CN109704978A - A kind of purification process of pentanediamine - Google Patents
A kind of purification process of pentanediamine Download PDFInfo
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- CN109704978A CN109704978A CN201811586227.3A CN201811586227A CN109704978A CN 109704978 A CN109704978 A CN 109704978A CN 201811586227 A CN201811586227 A CN 201811586227A CN 109704978 A CN109704978 A CN 109704978A
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- pentanediamine
- butanol
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Abstract
The present invention relates to a kind of purification process of pentanediamine, the sodium hydrate solid of every liter of 20~400g of addition in the pentanediamine HCI solution that purity is 5%~90%, stirring carries out desalination reaction at being 40~100 DEG C in temperature, obtains free pentanediamine aqueous solution after reaction；N-butanol is added, is that 20~60 DEG C of stirrings are extracted in temperature, stratification after extraction obtains upper layer n-butanol phase and lower layer's water phase；Water phase is cooled to room temperature, centrifuge separation obtains solid sodium hydroxide；N-butanol is mutually purified in rectifying column rectifying, rectifying purification condition is that reboiler temperature is 100~200 DEG C, and reflux ratio is 0.1~5；After rectifying, rectifying tower top recycles n-butanol, and tower bottom recycles pentanediamine product, and purity is higher than 99%.Present invention process is succinct, there is considerable prospects for commercial application.
Description
Technical field
The present invention relates to a kind of purification process of pentanediamine, belong to the purifies and separates technical field of fine chemicals.
Background technique
1,5- pentanediamine also known as 1,5- 1,5-DAP are catalyzed L- by lysine decarboxylase (E.C.4.1.1.18) and rely
Propylhomoserin decarboxylation is made, and is with a wide range of applications.Agriculturally, pentanediamine participates in various physiological processes, such as plant cell
Division, embryo generation, yield positive results；In terms of medicine, pentanediamine can be used for hastening parturition, reduce blood glucose etc.；Industrially
Pentanediamine can be with synthesizing new isocyanates, compared with the isocyanates of existing hexamethylene diamine synthesis, blanketing effect and anti-ization
Corrosive power enhancing is learned, it is more environmentally-friendly, it has a vast market foreground.
The production method of pentanediamine is broadly divided into chemical synthesis and biological fermentation process at present.In process of production, penta 2
Amine purifying is always a bottleneck problem, and the device is complicated mostly, cost input is high, environmental pollution is tight for the purification process of existing report
Weight.If patent CN101970393A is described, alkaline matter is added in the aqueous solution containing di-ammonium salts, then passes through the aqueous solution
Nanofiltration membrane is filtered desalination.But the hole of nanofiltration membrane only has several nanometers, is mainly used for permeating fine particle, salt etc., works as system
In there are in the case where a large amount of thallus, infusible precipitate, nanofiltration membrane easily blocks, it is necessary to using before nanofiltration membrane to solution into
Row pretreatment, to guarantee that the normal work of nanofiltration membrane, time consumption and energy consumption limit the industrial application of this method.Patent
The aqueous solution of CN104974046A description, pentanediamine crude product need to can just obtain pentanediamine after purification by rectifying three times.Three times
Rectifying tower plates number, reflux ratio used in rectifying are different, have increased considerably industrialization cost.Patent CN105612257A
Middle description changes distillation/evaporation system mobility by the way that high boiling organic solvent is added, so that in lower temperature/shorter
Time under distillation/evaporation, obtain the pentanediamine quality of the better pentanediamine rate of recovery/preferably.But its used solvent is
C14Alkane, C11/C14Paraffins mixture, diphenyl ether and lauryl alcohol, it is expensive, and easily cause environmental pollution.
Many bottleneck problems of existing pentanediamine purification process are directed to, the present invention provides a kind of purifying sides of pentanediamine
Method, including the desalination of pentanediamine hydrochloride, extraction and rectifying purifying, process flow and equipment are simple, and cost input is small, and this method
Sodium hydroxide and n-butanol used is repeatable to be recycled, and environmental pollution is small, with considerable economic benefit and social valence
Value, therefore this method has a vast market and prospects for commercial application.
Summary of the invention
It is an object of the invention to develop a kind of purification process (Fig. 1) of pentanediamine, including the desalination of pentanediamine hydrochloride and
Extraction also includes that the rectifying of n-butanol pentanediamine purifies.
