CN1413971A - Method for removing carbonyl material from 1,3-propylene-glycol - Google Patents
Method for removing carbonyl material from 1,3-propylene-glycol Download PDFInfo
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- CN1413971A CN1413971A CN 02133056 CN02133056A CN1413971A CN 1413971 A CN1413971 A CN 1413971A CN 02133056 CN02133056 CN 02133056 CN 02133056 A CN02133056 A CN 02133056A CN 1413971 A CN1413971 A CN 1413971A
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- ammediol
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- aqueous solution
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Abstract
A process for removing the carbonyl matter from 1,3-propanediol includes such steps as preparing 10-90% aqueous solution of 1,3-propanediol, adding one or more compounds with NH2-Y structure, stirring while reaction at 20-100 deg.c for 0.1-10 hr, and rectifying. Its advantages are short period, low reaction temp. and high effect.
Description
Technical field: the present invention relates to a kind of 1, the method for purification of ammediol, particularly a kind of structural formula that utilizes is NH
2The compound of-Y is to 1, the method for purification of ammediol.
Background technology: 1, ammediol (PDO) is an important chemical material, is mainly used in to produce poly terephthalic acid 1, ammediol ester (PTT), this polyester can be made film and fiber.1, ammediol can oxyethane be a raw material, makes its carbonylation under the cobalt catalyst effect, makes through hydrogenation again; Other method is to be raw material with the propenal, issues unboiled water in an acidic catalyst effect and closes reaction, makes through hydrogenation again.Usually, 1, contain the above carbonyl material (comprising acetal) of 300 μ g/g in the ammediol product.1, carbonyl material content height in the ammediol can be to poly terephthalic acid 1, and the multinomial quality index of ammediol ester (PTT) fiber product produces detrimentally affect, and is wherein particularly evident to the influence of dying effect and dye stability in the dyeing keratin-fiber.Therefore, 1, ammediol is used to prepare poly terephthalic acid 1, and ammediol ester (PTT) is preceding to be removed wherein residual carbonyl material and be very important.The method that removes micro-carbonyl in the document of notification number US5527973 is will contain carbonyl material 1 earlier, and the ammediol product is made into the aqueous solution of 20～70wt%; Adding organic acid or mineral acid make the solution pH value reach 2～6 in this solution then; In this solution, feed rare gas element again, so that carry out volatile impunty; Use the alkali neutralization solution at last, make pH value＞7, can produce yellow impurities, under 10～60kpa, obtain 1 again, ammediol by rectifying.This method can reduce carbonyl content.Notification number US6235948 and notification number are that all to adopt solid acid in the document of CN1345710 be catalyzer, make 1 under 90～150 ℃, and impurity contained in the ammediol reacts, and goes out polymeric impurity by fractionation by distillation then, finally obtains qualified product.Above method exist the treatment time long, temperature of reaction is high, can cause 1, weak points such as ammediol dehydration.
Summary of the invention: the purpose of this invention is to provide a kind of 1, the removal methods of carbonyl material in the ammediol, compared with the prior art, it had both simplified technology, can reduce by 1 effectively again, the content of ammediol carbonyl can solve the problem that prior art exists effectively.The present invention is achieved by the following technical solutions: will contain 1 of carbonyl material earlier, ammediol is mixed with 10～90% the aqueous solution, is NH to wherein adding structural formula then
2-Y (can be alkylamine, arylamine, azanol, hydrazine, phenylhydrazine, 2,4-dinitrophenylhydrazine and Urea,amino-) compound in one or more mixture, add-on is 1, in the ammediol aqueous solution 5～50 of carbonyl content times (molar fraction), thorough mixing, under agitation condition, under 20～100 ℃, reacted 0.1～10 hour, at last by rectification under vacuum, isolate highly purified 1, ammediol, wherein 1, the minimal residue carbonyl can be reduced to 50 μ g/g following (being as the criterion with C=O) in the ammediol.The analytical procedure of carbonyl compound of the present invention is to be undertaken by the method for GB6324.6-86.Carbonyl materials (comprising acetal and free carbonyl) all in this method all are converted into 2, the derivative of 4-dinitrophenylhydrazone, and the latter obtains the amount of total carbonyl material by colorimetry.The amount of total carbonyl material is as the criterion with C=O.Treatment time of the present invention shortens to minimum 0.1 hour, and temperature of reaction drops to minimum 20 ℃, solved the prior art treatment time long, temperature of reaction is high and 1, the problem of ammediol dehydration.
Embodiment one: present embodiment will contain 1 of carbonyl material, and ammediol is mixed with 10～30% the aqueous solution, be NH to wherein adding structural formula then
2The compound of-Y, hydrazine preferably, add-on is 1,10～45 of carbonyl content times of (molar fraction) thorough mixing in the ammediol aqueous solution under agitation condition, reacted 0.5～7.5 hour down in 30～90 ℃, go out by rectifying separation at last highly purified 1, ammediol.
Embodiment two: the difference of present embodiment and embodiment one is, will contain 1 of carbonyl material, and ammediol is mixed with 31～50% the aqueous solution.Other composition and processing condition are identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one is, will contain 1 of carbonyl material, and ammediol is mixed with 51～70% the aqueous solution.Other composition and processing condition are identical with embodiment one.
Embodiment four: the difference of present embodiment and embodiment one is, will contain 1 of carbonyl material, and ammediol is mixed with 71～90% the aqueous solution.Other composition and processing condition are identical with embodiment one.
