CN1168692C - Alkaline anionic exchange resin process of refining and purifying 1,3-propylene glycol - Google Patents
Alkaline anionic exchange resin process of refining and purifying 1,3-propylene glycol Download PDFInfo
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- CN1168692C CN1168692C CNB011321458A CN01132145A CN1168692C CN 1168692 C CN1168692 C CN 1168692C CN B011321458 A CNB011321458 A CN B011321458A CN 01132145 A CN01132145 A CN 01132145A CN 1168692 C CN1168692 C CN 1168692C
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- Prior art keywords
- ammediol
- exchange resin
- anion exchange
- strongly basic
- basic anion
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Abstract
The present invention relates to a method for refining and purifying 1, 3-propanediol, which comprises the following steps that strong alkaline anionic exchange resin for 1, 3-propanediol, which contains residual aldehyde group substances, is treated at a temperature of 30 to 90 DEG C, the treated material is depressurized and distilled at a temperature of 121 to 149 DEG C, and distillates are condensed so as to obtain the 1, 3-propanediol with high purity. The strong alkaline anionic exchange resin is in a spherical granular shape and has a surface functional group-N+(CH3)OH-, a granule size of the strong alkaline anionic exchange resin ranges from 0.315mm to 1.25mm, specific surface areas are controlled between 1m<2>/g and 20m<2>/g, and pore volume ranges from 0.1 ml/g to 10 ml/g. The strong alkaline anionic exchange resin can be treated in a fixed bed reactor or a suspension bed reactor. 1, 3-propanediol is prepared by hydrating common acrolein, and the method can reduce the content of residual aldehyde group substances to be less than 10 ppm under common conditions.
Description
Technical field
The present invention relates to 1, the refining purification of ammediol particularly removes 1, the method for micro residue aldehyde radical material in the ammediol.
Background technology
1, ammediol is a kind of broad-spectrum compound, and except that can be used for producing urethane and the ring compound, it still is a poly terephthalic acid 1, the principal monomer of ammediol ester fiber.Poly terephthalic acid 1, ammediol ester fiber are the polyester kinds of excellent performance, though just come out in the fifties, but because of 1, ammediol can't be realized industrialization, makes poly terephthalic acid 1, and the development of ammediol ester fiber stays cool for many years all the time.In recent years, along with 1, the success of ammediol suitability for industrialized production, poly terephthalic acid 1, the Application and Development of ammediol ester fiber receives publicity heavily again.Wherein generate the 3-hydroxy propanal by acrolein hydration, and then make 1 by hydrogenation, ammediol is one of successful suitability for industrialized production route.
Produce 1 at the acrolein hydration route, during ammediol, except the 3-hydroxy propanal, also contain unconverted propenal and hydration by product in the hydrated product of propenal.Though can reduce wherein remaining aldehyde radical by hydrogenation; if use relatively harsher hydroconversion condition even can make product not contain remaining aldehyde radical material substantially; but produce 1 with general existing industrialization acrolein hydration route; during ammediol, the remaining aldehyde radical material of the 500ppm that can have an appointment usually in the product.As with this 1, ammediol is produced poly terephthalic acid 1, and the ammediol ester can be to poly terephthalic acid 1, the multinomial quality index of ammediol ester fiber product exerts an influence, 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 removing wherein before the ammediol ester, micro residue aldehyde radical material is very necessary.
Summary of the invention
Technical problem to be solved by this invention provides a kind of removal 1, the method of micro residue aldehyde radical material in the ammediol, it adopts fairly simple technology just to make 1, and the remaining aldehyde group content of ammediol drops to below the 50ppm, thereby solves the problem that prior art exists.
Technical problem to be solved by this invention is achieved through the following technical solutions.
To contain 1 of remaining aldehyde radical material, ammediol is handled with strongly basic anion exchange resin, treatment temp is 30～90 ℃, the underpressure distillation under 121～149 ℃ of temperature of material after the processing, must make with extra care 1 behind the distillate condensing, ammediol, described strongly basic anion exchange resin has surface functional group:
-N
+(CH
3)
3OH
-。
Used strongly basic anion exchange resin is the spherical granules shape, and granularity is 0.315～1.25mm; Specific surface is 1～20m
2Between/the g, be preferably 2～10m
2/ g; Pore volume is 0.1～10ml/g, is preferably 0.2～5ml/g.Best treatment temp is 40～70 ℃.
