CN1550492A - Method for preparing high-purity acetonitrile - Google Patents
Method for preparing high-purity acetonitrile Download PDFInfo
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- CN1550492A CN1550492A CNA2004100380238A CN200410038023A CN1550492A CN 1550492 A CN1550492 A CN 1550492A CN A2004100380238 A CNA2004100380238 A CN A2004100380238A CN 200410038023 A CN200410038023 A CN 200410038023A CN 1550492 A CN1550492 A CN 1550492A
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- acetonitrile
- oxazole
- impurity
- sulfuric acid
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F19/00—Other details of constructional parts for finishing work on buildings
- E04F19/02—Borders; Finishing strips, e.g. beadings; Light coves
- E04F19/04—Borders; Finishing strips, e.g. beadings; Light coves for use between floor or ceiling and wall, e.g. skirtings
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F19/00—Other details of constructional parts for finishing work on buildings
- E04F19/02—Borders; Finishing strips, e.g. beadings; Light coves
- E04F19/04—Borders; Finishing strips, e.g. beadings; Light coves for use between floor or ceiling and wall, e.g. skirtings
- E04F2019/0404—Borders; Finishing strips, e.g. beadings; Light coves for use between floor or ceiling and wall, e.g. skirtings characterised by the material
- E04F2019/0431—Borders; Finishing strips, e.g. beadings; Light coves for use between floor or ceiling and wall, e.g. skirtings characterised by the material of two or more materials
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- Engineering & Computer Science (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention provides a method for producing high-purity acetonitrile, with which even if crude acetonitrile contains allyl alcohol, oxazole and impurities having strong ultraviolet absorption, they are safely and rapidly removed by an industrially suitable operation. The method for purifying acetonitrile comprises a process for distilling acetonitrile after bringing acetonitrile into contact with sulfuric acid and a process for carrying out adsorption with an adsorbent in purifying of acetonitrile. Especially, the impurities with maximum absorbance in the vicinity of 250 nm wavelength having difficulty in complete removal by a conventional method are effectively removed by the method.
Description
Technical field
The invention relates to the manufacture method of acetonitrile of high purity, more particularly, is about when making vinyl cyanide or methacrylonitrile by ammonia oxidation, makes the method for acetonitrile of high purity from the acetonitrile that contains the strong impurity of secondary ultraviolet radiation absorption of giving birth to.
Background technology
The acetonitrile of giving birth to as by-product when making vinyl cyanide or methacrylonitrile by ammonia oxidation carries out the purified method, in containing the crude acetonitrile of impurity, added sulfuric acid in the past, make contained vinyl carbinol formation sulfuric ester and reach high boiling pointization, isolating method is known (for example the spy opens clear 51-23218 communique) by distillation.In addition, the crude acetonitrile that obtains by ammonia oxidation is contacted with sulfuric acid, make contained De oxazole form vitriol and isolating method is known (for example the spy opens clear 55-20791 communique).In addition, make crude acetonitrile contact back separate sulfur acid moieties with sulfuric acid, then with after ozone gas contacts, obtaining not having the method for acetonitrile of the ultraviolet radiation absorption of wavelength 200nm～350nm by distillation is known (for example the spy opens flat 05-32605 communique).Have, behind the distillation crude acetonitrile, make it pass through acidic cation-exchange resin, the method that obtains the acetonitrile that high pressure liquid chromatography (hereinafter to be referred as HPLC) solvent uses also is known (for example the spy opens flat 11-35542 communique).
The acetonitrile that by-product is given birth to when making vinyl cyanide or methacrylonitrile by the ammonia oxidation of propylene etc. uses as organic compound synthetic starting material with as the solvent in the building-up reactions of various organic compound, but recently, uses such as solvent as HPLC solvent usefulness, pharmaceuticals manufacturing and film video picture usefulness, large-scale liquid crystal film manufacturing usefulness, nearest especially, acetonitrile of high purity there are big needs.Crude acetonitrile contains the pure and mild oxazole of allyl, prussic acid, vinyl cyanide, water, acetone, propenal, propionitrile, suitable-and impurity such as anti--crotononitrile, methacrylonitrile.Wherein especially vinyl carbinol is to have a smelly poisonous substance of strong stimulation, even smaller or equal to 1% content, also give operational all detrimentally affects of exciting eye and nose etc.And the pure and mild oxazole of this allyl is strong to ultraviolet radiation absorption,, must remove by less than the purposes such as HPLC solvent of 190nm the time as ultraviolet ray.