Embodiment five: present embodiment will contain 1 of carbonyl material, and ammediol is mixed with and is preferably 40～60% the aqueous solution, be NH to wherein adding structural formula then
2The compound of-Y, preferably 2,4 dinitrophenyl hydrazine, preferably add-on is 1, and 15～40 of carbonyl content times of (molar fraction) thorough mixing in the ammediol aqueous solution are under agitation condition, in 40～80 ℃ of down reactions 1～5 hour, go out by rectifying separation at last highly purified 1, ammediol.
Embodiment six: present embodiment is with 150 milliliter 1, and ammediol, its carbonyl content are 360 μ g/g, be mixed with 50% 1, the ammediol aqueous solution.The hydrazine hydrate that in this solution, adds 3 milliliter 50%, reacted 1 hour down at 70 ℃, after reaction finishes, reacted 1, it is in 26 the rectifying tower that the ammediol aqueous solution joins theoretical plate number, system pressure is controlled at 20kPa, and tower top temperature is controlled at 156 ℃, reflux ratio 8: 1, obtain 1, ammediol, purity is 99.5% after testing, wherein carbonyl content can be reduced to 46 μ g/g.
Claims (10)
1,1, the removal methods of carbonyl material in the ammediol is characterized in that and will contain 1 of carbonyl material that ammediol is mixed with 10～90% the aqueous solution, is NH to wherein adding structural formula then
2The compound thorough mixing of-Y, and in 20～100 ℃ of down reactions 0.1～10 hour, at last by rectifying, isolate highly purified 1, ammediol.
2, according to claim 11, the removal methods of carbonyl material in the ammediol is characterized in that and will contain 1 of carbonyl material that ammediol is mixed with 10～30% the aqueous solution.
3, according to claim 11, the removal methods of carbonyl material in the ammediol is characterized in that and will contain 1 of carbonyl material that ammediol is mixed with 31～50% the aqueous solution.
4, according to claim 11, the removal methods of carbonyl material in the ammediol is characterized in that and will contain 1 of carbonyl material that ammediol is mixed with 51～70% the aqueous solution.
5, according to claim 11, the removal methods of carbonyl material in the ammediol is characterized in that and will contain 1 of carbonyl material that ammediol is mixed with 71～90% the aqueous solution.
6, according to claim 11, the removal methods of carbonyl material in the ammediol is characterized in that and will contain 1 of carbonyl material that ammediol is mixed with and is preferably 40～60% the aqueous solution.
7, according to claim 11, the removal methods of carbonyl material in the ammediol is characterized in that structural formula is NH
2The compound of-Y can be alkylamine, arylamine, azanol, hydrazine, phenylhydrazine, 2,4 dinitrophenyl hydrazine and Urea,amino-, preferably hydrazine, 2,4 dinitrophenyl hydrazine.
8, according to claim 11, the removal methods of carbonyl material in the ammediol is characterized in that adding 1, and the NH2-Y compound in the ammediol aqueous solution is wherein a kind of at least.
9, according to claim 11, the removal methods of carbonyl material in the ammediol, the add-on that it is characterized in that the NH2-Y compound is 1, in the ammediol aqueous solution 5～50 of carbonyl content times, best 15～40 times.
10, according to claim 11, the removal methods of carbonyl material in the ammediol, it is characterized in that wherein 1, behind the ammediol aqueous solution and the NH2-Y compound thorough mixing 40～80 ℃ of reactions 1～5 hour down.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021330565A CN1176054C (en) | 2002-09-25 | 2002-09-25 | Method for removing carbonyl material from 1,3-propylene-glycol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021330565A CN1176054C (en) | 2002-09-25 | 2002-09-25 | Method for removing carbonyl material from 1,3-propylene-glycol |
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| CN1413971A true CN1413971A (en) | 2003-04-30 |
| CN1176054C CN1176054C (en) | 2004-11-17 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906020A (en) * | 2010-07-30 | 2010-12-08 | 东营市海科新源化工有限责任公司 | Novel process for purifying 1,2-propylene glycol by ester exchange method |
| CN114276216A (en) * | 2022-01-05 | 2022-04-05 | 江苏扬农化工集团有限公司 | Method for removing aldehyde impurities in 1, 3-propylene glycol |
| CN116323531A (en) * | 2021-06-04 | 2023-06-23 | Kh新化株式会社 | 1, 3-butanediol products |
-
2002
- 2002-09-25 CN CNB021330565A patent/CN1176054C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101906020A (en) * | 2010-07-30 | 2010-12-08 | 东营市海科新源化工有限责任公司 | Novel process for purifying 1,2-propylene glycol by ester exchange method |
| CN101906020B (en) * | 2010-07-30 | 2013-03-13 | 东营市海科新源化工有限责任公司 | Novel process for purifying 1,2-propylene glycol by ester exchange method |
| CN116323531A (en) * | 2021-06-04 | 2023-06-23 | Kh新化株式会社 | 1, 3-butanediol products |
| CN114276216A (en) * | 2022-01-05 | 2022-04-05 | 江苏扬农化工集团有限公司 | Method for removing aldehyde impurities in 1, 3-propylene glycol |
| CN114276216B (en) * | 2022-01-05 | 2023-08-01 | 江苏扬农化工集团有限公司 | Method for removing aldehyde impurities in 1, 3-propylene glycol |
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| Publication number | Publication date |
|---|---|
| CN1176054C (en) | 2004-11-17 |
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