In order to realize above-mentioned purpose, the present invention provides a kind of purification process of pentanediamine, and technical solution is as follows:
A kind of purification process of pentanediamine, includes the following steps:
1) desalination of pentanediamine hydrochloride and extraction: add for every liter in the pentanediamine HCI solution that purity is 5%~90%
The sodium hydrate solid for entering 20~400g, stirring carries out desalination reaction at being 40~100 DEG C in temperature, is swum after reaction
From pentanediamine aqueous solution；N-butanol is added, is extracted in temperature for 20~60 DEG C of stirrings, stratification after extraction, in acquisition
Layer n-butanol phase and lower layer's water phase；
2) sodium hydroxide recycling and reusing: water phase is cooled to room temperature, and centrifuge separation obtains solid sodium hydroxide；
3) rectifying of n-butanol phase pentanediamine purifies: n-butanol mutually being purified in rectifying column rectifying, rectifying purification condition is again
Boiling device temperature is 100~200 DEG C, and reflux ratio is 0.1~5；After rectifying, rectifying tower top recycles n-butanol, tower bottom recycling penta
Two amine products.
Sodium hydrate solid is added in the step 1) in one or many modes.
Mixing speed is 100~400rpm at described 40~100 DEG C.
Pentanediamine HCI solution and n-butanol volume ratio are 5:2~5:10.
The rectifying column is sieve-plate tower or packed tower.
The rectifying column effective plate number is 5~25.
Tower bottom recycles pentanediamine purity 99% or more.
The present invention provides a kind of purification process of pentanediamine, have compared with existing pentanediamine purification process following excellent
Point:
(1) in the purification process of pentanediamine of the present invention, whole process of purification does not occur high temperature, operation with high pressure, not
Using the high-risk reagent of high poison, concise in technology, equipment is simple, has considerable economic benefit and social value, therefore this method has
Wide market and prospects for commercial application.
(2) sodium hydroxide used in the present invention and the recyclable recycling of n-butanol, reduce production cost, reduce
Environmental pollution.
Detailed description of the invention
Fig. 1 is that pentanediamine of the invention purifies flow chart.
The change curve of 3 pentanediamine HCI solution desalination processes pH of Fig. 2 embodiment.
Specific embodiment
Technical solution of the present invention is further elaborated with reference to the accompanying drawings and examples, but institute's protection scope of the present invention
It is without being limited thereto.The specific embodiments described herein are only used for describing and explaining the disclosure, are not limited to the disclosure.It is right
The equivalent replacement that the content of present invention is done, or be correspondingly improved, it still falls within protection scope of the present invention.
Embodiment 1
The sodium hydroxide that final concentration of 20g/L is added in the pentanediamine HCI solution that 1L pentanediamine purity is 5% is solid
Body is added at one time whole sodium hydrate solids, and desalination reaction under the conditions of 100 DEG C and 100rpm reacts 10h, by free penta
Two amine aqueous solutions are down to room temperature, and pentanediamine HCI solution and n-butanol volume ratio is added as the n-butanol of 5:2, is 40 in temperature
DEG C and revolving speed be 200rpm under the conditions of extract, time 0.5h is down to room temperature, and settle and separate obtains upper layer n-butanol phase and lower layer
Water phase.Upper layer n-butanol is mutually used for rectifying, and the centrifugation of lower layer's water phase obtains solid sodium hydroxide, recycling.
The n-butanol that 1L pentanediamine purity is 12.5% is used for rectifying purifying reaction, the number of plates 5, reboiler temperature is
100~200 DEG C, reflux ratio 0.1, after rectifying 5h, for tower bottom pentanediamine purity up to 99.1%, the recycling of tower top n-butanol is used for penta
The extraction of diamines.
Embodiment 2
The hydrogen-oxygen that concentration is 200g/L is added at one time in the pentanediamine HCI solution for being 50% by 1L pentanediamine purity
Change sodium solid, free pentanediamine aqueous solution is down to room temperature, pentanediamine is added by desalination reaction 2h under the conditions of 40 DEG C and 200rpm
The n-butanol that HCI solution and n-butanol volume ratio are 5:4, extracts under the conditions of temperature is 60 DEG C and revolving speed is 50rpm, when
Between be 5h, be down to room temperature, settle and separate obtains upper layer n-butanol phase and lower layer's water phase.Upper layer n-butanol is mutually used for rectifying, lower layer
Water phase centrifugation obtains sodium hydrate solid, recycling.
