CN108997211A - A kind of method of solvent crystallisation by cooling separation 4- cyanopyridine - Google Patents

A kind of method of solvent crystallisation by cooling separation 4- cyanopyridine Download PDF

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Publication number
CN108997211A
CN108997211A CN201810673365.9A CN201810673365A CN108997211A CN 108997211 A CN108997211 A CN 108997211A CN 201810673365 A CN201810673365 A CN 201810673365A CN 108997211 A CN108997211 A CN 108997211A
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China
Prior art keywords
cyanopyridine
cooling separation
solvent
crystallisation
decolorization
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CN201810673365.9A
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纪红兵
冯政杰
张瑞
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Sun Yat Sen University
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Sun Yat Sen University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D213/00Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/84Nitriles

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)

Abstract

The invention discloses a kind of methods of solvent crystallisation by cooling separation 4- cyanopyridine, include the following steps: that the mixing cyanopyridine raw material containing nicotinonitrile and 4- cyanopyridine is carried out decolorization by (1) at high temperature;(2) the mixing cyanopyridine raw material after decolorization is dissolved in advantage solvent methanol in a crystallizer, is configured to supersaturated solution;(3) be cooled to final temperature to supersaturated solution with certain cooling rate is precipitated 4- cyanopyridine, 4- cyanopyridine enters filter with mixing cyanopyridine mother liquor crystallizer is discharged in a form of slurry, the two is separated in the filter, then obtains high-purity 4- cyanopyridine product after drying.The present invention only needs One-step crystallization after raw material decolorization since crystallisation by cooling separation has the advantage of low energy consumption, low cost, and product purity is up to 99.2% ~ 99.7%.Production cost of the invention is low, good in economic efficiency, while also solving the problem of waste recovery utilizes.