It is the method for removing vinyl carbinol that the spy opens clear 51-23218 communique.It is method from crude acetonitrile Chu Qu oxazole that the spy opens clear 55-20791 communique.But, promptly allow to from crude acetonitrile, remove fully the pure and mild oxazole of allyl, in fact also also have ultraviolet radiation absorption, can not use this problem with solvent as HPLC and exist.This means, in crude acetonitrile, except the pure and mild oxazole of allyl, also have the strong impurity of ultraviolet radiation absorption.
Open in the flat 05-32605 communique the spy and to have proposed, by carrying out the method that oxidation is removed with these impurity of ozonize.But it is difficult that ozonizer is increased to concentration of ozone gas more than or equal to 10 weight % on its performance, and residual ozone becomes air or oxygen.When in acetonitrile, being blown into ozone gas, fiery fried danger is arranged, in order to avoid explosive range, have to add rare gas elementes such as nitrogen or carbonic acid gas, and because the deterioration of gas liquid reaction reaction efficiency, need make a large amount of gas Long contact time, reclaim ozone and the acetonitrile that gasified is operated complicated operations such as necessitate, have the such problem of the industrial production of being unsuitable for.
Te Kaiping 11-35542 communique is to handle by acidic cation-exchange resin, and absorption removes the method for removing alkaline matters such as oxazole, but this method has the problem that can not remove the strong vinyl carbinol of ultraviolet radiation absorption.
Summary of the invention
The object of the present invention is to provide, even crude acetonitrile contains vinyl carbinol, oxazole, other the strong impurity of ultraviolet radiation absorption, also with safety, rapidly, be suitable for operating industrially and remove these materials, make the method for acetonitrile of high purity.
The inventor etc. are in order to address the above problem, carried out found that of research with keen determination, by making crude acetonitrile through contact still-process after the processing and two processes of adsorption treatment process with sulfuric acid, even crude acetonitrile contains vinyl carbinol, oxazole, other the strong impurity of ultraviolet radiation absorption, also can be with safety, rapidly, be suitable for operating industrially and remove these materials, thereby can make acetonitrile of high purity, reach the present invention.
That is, the invention relates to the manufacture method of acetonitrile of high purity, it is characterized in that, with impure acetonitrile by handling with still-process after sulfuric acid contacts with the adsorption treatment process of sorbent material.
Embodiment
(slightly) acetonitrile of Shi Yonging can be obtained by any manufacture method in the present invention, but is effective to secondary the refining of (slightly) acetonitrile of giving birth in the ammonia oxidations such as propylene, propane, iso-butylene, Trimethylmethane especially.When making vinyl cyanide or methacrylonitrile in the secondary crude acetonitrile of giving birth to by the ammonia oxidation of propylene etc., though contain the pure and mild oxazole of allyl, water, acetone, prussic acid, vinyl cyanide, methacrylonitrile, propenal, propionitrile, suitable-and anti--impurity such as crotononitrile, these impurity are reduced to smaller or equal to 1 weight % in the preceding process of technology of the present invention.Though according to the value change of condition foreign matter contents such as distillation tower, for example vinyl carbinol is that 180ppm ， oxazole is 50ppm, water is 500ppm, and propionitrile is 8500ppm, and other are smaller or equal to 10ppm.At this state, ultraviolet cutoff surpasses 190nm.
Contact with sulfuric acid by this crude acetonitrile, vinyl carbinol generation esterification and become sulfuric ester, and etherificate takes place also become diallyl ether.Its result, with the boiling-point difference expansion of acetonitrile, separated easily in distillation.Oxazole becomes vitriol, becomes stillage residue when distillation.Promptly can remove the pure and mild oxazole of the strong allyl of ultraviolet radiation absorption simultaneously by above operation.Organic acids such as mineral acid beyond the sulfuric acid and methylsulfonic acid, Phenylsulfonic acid, tosic acid do not have the effect that can assert fully as above.The impurity that ultraviolet radiation absorption except that vinyl carbinol, oxazole is strong (below, be called impurity A) has the maximum value of absorbancy near wavelength 250nm, finding has the character that is adsorbed agent absorption easily.According to the above-mentioned described pure and mild oxazole of the allyl strong impurity A of ultraviolet radiation absorption in addition of also can removing, can make ultraviolet cutoff less than 190nm.
