CN101205185B - Method for purifying acetyl citrate - Google Patents
Method for purifying acetyl citrate Download PDFInfo
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- CN101205185B CN101205185B CN2006101615329A CN200610161532A CN101205185B CN 101205185 B CN101205185 B CN 101205185B CN 2006101615329 A CN2006101615329 A CN 2006101615329A CN 200610161532 A CN200610161532 A CN 200610161532A CN 101205185 B CN101205185 B CN 101205185B
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Abstract
A method for purifying the acetyl citrate relates to the purification technique and comprises the following steps: (1) the citrate reacts with an excessive amount of acetic anhydrides and then is preliminarily dehydrated in a reaction vessel on the vacuum condition after being deacidified, neutralized and washed so as to obtain the crude products of the acetyl citrates; (2) the crude products aresubject to the secondary treatment utilizing a film evaporator, the vacuum degree is controlled to range from 100Pa to 13300Pa and the flow of the film evaporator ranges from 2kg/m<2> h to 200kg/m<2>h; the film evaporator and the preheater are heated by the steam or heat conduction oil; when the steam is used for heating, the heating steam pressure of the preheater is controlled to range from 0.5kgf/cm<2> to 1.5kgf/cm<2> and the steam pressure of the evaporator ranges from 2.0 to 5.0kgf/cm<2>; when the heat conduction oil is used for heating, the temperature of the heat conduction oil rangesfrom 100 to 140 DEG C. The method is very effective for reducing the purities in the acetyl tri-n-butyl citrate and lowering the water and acid value so as to enhance the quality purity of the acetylcitrate.
Description
Technical field
The invention belongs to the purification technique of chemical industry, refer in particular to a kind of method of utilizing thin-film evaporator purification acetyl citrate.
Background technology
Citrate mainly contains triethyl citrate (TEC), tributyl citrate (TBC), citric acid tri-n-hexyl ester (THC) and citric acid three different monooctyl esters (TOC) at present as softening agent.Citrate through acidylate is more superior as the softening agent performance.Citrate and acetyl citrate be a kind of green capable of circulation, nontoxic and with eco-friendly asepsis environment-protecting softening agent, as aspect the softening agent of PVC, with advantages such as its good soffening and asepsis environment-protectings, part replaces the oil softening agent.
Tributyl acetylcitrate is the most frequently used in all citrates, also is the kind of output maximum.Traditional tributyl acetylcitrate (ATBC) manufacture method is with tributyl citrate (TBC) and aceticanhydride reaction, after depickling, neutralization, washing, place in the sealed reactor again, be heated to 120～135 ℃, constantly vacuumize, remove moisture wherein and make.Prepared in this way product, except having high boiling point impurity such as tributyl citrate (TBC), aconitic acid tri-n-butyl, generally also contain low-boiling-point substances such as a spot of acetic acid, butanols and N-BUTYL ACETATE, not only reduced the content of principal constituent, also make the smell of prepared ATBC finished product heavier, particularly in the PVC course of processing, it is big that smell obviously becomes, and influences workshop condition; And this type of low-boiling-point substance not only do not have the effect of softening agent when entering the PVC goods, overflows from goods easily on the contrary, increases the weight of the fuel-displaced phenomenon of goods, influences the quality of prepared PVC goods.
In order to improve prepared tributyl acetylcitrate quality; in general the method that can take to increase neutralization, washing times in the neutralization, washing workshop section after acidylate is removed the low-boiling-point substances such as acetic acid, N-BUTYL ACETATE and butanols that influence the tributyl acetylcitrate quality; but can increase again thus tributyl acetylcitrate loss, reduce output and increase cost; and can increase the generation of waste water and cause the pressure of environmental protection treatment, so this kind method is in large-scale commercial process and be not suitable for.If in dehydration, keep higher vacuum, improve temperature and time expand and also can remove acetic acid, low-boiling-point substance such as N-BUTYL ACETATE and butanols, but because citrate is a kind of thermographic compound, if temperature is too high, overlong time, can cause the finished product color and luster to be deepened again, promote tributyl acetylcitrate to decompose, generate acetic acid and aconitic acid tri-n-butyl, sometimes can increase the acid number of finished product on the contrary, so-called acid returning phenomenon appears, the difficult control of technology in the production process of concrete tributyl acetylcitrate is so this kind method also is unfavorable for large-scale industrial production.
Exist equally also in the production process of the alcohol of producing highly purified acetyl triethyl citrate, the just own ester of acetyl tributyl citrate three, acetyl tributyl citrate three different monooctyl esters or different carbonatomss and the acetylate of the mixed ester of citric acid reactions generation that similar impurity is on the high side, acid number is higher, the difficult control of technology, be unfavorable for problem such as scale operation.