Description

A kind of method of solvent crystallisation by cooling separation 4- cyanopyridine
Technical field
The present invention relates to a kind of methods of solvent crystallisation by cooling separation 4- cyanopyridine.
Background technique
Cyanopyridine be widely used in pesticide and pesticide intermediate, medical product and medicine intermediate, feed and its raw material, The production fields such as fragrance.Cyanopyridine mixture is mainly derived from the ammoxidation synthesis of alkyl pyridine, there are two types of which contains Isomer: nicotinonitrile and 4- cyanopyridine.Wherein, the important use of nicotinonitrile be hydrolyzed obtained niacin or Niacinamide also can be used as intermediate for synthesizing derivative products nicotinate chromium as feed addictive and nutritional additive.4- cyano Pyridine is mainly used for synthesizing anti-tuberculosis drugs rimifon as important medicine, dyestuff intermediate.In order to obtain required height Purity intermediates raw material, it is necessary to carry out separation and purification.
The method that industrial separation mostly uses rectification under vacuum at present is divided from nicotinonitrile and 4- cyanopyridine mixed system 4- cyanopyridine is separated out to increase economic efficiency.Since there are a small amount of picolines in ammonia oxygen in 3/4- cyanopyridine mixture Change the by-product-anti-maleic nitrile (2-Butenedinitritle(Trans-) generated in reaction process), its presence will be tight The separation of cyanopyridine mixture system is interfered again.Anti-maleic nitrile holds very much in cyanopyridine mixture system rectifying separation process Polymerization reaction easily occurs, generated polymer not only influences the variation of material component in rectifying column, and polymerization generated Object easily blocks rectifier unit equipment and influences its normal operation, causes the inferior separating effect of 4- cyanopyridine in industrial production strong People's will, and it is high to operate operating cost.Consider that manufacturing enterprise is usually by the 3/4- cyano pyrrole of the cyanopyridine containing 4- based on economic cost Pyridine homologous mixture works as offal treatment, or directly as chemical spent material burning disposal, leads to cyanopyridine homologous mixture Recovery utilization rate it is low, cause greatly waste and environmental pollution.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of solvent crystallisation by cooling separation 4- cyanopyridine Method.This method has the advantages that high efficiency, high-purity, low cost, low energy consumption.
The present invention utilizes solvent crystallisation by cooling partition method, dissolves in a solvent according to cyanopyridine admixture of isomeric compound The difference of degree carries out separation 4- cyanopyridine.
Technical scheme is as follows:
A kind of method of solvent crystallisation by cooling separation 4- cyanopyridine, it is characterised in that include the following steps:
(1) the mixing cyanopyridine raw material containing nicotinonitrile and 4- cyanopyridine is subjected to decolorization at high temperature;
(2) the mixing cyanopyridine raw material after decolorization is dissolved in advantage solvent (methanol) in a crystallizer, is configured to satiate And solution;Advantage solvent methanol selected by the present invention is from methanol, ethyl alcohol, n-butanol, normal propyl alcohol, isobutanol, acetone, acetic acid It is screened in this 8 kinds of ethyl ester and carbon tetrachloride.Screening be at identical temperature nicotinonitrile and 4- cyanopyridine in the solvent In the biggish solvent of dissolubility difference.
(3) be cooled to final temperature to supersaturated solution with certain cooling rate is precipitated 4- cyanopyridine, 4- Cyanopyridine enters filter with mixing cyanopyridine mother liquor crystallizer is discharged in a form of slurry, and the two obtains in the filter Separation, then high-purity 4- cyanopyridine product is obtained after drying.
In the method for above-mentioned solvent crystallisation by cooling separation 4- cyanopyridine, the temperature of step (1) described decoloration is 80 DEG C, and with stirring in decolorization.
In the method for above-mentioned solvent crystallisation by cooling separation 4- cyanopyridine, the operating temperature range of the crystallizer is 50 ~ 5 DEG C, operating pressure is normal pressure.
In the method for above-mentioned solvent crystallisation by cooling separation 4- cyanopyridine, the operation temperature of the filter is 0 ~ 5 DEG C, operating pressure is normal pressure.
In the method for above-mentioned solvent crystallisation by cooling separation 4- cyanopyridine, step (3) cooling rate is 0.05 ~ 0.3℃/min。
In the method for above-mentioned solvent crystallisation by cooling separation 4- cyanopyridine, the crystallizer has agitating device.
Compared with prior art, the invention has the following beneficial effects: the present invention using one-step method solvent crystallisation by cooling point From 4- cyanopyridine.Since crystallisation by cooling separation has the advantage of low energy consumption, low cost, and a step is only needed after raw material decolorization Crystallization, product purity is up to 99.2% ~ 99.7%.Method production cost of the invention is low, good in economic efficiency, while also solving useless The problem of material recycles.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
Embodiment 1:
Mixing cyanopyridine raw material containing nicotinonitrile and 4- cyanopyridine is decolourized in decoloration device at 80 DEG C, The filtrate after filtration treatment is added in methanol again, prepare the solution that degree of supersaturation is 0.05 at 45 DEG C and continues to stir, is stirred Rate is 150 rpm, and crystallization temperature is down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.05 DEG C/min, the crystal that final filter is precipitated For 99.4% high-purity 4- cyanopyridine product.
Embodiment 2:
According to condition described in embodiment 1 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.1, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.05 DEG C/min, and the crystal that final filter is precipitated is 99.5% high Purity 4- cyanopyridine product.
Embodiment 3:
According to condition described in embodiment 1 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.2, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.05 DEG C/min, and the crystal that final filter is precipitated is 99.4% high Purity 4- cyanopyridine product.
Embodiment 4:
According to condition described in embodiment 1 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.3, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.05 DEG C/min, and the crystal that final filter is precipitated is 99.4% high Purity 4- cyanopyridine product.
Embodiment 5:
According to condition described in embodiment 1 and step, preparing solution degree of supersaturation at 45 DEG C is 0.05, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is changed to 0.1 DEG C/min, and the crystal that final filter is precipitated is 99.6% high Purity 4- cyanopyridine product.
Embodiment 6:
According to condition described in embodiment 5 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.1, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.1 DEG C/min, and the crystal that final filter is precipitated is 99.7% high Purity 4- cyanopyridine product.
Embodiment 7:
According to condition described in embodiment 6 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.2, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.1 DEG C/min, and the crystal that final filter is precipitated is 99.4% high-purity Spend 4- cyanopyridine product.
Embodiment 8:
According to condition described in embodiment 7 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.3, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.1 DEG C/min, and the crystal that final filter is precipitated is 99.5% high Purity 4- cyanopyridine product.
Embodiment 9:
According to condition described in embodiment 1 and step, preparing solution degree of supersaturation at 45 DEG C is 0.05, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is changed to 0.2 DEG C/min, and the crystal that final filter is precipitated is 99.6% high Purity 4- cyanopyridine product.
Embodiment 10:
According to condition described in embodiment 9 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.1, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.2 DEG C/min, and the crystal that final filter is precipitated is 99.2% high-purity Spend 4- cyanopyridine product.
Embodiment 11:
According to condition described in embodiment 10 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.2, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.2 DEG C/min, and the crystal that final filter is precipitated is 99.3% high Purity 4- cyanopyridine product.
Embodiment 12:
According to condition described in embodiment 11 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.3, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.2 DEG C/min, and the crystal that final filter is precipitated is 99.4% high Purity 4- cyanopyridine product.
Embodiment 13:
According to condition described in embodiment 1 and step, preparing solution degree of supersaturation at 45 DEG C is 0.05, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is changed to 0.3 DEG C/min, and the crystal that final filter is precipitated is 99.2% high Purity 4- cyanopyridine product.
Embodiment 14:
According to condition described in embodiment 13 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.1, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.3 DEG C/min, and the crystal that final filter is precipitated is 99.6% high Purity 4- cyanopyridine product.
Embodiment 15:
According to condition described in embodiment 13 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.2, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.3 DEG C/min, and the crystal that final filter is precipitated is 99.3% high Purity 4- cyanopyridine product.
Embodiment 16:
According to condition described in embodiment 13 and step, prepares solution degree of supersaturation at 45 DEG C and be changed to 0.3, stirring rate 150 Rpm, crystallization temperature are down to 5 DEG C from 50 DEG C, and rate of temperature fall is 0.3 DEG C/min, and the crystal that final filter is precipitated is 99.5% high-purity Spend 4- cyanopyridine product.