Though the sulfuric acid concentration of Shi Yonging is arbitrarily in the present invention, but be dehydration reaction and be balanced reaction from reaction with vinyl carbinol, be not suitable for existing a lot of water in reaction system, the preferred sulfuric acid that uses the high density that is higher than 95 weight % also can use oleum.The total mole number of the pure and mild oxazole of the relative allyl of employed vitriolic amount is 0.5～300 times of mole, preferred 1～100 times of mole.Reaction times is if normal temperature is 5～50 hours, if but to be heated near the boiling point be 0.01～5 hour.Be reflected in the line mixer or in the steel basin and carry out, when increasing sulfuric acid concentration,, also can not use reactive tank owing to be swift in response.After the reaction, superfluous sulfuric acid can neutralize, but because there is crystallization to separate out, so in the case, preferably before distillation or fractional crystallization, or passes through strainer.
The acetonitrile of crossing by the distillation vitriolization makes sulfuric acid separate from acetonitrile with resultant of reaction like this, and the distillatory method is arbitrarily.Or increase progression, while or reflux with the distillation tower that possesses return channel and to distill, the purity of acetonitrile then improves.In order to suppress the side reaction of sulfuric acid and acetonitrile, also can carry out underpressure distillation and reduce distillation temperature.Distillate is extracted out from overhead streams or effluent.
The sorbent material that uses in adsorption treatment of the present invention for example can be enumerated gac, silica gel, zeolite, molecular sieve, ion exchange resin etc.For adsorption moisture, preferred zeolite, molecular sieve.In order to adsorb the acetate by the hydrolysis reaction generation of acetonitrile, preferred basic anion exchange resin.In addition, the necessity from the impurity A of vinyl carbinol, oxazole demonstration intensive ultraviolet absorption is in addition removed in absorption preferably comprises acidic cation-exchange resin in adsorption bed.If weakly acidic cation-exchange resin, the weakly acidic cation-exchange resin that preferably has carboxyl, if storng-acid cation exchange resin, the storng-acid cation exchange resin that preferably has sulfo group, but more preferably use storng-acid cation exchange resin with sulfo group.In the case, can be with acid with Na
+The resin of type carries out using after the manipulation of regeneration, but in the non-aqueous solution spent ion exchange resin with H
+Type be good.Amberlitel006F H, the Amberlyst15H of for example commercially available enumerated Rohm and Haas company or the HCR-W2 of Dow Chemical company, モ ノ ス Off イ ア-650C etc.
Adsorption treatment can be to flow to the top of the post of filling sorbent material, also can be mobile downwards, also can be to the logical liquid of the steel basin of putting into sorbent material, even also have no relations to fiber with absorption function or the logical liquid of film.Logical liquid temp is-10～80 ℃, preferably 5～40 ℃.Space velocity (SV) is SV=0.1～300[l/h] scope, but also can be outside this scope.Be generally SV=0.5～20[l/h].Here space velocity (SV) defines with space velocity [l/h]=(logical liquid speed [L/h])/(adsorption bed volume [L]).Utilize the adsorption treatment of sorbent material, can be preceding " contacting the back still-process with sulfuric acid ", any time during back or sulfuric acid contact and the distillation carries out, but from the adsorption efficiency or the viewpoint in sorbent material life-span of impurity A, particularly preferably in carrying out after " contact still-process afterwards with sulfuric acid ".
Embodiment
Embodiments of the invention below are described, but the present invention is not subjected to the restriction of these embodiment.Measure ultra-violet absorption spectrum and absorbancy by following condition.