The n-butanol that 1L pentanediamine purity is 62.5% is used for rectifying purifying reaction, the number of plates 10, reboiler temperature
It is 100~190 DEG C, reflux ratio 0.5, after rectifying 2h, up to 99.9%, the recycling of tower top n-butanol is used for tower bottom pentanediamine purity
The extraction of pentanediamine.
Embodiment 3
The sodium hydroxide of final concentration of 400g/L is added in the pentanediamine HCI solution that 1L pentanediamine purity is 90%
Solid, average every 30min add once, every time plus the sodium hydrate solid of final concentration of 50g/L, under the conditions of 80 DEG C with 400rpm
Free pentanediamine aqueous solution is down to room temperature by desalination reaction 5h, and it is 5 that pentanediamine HCI solution and n-butanol volume ratio, which is added:
10 n-butanol extracts under the conditions of temperature is 20 DEG C and revolving speed is 300rpm, and time 1h is down to room temperature, and settle and separate obtains
Obtain upper layer n-butanol phase and lower layer's water phase.Upper layer n-butanol is mutually used for rectifying, and the centrifugation of lower layer's water phase obtains sodium hydrate solid, returns
Receipts recycle.
The n-butanol that 1L pentanediamine purity is 45% is used for rectifying purifying reaction, the number of plates 25, reboiler temperature is
100~190 DEG C, reflux ratio 1, after rectifying 2h, for tower bottom pentanediamine purity up to 99.5%, the recycling of tower top n-butanol is used for penta 2
The extraction of amine.
Claims (7)
1. a kind of purification process of pentanediamine, it is characterised in that include the following steps:
It 1) is the sodium hydrate solid of every liter of 20~400g of addition in 5%~90% pentanediamine HCI solution in purity,
Temperature is that stirring carries out desalination reaction at 40~100 DEG C, obtains free pentanediamine aqueous solution after reaction；N-butanol is added,
It is that 20~60 DEG C of stirrings are extracted in temperature, stratification after extraction obtains upper layer n-butanol phase and lower layer's water phase；
2) water phase is cooled to room temperature, centrifuge separation obtains solid sodium hydroxide；
3) n-butanol is mutually purified in rectifying column rectifying, rectifying purification condition is that reboiler temperature is 100~200 DEG C, reflux ratio
It is 0.1~5；After rectifying, rectifying tower top recycles n-butanol, and tower bottom recycles pentanediamine product.
2. the method as described in claim 1, it is characterized in that sodium hydrate solid is in the step 1) with one or many sides
Formula is added.
3. the method as described in claim 1, it is characterized in that mixing speed is 100~400rpm at described 40~100 DEG C.
4. the method as described in claim 1, it is characterized in that pentanediamine HCI solution and n-butanol volume ratio are 5:2~10.
5. the method as described in claim 1, it is characterized in that the rectifying column is sieve-plate tower or packed tower.
6. the method as described in claim 1, it is characterized in that the rectifying column effective plate number is 5~25.
7. the method as described in claim 1, it is characterized in that tower bottom recycles pentanediamine purity 99% or more.
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Cited By (4)
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|---|---|---|---|---|
| CN111117940A (en) * | 2019-12-04 | 2020-05-08 | 天津大学 | Escherichia coli engineering bacterium and method for high yield of pentamethylene diamine |
| CN114057582A (en) * | 2021-11-16 | 2022-02-18 | 南京工业大学 | Method for continuously separating and purifying pentanediamine hydrochloride crystals |
| CN115611748A (en) * | 2021-07-14 | 2023-01-17 | 上海凯赛生物技术股份有限公司 | Separation method of 1, 5-pentanediamine |
| CN116410094A (en) * | 2021-12-31 | 2023-07-11 | 惠州市绿色能源与新材料研究院 | Polymer grade bio-based pentylene diamine refining and purifying process |
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|---|---|---|---|---|
| CN111117940A (en) * | 2019-12-04 | 2020-05-08 | 天津大学 | Escherichia coli engineering bacterium and method for high yield of pentamethylene diamine |
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| CN114057582A (en) * | 2021-11-16 | 2022-02-18 | 南京工业大学 | Method for continuously separating and purifying pentanediamine hydrochloride crystals |
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