Claims (6)

1. a kind of method of solvent crystallisation by cooling separation 4- cyanopyridine, it is characterised in that include the following steps:
(1) the mixing cyanopyridine raw material containing nicotinonitrile and 4- cyanopyridine is subjected to decolorization at high temperature;
(2) the mixing cyanopyridine raw material after decolorization is dissolved in advantage solvent methanol in a crystallizer, is configured to supersaturation Solution;
(3) be cooled to final temperature to supersaturated solution with certain cooling rate is precipitated 4- cyanopyridine, 4- cyano Pyridine enters filter with mixing cyanopyridine mother liquor crystallizer is discharged in a form of slurry, and the two is divided in the filter From, then high-purity 4- cyanopyridine product is obtained after drying.
2. the method for solvent crystallisation by cooling separation 4- cyanopyridine as described in claim 1, which is characterized in that step (1) institute The temperature for stating decoloration is 80 DEG C, and with stirring in decolorization.
3. the method for solvent crystallisation by cooling separation 4- cyanopyridine as described in claim 1, which is characterized in that the crystallizer Operating temperature range be 50 ~ 5 DEG C, operating pressure is normal pressure.
4. the method for solvent crystallisation by cooling separation 4- cyanopyridine as described in claim 1, which is characterized in that the filter Operation temperature be 0 ~ 5 DEG C, operating pressure is normal pressure.
5. the method for solvent crystallisation by cooling separation 4- cyanopyridine as described in claim 1, which is characterized in that step (3) institute Stating cooling rate is 0.05 ~ 0.3 DEG C/min.
6. the method for solvent crystallisation by cooling separation 4- cyanopyridine as described in claim 1, which is characterized in that the crystallizer With agitating device.
CN201810673365.9A 2018-06-27 2018-06-27 A kind of method of solvent crystallisation by cooling separation 4- cyanopyridine Pending CN108997211A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110746352A (en) * 2019-11-11 2020-02-04 安徽瑞邦生物科技有限公司 Method for separating 4-cyanopyridine by solvent cooling crystallization
BE1027319B1 (en) * 2019-08-01 2021-01-13 Anhui Redpont Biotechnology Co Ltd Process for the purification of 4-cyanopyridine by melt crystallization
CN114539143A (en) * 2022-01-28 2022-05-27 安徽瑞邦生物科技有限公司 Purification method of 4-cyanopyridine

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Publication number Priority date Publication date Assignee Title
CN101602719A (en) * 2009-04-29 2009-12-16 南通醋酸化工股份有限公司 The synthetic method of 4-cyanopyridine
CN103467370A (en) * 2013-09-12 2013-12-25 南通天泽化工有限公司 Synthesis method of cyanopyridine and derivatives thereof
CN106478498A (en) * 2016-09-23 2017-03-08 哈尔滨理工大学 Using chemical recrystallization and physical separation combine purification 4 cyanopyridines method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101602719A (en) * 2009-04-29 2009-12-16 南通醋酸化工股份有限公司 The synthetic method of 4-cyanopyridine
CN103467370A (en) * 2013-09-12 2013-12-25 南通天泽化工有限公司 Synthesis method of cyanopyridine and derivatives thereof
CN106478498A (en) * 2016-09-23 2017-03-08 哈尔滨理工大学 Using chemical recrystallization and physical separation combine purification 4 cyanopyridines method

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Title
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1027319B1 (en) * 2019-08-01 2021-01-13 Anhui Redpont Biotechnology Co Ltd Process for the purification of 4-cyanopyridine by melt crystallization
CN110746352A (en) * 2019-11-11 2020-02-04 安徽瑞邦生物科技有限公司 Method for separating 4-cyanopyridine by solvent cooling crystallization
CN110746352B (en) * 2019-11-11 2023-03-14 安徽瑞邦生物科技有限公司 Method for separating 4-cyanopyridine by solvent cooling crystallization
CN114539143A (en) * 2022-01-28 2022-05-27 安徽瑞邦生物科技有限公司 Purification method of 4-cyanopyridine

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Application publication date: 20181214