CN102199108A - Method for removing oxazole from acrylonitrile - Google Patents
Method for removing oxazole from acrylonitrile Download PDFInfo
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- CN102199108A CN102199108A CN2010101337508A CN201010133750A CN102199108A CN 102199108 A CN102199108 A CN 102199108A CN 2010101337508 A CN2010101337508 A CN 2010101337508A CN 201010133750 A CN201010133750 A CN 201010133750A CN 102199108 A CN102199108 A CN 102199108A
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- oxazole
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- vinyl cyanide
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Abstract
The invention relates to a method for removing oxazole from acrylonitrile, which mainly solves the problems that the space velocity of an acrylonitrile raw material is low, the treatment capacity of removing the oxazole is low when the oxazole is removed from the acrylonitrile raw material in the prior art. The method comprises the following step of: contacting cation exchange resin with the acrylonitrile raw material to remove the oxazole from the acrylonitrile raw material, wherein the cation exchange resin is at least one of 001 gel type strong basic styrene cation exchange resin, D001 macroporous strong acid styrene cation exchange resin, D112 weakly acidic acrylic acid cation exchange resin and D113 weakly acidic acrylic acid cation exchange resin. The technical scheme better solves the problems, and the method can be applied to industrial production of purification treatment of high performance polyacrylonitrile-based carbon fiber materials.
Description
Technical field
The present invention relates to a kind of removal methods of vinyl cyanide Zhong oxazole.
Background technology
High-performance polyacrylonitrile-based carbon fiber has good material over-all properties: high strength, high-modulus, low density, high-low temperature resistant, resistance to chemical attack, good conductivity, thermal expansivity are little, radiation hardness, good biocompatibility, be the most important strongthener of advanced composite material, be widely used in aerospace leading-edge fields such as satellite, launch vehicle, tactical missile, aircraft, spaceship.
Vinyl cyanide is a main raw material of producing high-performance polyacrylonitrile-based carbon fiber.One of key of carbon fiber performance quality is the quality of vinyl cyanide material quality, and the preparation high-performance polyacrylonitrile-based carbon fiber is high to the purity requirement of raw material propylene nitrile.Present domestic vinyl cyanide raw material is mainly derived from the finished product by propylene, ammonoxidizing fluid bed explained hereafter, contain metallic impurity such as organic impurity such as micro-acetaldehyde, prussic acid, acetone, propenal, methacrylonitrile, oxazole, propionitrile, crotononitrile, stopper, superoxide and iron ion in the industry top grade product vinyl cyanide, these impurity have a strong impact on properties of carbon.The existence of Qi Shi oxazole of impurity You in the raw material propylene nitrile is to cause one of important factor in order of carbon fiber defective, and these defectives can't be eliminated in post-treatment.Vinyl cyanide Zhong oxazole impurity will cause colourity, intensity, the degradation of carbon fiber.Therefore, must carry out further refining purifying to industrial top grade product vinyl cyanide before use, remove the organic impuritys such as oxazole in it, to satisfy of the requirement of high-performance polyacrylonitrile-based carbon fiber precursor to raw material.
Document US 5476883 has been introduced the technology that the pure vinyl cyanide of a kind of usefulness prepares acrylamide, wherein pure vinyl cyanide obtains by two separation phases at least, at first vinyl cyanide contacts with a kind of storng-acid cation exchange resin, this resin can be gel type resin or macroporous resin, handles the H type that changes into diluted acid before using; Contact or contact with activated carbon with a kind of resin that contains primary amine and/or secondary amine group then, this resin can be porous resin or gel resin, handles with dilute alkaline soln before using, and activated carbon can be coal-based or the shell base.Resin or activated carbon can be installed in the fixed bed, and with the vinyl cyanide Continuous Contact, treatment temp is usually at 5～50 ℃, preferred 15～30 ℃.The vinyl cyanide flow is resin or activated carbon 0.1～50 times/hour, preferred 0.5～10 times/hour.Propenal, oxazole disappears in the vinyl cyanide after two steps handled, and superoxide can't check.
Document US 4208329 has been introduced with sulfuric acid and has been contacted with acrylonitrile monemer, and Xing Cheng oxazole vitriol is removed oxazole vitriol in evaporation or distillation Shi from vinyl cyanide.This method sulfuric acid is Yu the optimization mol ratio of oxazole is 2: 1 to 15: 1.