Summary of the invention
Problem to be solved by this invention provides the method for purification of the acetyl citrate of the manageable suitable suitability for industrialized production of a kind of technology, can more effectively remove contained lower-boiling impurity of acetyl citrate and moisture, makes that its acid number is lower, purity is higher.
For solving the problems of the technologies described above; thinking of the present invention is to adopt existing technology to make the thick finished product of acetyl citrate earlier; relend the lower-boiling impurity and the moisture that help to be contained in the thick finished product of the further effective elimination acetylize of thin-film evaporator citrate, reduce its acid number, thereby improve the purity and the quality of acetyl citrate.
Concrete technical scheme of the present invention is: (1) citrate and the reaction of excessive aceticanhydride, and through depickling, neutralization, washing, preliminary hydro-extraction in reactor under vacuum condition makes the thick finished product of acetyl citrate; (2) should utilize thin-film evaporator to carry out secondary treatment by thick finished product again, vacuum degree control be 100～13300Pa, and the thin-film evaporator flow is 2～200kg/m
2H, described thin-film evaporator and preheater thereof are by steam or heat-conducting oil heating, and during steam heating, the preheater heating steam pressure is controlled to be 0.5～1.5kgf/cm
2, the vapor pressure of vaporizer is 2.0～5.0kgf/cm
2As when using heat-conducting oil heating, the thermal oil temperature is 100-150 ℃.
The acetyl citrate of this method indication can be acetyl triethyl citrate or tributyl acetylcitrate or just own ester of acetyl tributyl citrate three or acetyl tributyl citrate three different monooctyl esters, also can be the alcohol of different carbonatomss and the acetylate of the mixed ester that citric acid reactions generates.
In the production in order to obtain better treatment effect, the preferred 400-680Pa of the vacuum tightness of thin-film evaporator among the present invention, the preferred 50～100kg/m of the flow velocity of thin-film evaporator
2H, the preferred 125-130 of the temperature of thermal oil ℃, the vapor pressure of vaporizer is 3.0～3.5kgf/cm
2
In the inventive method, the evaporation area of thin-film evaporator can determine as the case may be, from 0.2-100m
2, serve as preferred with thinfilm rotary evaporator especially rotary moveable wiped film evaporator.
From actual effect, to adopt the obtained tributyl acetylcitrate sample of the present invention, with the trade mark produced in USA be that the tributyl acetylcitrate of A-4, the trade mark that Germany produces are that the tributyl acetylcitrate of B-II carries out sampling fraction, the contrast of correlation technique index is as follows:
| The sample title | U.S. A-4 | Germany B-II | The present invention | Conclusion |
| Purity GC% | 99.199? | 99.197? | 99.453? | Raising is arranged |
| Colourity APHA | 10? | 10? | 10? | Consistent |
| 25 ℃ of refractive powers | 1.4410? | 1.4410? | 1.4410? | Consistent |
| Acid number mgKOH/g | 0.032? | 0.042? | 0.010? | Obviously reduce |
| Moisture % | 0.060? | 0.040? | 0.020? | Obviously reduce |
As can be seen from the above table, the present invention is highly effective to reducing impurity in the tributyl acetylcitrate, reducing its moisture and acid number thereby improve its quality purity.
Embodiment
Embodiment 1-4 is that 0.105mgKOH/g, moisture are that 0.081% ATBC crude product is an example with the acid number, when it adopts the 0.2m of heat-conducting oil heating
2Thin-film evaporator handle, control thin-film evaporator gentle vacuum tightness of oil and flow, result such as following table:
Embodiment 5-8 is that 0.082mgKOH/g, moisture are that 0.054% ATBC crude product is an example with the acid number, as its steam heated 6m
2Rotary moveable wiped film evaporator when handling, vapor pressure, vacuum tightness and the flow of control preheater and vaporizer, result such as following table:
Embodiment 9-12 is an example with the ATBC crude product of different acidity and moisture, at 6m
2When steam-heated rotary moveable wiped film evaporator is handled, embodiment result such as following table:
The technical program also can have other distortion.Form as thin-film evaporator distribution material can be multiple, as employing rotary moveable wiped film evaporator, and can select suitable scraper plate form according to the physical and chemical performances such as viscosity of material, determines suitable material.The purification that the present invention can be used for having the chemical substance of similar quality equally separates; the every employing earlier has the thick finished product of chemical substance that technology makes certain content now; adopt thin-film evaporator to carry out secondary treatment again; described thin-film evaporator vacuum tightness, temperature, flow number do not exceed scope that the present invention announces, all belong to protection scope of the present invention.