(1) device: the automatic spectrophotometer UV-3100 of Shimadzu Seisakusho Ltd. type
(2) SCAN SPEED (wavelength speed of feed): FAST
(3) SLIT (the wavelength width of a slit set(ting)value nm of optical splitter): 2.0
(4)RANGE：0～1.000
(5) wavelength: 190～500nm
Embodiment 1
In the manufacturing of the vinyl cyanide of the ammonia oxidation by propylene, will carry out the purified result as the acetonitrile that by product obtains, obtain containing the acetonitrile (below, be called crude acetonitrile) of following impurity.
Vinyl carbinol 51ppm
Oxazole 10ppm
Propionitrile 144ppm
H
2O 164ppm
Other impurity is smaller or equal to 1ppm.Measure the ultra-violet absorption spectrum of this crude acetonitrile, the luminous point data of absorbancy (abs) are as follows.
abs(190nm)＞5.000
abs(250nm)＝0.301
abs(254nm)＝0.290
Crude acetonitrile adds the 97 weight % sulfuric acid (is that 42 times of mole ， Dui oxazoles are 253 times of moles to vinyl carbinol) of 0.36 weight % relatively in this crude acetonitrile, carries out reaction in 3 hours while reflux.After this, when distilling under normal pressure, in the impurity from its distillate, the pure and mild oxazole of allyl is smaller or equal to detecting boundary.In addition, measure ultra-violet absorption spectrum, the luminous point data of absorbancy (abs) are as follows, though ultraviolet cutoff is reached less than 190nm, but still near wavelength 250nm, have the maximum value of absorbancy, show remaining impurity A.
abs(190nm)＝0.883
abs(250nm)＝0.039
abs(254nm)＝0.035
Use HPLC with acetonitrile the post of the 15mm * 300mm of this distillate by having filled strong-acid ion exchange resin Amberlyst15H weight in wet base (wet) 20.0g to be carried out after logical fully liquid cleans, SV=3.9 leads to liquid from the top with space velocity.The ultra-violet absorption spectrum of the acetonitrile behind the logical liquid of mensuration, the luminous point data of absorbancy (abs) are as follows, and ultraviolet cutoff is reached less than 190nm, and do not have the very big of wavelength 250nm, can adsorb and remove impurity A.
abs(190nm)＝0.734
abs(250nm)＝0.006
abs(254nm)＝0.005
Comparative example 1
The crude acetonitrile that uses among the embodiment 1 is not carried out vitriolization, the post that uses HPLC will fill 15mm * 300mm of strong-acid ion exchange resin Amberlyst15H weight in wet base (wet) 20.0g with acetonitrile lead to fully liquid clean after, SV=3.9 leads to liquid from the top with space velocity.The acetonitrile behind the liquid is led in analysis, detects the vinyl carbinol of 33ppm, has confirmed that only carrying out adsorption treatment can not remove vinyl carbinol.In addition, measure ultra-violet absorption spectrum, do not have the maximum value of wavelength 250nm, can adsorb and remove impurity A, but the luminous point data of absorbancy (abs) are as follows, ultraviolet cutoff is reached less than 190nm.
abs(190nm)＝3.151
abs(250nm)＝0.013
abs(254nm)＝0.014
By the present invention, make secondary acetonitrile of giving birth to and still-process after sulfuric acid contacts and make with extra care by containing with the adsorption treatment process of sorbent material, with industrial easy method, remove vinyl carbinol, oxazole, other the strong impurity of ultraviolet radiation absorption rapidly, safely, can make acetonitrile of high purity.Especially be effective near the removing of impurity that is difficult to remove fully in the method in the past, maximum value is arranged wavelength 250nm.
Claims (2)
1. the manufacture method of an acetonitrile of high purity is characterized in that, with impure acetonitrile by handling with still-process after sulfuric acid contacts with the adsorption treatment process of sorbent material.