Above-mentioned document relates to the removal methods of vinyl cyanide Zhong oxazole, will introduce new impurity but add sulfuric acid in vinyl cyanide, has increased the intractability that removes impurity and has distilled the cost of handling.Adopt the described Zeo-karb of above-mentioned document, the vinyl cyanide air speed is less, and the processing power of Tuo Chu oxazole is less.
Summary of the invention
Technical problem to be solved by this invention is to existing the vinyl cyanide air speed less during oxazole Zhong removing vinyl cyanide Yuan Liao in the prior art, and the processing power problem of smaller of Tuo Chu oxazole provides a kind of removal methods of new vinyl cyanide Zhong oxazole.It is big that this method has the vinyl cyanide air speed, the big advantage of processing power of Tuo Chu oxazole.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of removal methods of vinyl cyanide Zhong oxazole, adopt Zeo-karb to contact with the vinyl cyanide raw material, remove raw material propylene nitrile Zhong De oxazole, wherein Zeo-karb is selected from least a in 001 gel-type polystyrene strong-acid cation-exchange resin, D001 macroporous type polystyrene strong-acid cation-exchange resin, D112 used for acrylic weak Zeo-karb or the D113 used for acrylic weak Zeo-karb.
In the technique scheme, the volume space velocity of raw material propylene nitrile is 1～300 hour
-1, preferable range is 51～300 hours
-1, more preferably scope is 100～250 hours
-1The treatment temp that removes vinyl cyanide Zhong oxazole is 5～70 ℃, and preferable range is 10～35 ℃.
The Zeo-karb that adopts among the present invention should carry out pre-treatment and activation treatment before using.Preprocessing process is as follows: Zeo-karb is placed exchange column, carried out backwash 30 minutes with pure water, remove impurity, be 4% salt acid treatment 1 hour with concentration then, the dilute hydrochloric acid solution consumption is 2～3 times of resin volume, is 4% sodium hydroxide solution processing 1 hour with concentration again after washing, and the diluted sodium hydroxide solution consumption is 2～3 times of resin volume, after washing, handled 1 hour with dilute hydrochloric acid is same again, wash at last.With pretreated ion exchange resin carry out under 20～70 ℃ the vacuum condition drying activation after 8～12 hours with standby.
You Yu oxazole has weakly alkaline ， oxazole class material can generate salt with acid-respons, with acidic-group generation nucleophilic addition.Zeo-karb contains sulfonic group (SO
3H), carboxyl (COOH) or phenylol (C
6H
4OH) etc. the acidic-group on acidic-group ， oxazole and the Zeo-karb reacts and is attracted on the ion exchange resin and is removed.
Adopting method of the present invention, is that its vinyl cyanide raw material volume space velocity can reach 300 hours under 5～70 ℃ the condition in temperature of reaction
-1, the vinyl cyanide Zhong De oxazole after the processing for can't check, has been obtained better technical effect on mass spectrum.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1]
The adsorption tower internal diameter is 32mm, and 001 gel-type polystyrene strong-acid cation-exchange resin is dry under 70 ℃ vacuum condition after pre-treatment such as washing, 4% chlorohydric acid pickling, washing, 4% sodium hydroxide alkali cleaning, washing, 4% chlorohydric acid pickling, washing to activate 8 hours.The raw material propylene nitrile contacts with 001 gel-type polystyrene strong-acid cation-exchange resin, and treatment temp is 5 ℃, and raw material propylene nitrile volume space velocity is 100 hours
-1, vinyl cyanide Yuan Liao Zhong oxazole content is 50ppm, removes back vinyl cyanide Zhong De oxazole for can't check.
[embodiment 2]
The adsorption tower internal diameter is 25mm, and D001 macroporous type polystyrene strong-acid cation-exchange resin is dry under 70 ℃ vacuum condition after pre-treatment such as washing, 4% chlorohydric acid pickling, washing, 4% sodium hydroxide alkali cleaning, washing, 4% chlorohydric acid pickling, washing to activate 12 hours.The raw material propylene nitrile contacts with D001 macroporous type polystyrene strong-acid cation-exchange resin, and treatment temp is 10 ℃, and raw material propylene nitrile volume space velocity is 300 hours
-1, vinyl cyanide Yuan Liao Zhong oxazole content is 50ppm, removes back vinyl cyanide Zhong De oxazole for can't check.