1, ammediol can carry out in fixed-bed reactor with the processing of strongly basic anion exchange resin, and this hourly space velocity is controlled to be 1～6hr
-1, be preferably 2～5hr
-1Also can carry out in suspended-bed reactor, this moment, the content of reaction solution strongly basic anion exchange resin was 0.1～10wt%, was preferably 2～9wt%.
From being present in 1, the structure that contains the aldehyde radical material of ammediol, they all have active hydrogen on the α position, under acid or alkali effect all condensation reaction can take place, form the molecule of structure more complicated, and these molecules are because boiling point and 1, and it is bigger that ammediol differs, and is easy to be separated by distilling.According to above analysis, the contriver studies the solid catalyst that has certain acid/alkalescence in a large number, and emphasis has been selected molecular sieve, diatomite, strongly basic anion exchange resin and tested.Find that by experiment above-mentioned acid/alkaline matter all is that feasible full gear is catalyst based, yet by relatively comprehensive, strongly basic anion exchange resin is adopted by the present invention because of advantages such as catalytic effect and prices.
Aldehyde radical generally has been considered to following process in the reaction mechanism of strongly basic anion exchange resin:
(1)
(2)
(3) aldehyde that contains active α-H both can continue reaction in the basic center position, also can with other aldehyde generation condensation reaction that does not contain α-H, finally generate the high material of high molecular and boiling point.
In reaction conditions, treatment temp is very big to the influence of aldehyde radical substances content in the product, and the high more aldehyde radical of temperature is removed thorough more.But because 1, intermolecular or molecule inner dewatering reaction can take place in ammediol equally in sour environment, therefore, treatment temp has an optimum range, find that from experiment can both obtain better all effects between 30～90 ℃, wherein Zui Jia treatment temp is between 40～70 ℃.
By 1 of general acrolein hydration route production, ammediol adopts method provided by the invention generally can make 1, and remaining aldehyde radical substances content drops to below the 10ppm in the ammediol.Because method technology provided by the invention is fairly simple, its cost is more much lower than strengthening hydroconversion condition, so its positively effect is very tangible.
Embodiment
To come below that the invention will be further described by a series of embodiment, among the embodiment:
Used strongly basic anion exchange resin has surface functional group :-N
+(CH
3)
3OH
-, granularity is 0.315～1.25mm, specific surface 2～10m
2/ g; Pore volume is 0.2～5ml/g.
[embodiment 1～7]
To contain 1 of remaining aldehyde radical material, ammediol solution is preheated to 30～90 ℃, squeezes into pump in 500 * 30mm reactor of filling strongly basic anion exchange resin and reacts, and air speed is controlled at 4～5hr
-1After the processing 1, ammediol distills, and top temperature is 149 ℃ at the bottom of the still, and 121 ℃ of cat head top temperatures, vacuum tightness are 20mmHg.Treatment temp and treatment effect that each embodiment adopts see Table 1.
[embodiment 8～14]
To contain 1 of remaining aldehyde radical material, ammediol solution is preheated to 60 ℃, squeeze into pump in 500 * 30mm reactor of filling strongly basic anion exchange resin and react, after the processing 1, ammediol distills, top temperature is 149 ℃ at the bottom of the still, and 121 ℃ of cat head top temperatures, vacuum tightness are 20mmHg.Air speed and treatment effect that each embodiment adopts see Table 2.
[embodiment 15～21]
Add in tank reactor and contain 1 of remaining aldehyde radical material, the strongly basic anion exchange resin of ammediol solution and aequum is warming up to 30～90 ℃, react and distill after 1 hour, top temperature is 149 ℃ at the bottom of the still, and 121 ℃ of cat head top temperatures, vacuum tightness are 20mmHg.The concrete consumption and the treatment effect of catalyzer see Table 3..
Table 1.
| Treatment temp (℃) | Raw material aldehyde group content (ppm) | Handle back aldehyde group content (ppm) | Yield (%) | |
| Embodiment 1 | 30 | 2000 | 30 | 99％ |
| Embodiment 2 | 40 | 2000 | 20 | 99％ |
| Embodiment 3 | 50 | 2000 | ＜10 | 99％ |
| Embodiment 4 | 60 | 2000 | ＜10 | 99％ |
| Embodiment 5 | 70 | 2000 | ＜10 | 98％ |
| Embodiment 6 | 80 | 2000 | ＜10 | 98％ |
| Embodiment 7 | 90 | 2000 | ＜10 | 97％ |
Table 2.