2. the manufacture method of acetonitrile of high purity according to claim 1 is characterized in that, sorbent material contains and has carboxyl or sulfonic acidic cation-exchange resin.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003135980 | 2003-05-14 | ||
| JP2003135980A JP2004339112A (en) | 2003-05-14 | 2003-05-14 | Method for producing high-purity acetonitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1550492A true CN1550492A (en) | 2004-12-01 |
| CN100341849C CN100341849C (en) | 2007-10-10 |
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ID=33526092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100380238A Expired - Lifetime CN100341849C (en) | 2003-05-14 | 2004-05-12 | Method for preparing high-purity acetonitrile |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2004339112A (en) |
| KR (1) | KR20040098576A (en) |
| CN (1) | CN100341849C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101665451B (en) * | 2009-09-14 | 2013-04-24 | 郑州正力聚合物科技有限公司 | Acrylonitrile purifying unit |
| CN101570498B (en) * | 2009-05-27 | 2013-07-17 | 安徽时联特种溶剂股份有限公司 | Method for producing HPLC acetonitrile by multistage reaction-fractionating method |
| CN107074749A (en) * | 2014-10-31 | 2017-08-18 | 旭化成株式会社 | The manufacture method of acetonitrile |
| CN111960966A (en) * | 2020-09-14 | 2020-11-20 | 永华化学股份有限公司 | Preparation method of chromatographic grade acetonitrile |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5173897B2 (en) * | 2009-03-11 | 2013-04-03 | 広栄化学工業株式会社 | Acetonitrile production method |
| CN102993046A (en) * | 2011-09-15 | 2013-03-27 | 上海安谱科学仪器有限公司 | Purification method of HPLC-grade acetonitrile for LC-MS |
| US10336690B2 (en) * | 2014-02-24 | 2019-07-02 | Honeywell International Inc. | Methods and systems for processing an acetonitrile waste stream |
| CN112587950A (en) * | 2014-09-29 | 2021-04-02 | 英尼奥斯欧洲股份公司 | Vaporization system for process streams |
| JP6251821B2 (en) * | 2014-10-31 | 2017-12-20 | 旭化成株式会社 | Acetonitrile production method |
| CN107108474B (en) * | 2014-10-31 | 2019-08-06 | 旭化成株式会社 | The manufacturing method of acetonitrile |
| CN109704990B (en) * | 2017-10-26 | 2022-02-01 | 中国石油化工股份有限公司 | Refining method of high-purity acetonitrile |
| WO2022173933A1 (en) * | 2021-02-11 | 2022-08-18 | Ascend Performance Materials Operations Llc | Acetonitrile separation process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3001020B2 (en) * | 1991-08-01 | 2000-01-17 | 旭化成工業株式会社 | Acetonitrile purification method |
| CN1105099C (en) * | 1997-08-05 | 2003-04-09 | 标准石油公司 | Purification of acetonitrile by distillative recovery/ion exchange resin treatment process |
-
2003
- 2003-05-14 JP JP2003135980A patent/JP2004339112A/en active Pending
-
2004
- 2004-05-12 CN CNB2004100380238A patent/CN100341849C/en not_active Expired - Lifetime
- 2004-05-13 KR KR1020040033885A patent/KR20040098576A/en not_active Application Discontinuation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101570498B (en) * | 2009-05-27 | 2013-07-17 | 安徽时联特种溶剂股份有限公司 | Method for producing HPLC acetonitrile by multistage reaction-fractionating method |
| CN101665451B (en) * | 2009-09-14 | 2013-04-24 | 郑州正力聚合物科技有限公司 | Acrylonitrile purifying unit |
| CN107074749A (en) * | 2014-10-31 | 2017-08-18 | 旭化成株式会社 | The manufacture method of acetonitrile |
| CN107074749B (en) * | 2014-10-31 | 2019-07-16 | 旭化成株式会社 | The manufacturing method of acetonitrile |
| CN111960966A (en) * | 2020-09-14 | 2020-11-20 | 永华化学股份有限公司 | Preparation method of chromatographic grade acetonitrile |
| CN111960966B (en) * | 2020-09-14 | 2022-03-08 | 永华化学股份有限公司 | Preparation method of chromatographic grade acetonitrile |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100341849C (en) | 2007-10-10 |
| JP2004339112A (en) | 2004-12-02 |
| KR20040098576A (en) | 2004-11-20 |
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Address after: Tokyo, Japan, Japan Patentee after: Mitsubishi Kasei Corporation Address before: Tokyo, Japan, Japan Patentee before: Mitsubishi Reiyon Co., Ltd. |