[embodiment 3]
The adsorption tower internal diameter is 14mm, and D112 used for acrylic weak Zeo-karb is dry under 70 ℃ vacuum condition after pre-treatment such as washing, 4% chlorohydric acid pickling, washing, 4% sodium hydroxide alkali cleaning, washing, 4% chlorohydric acid pickling, washing to activate 12 hours.The raw material propylene nitrile contacts with D112 used for acrylic weak Zeo-karb, and treatment temp is 35 ℃, and raw material propylene nitrile volume space velocity is 250 hours
-1, vinyl cyanide Yuan Liao Zhong oxazole content is 50ppm, removes back vinyl cyanide Zhong De oxazole for can't check.
[embodiment 4]
The adsorption tower internal diameter is 25mm, and D113 used for acrylic weak Zeo-karb is dry under 70 ℃ vacuum condition after pre-treatment such as washing, 4% chlorohydric acid pickling, washing, 4% sodium hydroxide alkali cleaning, washing, 4% chlorohydric acid pickling, washing to activate 8 hours.The raw material propylene nitrile contacts with D113 used for acrylic weak Zeo-karb, and treatment temp is 70 ℃, and raw material propylene nitrile volume space velocity is 51 hours
-1, vinyl cyanide Yuan Liao Zhong oxazole content is 50ppm, removes back vinyl cyanide Zhong De oxazole for can't check.
[embodiment 5]
The adsorption tower internal diameter is 25mm, and D001 macroporous type polystyrene strong-acid cation-exchange resin is dry under 70 ℃ vacuum condition after pre-treatment such as washing, 4% chlorohydric acid pickling, washing, 4% sodium hydroxide alkali cleaning, washing, 4% chlorohydric acid pickling, washing to activate 8 hours.The raw material propylene nitrile contacts with D001 macroporous type polystyrene strong-acid cation-exchange resin, and treatment temp is 70 ℃, and raw material propylene nitrile volume space velocity is 1 hour
-1, vinyl cyanide Yuan Liao Zhong oxazole content is 50ppm, removes back vinyl cyanide Zhong De oxazole for can't check.
Claims (4)
1. the removal methods of oxazole in the vinyl cyanide, adopt Zeo-karb to contact with the vinyl cyanide raw material, remove raw material propylene nitrile Zhong De oxazole, wherein Zeo-karb is selected from least a in 001 gel-type polystyrene strong-acid cation-exchange resin, D001 macroporous type polystyrene strong-acid cation-exchange resin, D112 used for acrylic weak Zeo-karb or the D113 used for acrylic weak Zeo-karb.
2. the removal methods of vinyl cyanide Zhong oxazole according to claim 1, the volume space velocity that it is characterized in that the raw material propylene nitrile is 1～300 hour
-1, the treatment temp that removes vinyl cyanide Zhong oxazole is 5～70 ℃.
3. the removal methods of vinyl cyanide Zhong oxazole according to claim 2, the volume space velocity that it is characterized in that the raw material propylene nitrile is 51～300 hours
-1, the treatment temp that removes vinyl cyanide Zhong oxazole is 10～35 ℃.
4. the removal methods of vinyl cyanide Zhong oxazole according to claim 3, the volume space velocity that it is characterized in that the raw material propylene nitrile is 100～250 hours
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101337508A CN102199108A (en) | 2010-03-26 | 2010-03-26 | Method for removing oxazole from acrylonitrile |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101337508A CN102199108A (en) | 2010-03-26 | 2010-03-26 | Method for removing oxazole from acrylonitrile |
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|---|---|
| CN102199108A true CN102199108A (en) | 2011-09-28 |
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| CN2010101337508A Pending CN102199108A (en) | 2010-03-26 | 2010-03-26 | Method for removing oxazole from acrylonitrile |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925212A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | A kind of adsorbent and method for removing oxazole from acrylonitrile |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4237303A (en) * | 1979-04-30 | 1980-12-02 | The Dow Chemical Company | Removal of oxazole from acrylonitrile |
-
2010
- 2010-03-26 CN CN2010101337508A patent/CN102199108A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4237303A (en) * | 1979-04-30 | 1980-12-02 | The Dow Chemical Company | Removal of oxazole from acrylonitrile |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106925212A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | A kind of adsorbent and method for removing oxazole from acrylonitrile |
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Application publication date: 20110928 |