Claims (9)
1. the method for purification of an acetyl citrate is characterized in that this method comprises: (1) citrate and the reaction of excessive aceticanhydride, and through depickling, neutralization, washing, preliminary hydro-extraction in reactor under vacuum condition obtains the thick finished product of acetyl citrate; (2) should utilize thin-film evaporator to carry out secondary treatment by thick finished product again, vacuum degree control be 100～13300Pa, and the thin-film evaporator flow is 2～200kg/m
2H, described thin-film evaporator and preheater thereof are by steam or heat-conducting oil heating, and during steam heating, the preheater heating steam pressure is controlled to be 0.5～1.5kgf/cm
2, the vapor pressure of vaporizer is 2.0～5.0kgf/cm
2As when using heat-conducting oil heating, the thermal oil temperature is 100-150 ℃.
2. the method for purification of acetyl citrate according to claim 1, the vacuum tightness that it is characterized in that thin-film evaporator is 400-680Pa.
3. the method for purification of acetyl citrate according to claim 1, the flow that it is characterized in that thin-film evaporator is 50～100kg/m
2H.
4. the method for purification of acetyl citrate according to claim 1, the temperature that it is characterized in that thermal oil is 125-135 ℃.
5. the method for purification of acetyl citrate according to claim 1, the vapor pressure that it is characterized in that vaporizer is 3.0～3.5kgf/cm
2
6. the method for purification of acetyl citrate according to claim 1 is characterized in that acetyl citrate is acetyl triethyl citrate or tributyl acetylcitrate or just own ester of acetyl tributyl citrate three or acetyl tributyl citrate three different monooctyl esters.
7. according to the method for purification of claim 1,2,3,4,5, one of 6 described acetyl citrates, the evaporation area that it is characterized in that described thin-film evaporator is 0.2-100m
2
8. the method for purification of acetyl citrate according to claim 7 is characterized in that described thin-film evaporator is a thinfilm rotary evaporator.
9. the method for purification of acetyl citrate according to claim 8 is characterized in that described thin-film evaporator is the rotary moveable wiped film evaporator.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101615329A CN101205185B (en) | 2006-12-21 | 2006-12-21 | Method for purifying acetyl citrate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006101615329A CN101205185B (en) | 2006-12-21 | 2006-12-21 | Method for purifying acetyl citrate |
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| CN101205185A CN101205185A (en) | 2008-06-25 |
| CN101205185B true CN101205185B (en) | 2011-05-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101830803B (en) * | 2010-01-25 | 2013-04-03 | 西北师范大学 | Method for synthesizing citric acid ester type compound |
| CN107349614A (en) * | 2016-06-24 | 2017-11-17 | 湖南力健机械有限公司 | One kind rotation is without coking continuous cracking carbonized film evaporation equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557800A (en) * | 2004-02-06 | 2004-12-29 | 江南大学 | Process for preparing ethyl citrate suitable for industrialized production |
| CN1709854A (en) * | 2005-06-24 | 2005-12-21 | 浙江大学 | Catylatic synthesizing method of acetyl tri-in-butyl citrate |
| CN1803755A (en) * | 2005-10-22 | 2006-07-19 | 方雅悯 | Method for extracting acetylformic acid by fermentation in the absence of calcium salt |
| CN1844079A (en) * | 2006-03-22 | 2006-10-11 | 浙江大学 | Device and method for catalytic synthesis of acetyl tri-n-butyl citrate by fixed bed reactor |
-
2006
- 2006-12-21 CN CN2006101615329A patent/CN101205185B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1557800A (en) * | 2004-02-06 | 2004-12-29 | 江南大学 | Process for preparing ethyl citrate suitable for industrialized production |
| CN1709854A (en) * | 2005-06-24 | 2005-12-21 | 浙江大学 | Catylatic synthesizing method of acetyl tri-in-butyl citrate |
| CN1803755A (en) * | 2005-10-22 | 2006-07-19 | 方雅悯 | Method for extracting acetylformic acid by fermentation in the absence of calcium salt |
| CN1844079A (en) * | 2006-03-22 | 2006-10-11 | 浙江大学 | Device and method for catalytic synthesis of acetyl tri-n-butyl citrate by fixed bed reactor |
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Inventor after: Zhou Jianan Inventor after: Zhou Yongfang Inventor after: Chen Ping Inventor after: Cao Lijun Inventor after: Wu Xiaoliang Inventor before: Zhou Yongfang Inventor before: Cao Lijun Inventor before: Chen Ping Inventor before: Wu Xiaoliang |
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Address after: Qiting street of Yixing city Jiangsu province 214213 Kaixuan Road No. 1 Patentee after: Jiangsu Raymond New Material Co., Ltd. Address before: Yongan Lu Qiting Street Office of Yixing city in Jiangsu province 214213 Jiangsu Yixing Economic Development Zone No. 8 Patentee before: Jiangsu Lemon Chemical Industry Technology Co., Ltd. |