| Air speed (hr -1) | Raw material aldehyde group content (ppm) | Handle back aldehyde group content (ppm) | Yield (%) | |
| Embodiment 8 | 1 | 2000 | ＜10 | 99％ |
| Embodiment 9 | 1.5 | 2000 | ＜10 | 99％ |
| Embodiment 10 | 2 | 2000 | ＜10 | 99％ |
| Embodiment 11 | 4 | 2000 | ＜10 | 99％ |
| Embodiment 12 | 4.5 | 2000 | ＜10 | 99％ |
| Embodiment 13 | 5 | 2000 | ＜10 | 99％ |
| Embodiment 14 | 6 | 2000 | 13 | 99％ |
Table 3.
| Catalytic amount (wt%) | Raw material aldehyde group content (ppm) | Handle back aldehyde group content (ppm) | Yield (%) | |
| Embodiment 15 | 0.1 | 2000 | 30 | 99％ |
| Embodiment 16 | 1 | 2000 | 15 | 99％ |
| Embodiment 17 | 1.5 | 2000 | 13 | 99％ |
| Embodiment 18 | 2 | 2000 | ＜10 | 99％ |
| Embodiment 19 | 6 | 2000 | ＜10 | 99％ |
| Embodiment 20 | 7 | 2000 | ＜10 | 99％ |
| Embodiment 21 | 9 | 2000 | ＜10 | 99％ |
Claims (8)
1, a kind of refining purification 1, the method of ammediol, to contain 1 of remaining aldehyde radical material, ammediol is handled with strongly basic anion exchange resin, treatment temp is 30～90 ℃, and the underpressure distillation under 121～149 ℃ of temperature of the material after the processing must make with extra care 1 behind the distillate condensing, ammediol, described strongly basic anion exchange resin has surface functional group :-N
+(CH
3)
3OH
-
2, refining purification 1 according to claim 1, the method for ammediol is characterized in that described strongly basic anion exchange resin is the spherical granules shape, and granularity is 0.315～1.25mm, and specific surface is 1～20m
2Between/the g, pore volume is 0.1～10ml/g.
3, refining purification 1 according to claim 2, the method for ammediol, the specific surface that it is characterized in that described strongly basic anion exchange resin is 2～10m
2/ g, pore volume are 0.2～5ml/g.
4, refining purification 1 according to claim 1 and 2, the method for ammediol is characterized in that described treatment temp is 40～70 ℃.
5, refining purification 1 according to claim 1 and 2, the method for ammediol is characterized in that described treating processes carries out in fixed-bed reactor, air speed is 1hr
-1～6hr
-1
6, refining purification 1 according to claim 5, the method for ammediol is characterized in that described air speed is 2～5hr
-1
7, refining purification 1 according to claim 1 and 2, the method for ammediol is characterized in that described treating processes carries out in suspended-bed reactor, the content of strongly basic anion exchange resin is 0.1～10wt% in the reaction solution.
8, refining purification 1 according to claim 7, the method for ammediol, the content that it is characterized in that strongly basic anion exchange resin in the described reaction solution is 2～9wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011321458A CN1168692C (en) | 2001-11-08 | 2001-11-08 | Alkaline anionic exchange resin process of refining and purifying 1,3-propylene glycol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011321458A CN1168692C (en) | 2001-11-08 | 2001-11-08 | Alkaline anionic exchange resin process of refining and purifying 1,3-propylene glycol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1417185A CN1417185A (en) | 2003-05-14 |
| CN1168692C true CN1168692C (en) | 2004-09-29 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011321458A Expired - Fee Related CN1168692C (en) | 2001-11-08 | 2001-11-08 | Alkaline anionic exchange resin process of refining and purifying 1,3-propylene glycol |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347138C (en) * | 2006-01-23 | 2007-11-07 | 上海华谊丙烯酸有限公司 | Method for removing micro aldehyde group from 1,3-propylene glycol |
| CN102199107B (en) * | 2010-03-26 | 2014-03-26 | 中国石油化工股份有限公司 | Method for removing acrolein from acrylonitrile |
| CN110790636B (en) * | 2018-08-03 | 2022-07-12 | 万华化学集团股份有限公司 | Refining method for removing trace aldehyde group in 1, 3-propylene glycol |
| CN112979420B (en) * | 2021-03-03 | 2022-11-25 | 江苏扬农化工集团有限公司 | Method for purifying 1,3-propylene glycol |
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2001
- 2001-11-08 CN CNB011321458A patent/CN1168692C/en not_active Expired - Fee Related
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| CN1417185A (en) | 2003-05-14 |
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