and the method for purification propanoic acid tert-butyl ester, it is characterised in that add matter in described propanoic acid
Amount mark is the alcohol compound of 5-20%, to suppress the polymerization of isobutene..
7. preparation as claimed in claim 1 and the method for purification propanoic acid tert-butyl ester, it is characterised in that described mixing containing isobutene.
Close gas raw material be pure isobutene., oil refining product C4, described oil refining product C4 containing isobutene. be containing four by petroleum cracking product
The admixture of gas of individual carbon atom composition.
8. preparation as claimed in claim 1 and the method for purification propanoic acid tert-butyl ester, it is characterised in that the first temperature of described de-hydrocarbon
Degree is for 70-85 DEG C, and the second temperature of described dealcoholysis is 78-90 DEG C, the 3rd temperature of the polymer of described deacidification and removing isobutene.
Degree is for 90-110 DEG C.
9. preparation as claimed in claim 1 and the method for purification propanoic acid tert-butyl ester, it is characterised in that described esterification reaction process
Use the first esterification column and two esterification columns of the second esterification column, the thick ester of product of described first esterification column with containing isobutene.
Mixed gas feed enter second esterification column react.
10. preparation as claimed in claim 9 and the method for purification propanoic acid tert-butyl ester, it is characterised in that described entrance second
The Feed space velocities of the thick ester of esterification column is 1.0-2.0h-1, other reaction conditions in second esterification column and the first esterification column phase
With.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610702328.7A CN106316840A (en) | 2016-08-23 | 2016-08-23 | Method for preparing and purifying tertbutyl propionate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610702328.7A CN106316840A (en) | 2016-08-23 | 2016-08-23 | Method for preparing and purifying tertbutyl propionate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884248A (en) * | 2006-07-04 | 2006-12-27 | 湖南长岭石化科技开发有限公司 | Process for preparing and extracting tert-butyl acetate |
| CN101560152A (en) * | 2009-05-27 | 2009-10-21 | 南京工业大学 | Method for synthesizing propionate |
| CN102924271A (en) * | 2012-11-20 | 2013-02-13 | 南京工业大学 | Method for producing tert-butyl ester compound by esterification, rectification and coupling of organic carboxylic acid and isobutene |
-
2016
- 2016-08-23 CN CN201610702328.7A patent/CN106316840A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884248A (en) * | 2006-07-04 | 2006-12-27 | 湖南长岭石化科技开发有限公司 | Process for preparing and extracting tert-butyl acetate |
| CN101560152A (en) * | 2009-05-27 | 2009-10-21 | 南京工业大学 | Method for synthesizing propionate |
| CN102924271A (en) * | 2012-11-20 | 2013-02-13 | 南京工业大学 | Method for producing tert-butyl ester compound by esterification, rectification and coupling of organic carboxylic acid and isobutene |
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Application publication date: 20170111 |