JP2003238533A - Method for deodorizing n-vinyl-2-pyrrolidone - Google Patents
Method for deodorizing n-vinyl-2-pyrrolidoneInfo
- Publication number
- JP2003238533A JP2003238533A JP2002043174A JP2002043174A JP2003238533A JP 2003238533 A JP2003238533 A JP 2003238533A JP 2002043174 A JP2002043174 A JP 2002043174A JP 2002043174 A JP2002043174 A JP 2002043174A JP 2003238533 A JP2003238533 A JP 2003238533A
- Authority
- JP
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- Prior art keywords
- pyrrolidone
- vinyl
- distillation column
- nvp
- purity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Pyrrole Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｎ−ビニル−２−
ピロリドンの脱臭方法に関するものである。Ｎ−ビニル
−２−ピロリドンは、医薬品、食品添加剤、パーソナル
ケア品等の原料として広範な用途のあるポリ−Ｎ−ビニ
ル−２−ピロリドンの原料モノマーとして有用な化合物
である。TECHNICAL FIELD The present invention relates to N-vinyl-2-
The present invention relates to a method for deodorizing pyrrolidone. N-vinyl-2-pyrrolidone is a compound useful as a raw material monomer for poly-N-vinyl-2-pyrrolidone, which has a wide range of uses as a raw material for drugs, food additives, personal care products and the like.
【０００２】[0002]
【従来の技術】Ｎ−ビニル−２−ピロリドンは、従来よ
り２−ピロリドンとアセチレンとを加圧下に液相でアル
カリ触媒の存在下に反応するレッペ法により工業生産さ
れている。また、アセチレンを用いないＮ−ビニル−２
−ピロリドンの製造方法も提案されている。例えば、Ｎ
−（２−ヒドロキシエチル）−２−ピロリドンとオクチ
ニルクロライドとの反応によって得られるＮ−（２−ク
ロロエチル）−２−ピロリドンを脱塩化水素する方法
（米国特許第２７７５５９９号公報）や、Ｎ−（２−ヒ
ドロキシエチル）−２−ピロリドンと無水酢酸との反応
によって得られる酢酸エステル中間体を脱酢酸する方法
や、Ｎ−（２−ヒドロキシエチル）−２−ピロリドンを
触媒の存在下に気相で分子内脱水反応させる方法（特開
平８−１４１４０２号公報）等である。2. Description of the Related Art N-vinyl-2-pyrrolidone has hitherto been industrially produced by the Reppe process in which 2-pyrrolidone and acetylene are reacted under pressure in the liquid phase in the presence of an alkali catalyst. In addition, N-vinyl-2 that does not use acetylene
-A method for producing pyrrolidone has also been proposed. For example, N
A method of dehydrochlorinating N- (2-chloroethyl) -2-pyrrolidone obtained by the reaction of-(2-hydroxyethyl) -2-pyrrolidone and octynyl chloride (US Pat. No. 2,775,599) and N- A method of deaceticating an acetic acid ester intermediate obtained by the reaction of (2-hydroxyethyl) -2-pyrrolidone and acetic anhydride, or N- (2-hydroxyethyl) -2-pyrrolidone in the gas phase in the presence of a catalyst. Intramolecular dehydration reaction (Japanese Patent Application Laid-Open No. 8-141402).
【０００３】上記の製造方法によって得られるＮ−ビニ
ル−２−ピロリドンには、それぞれ未反応原料、触媒、
副生成物等が含まれているので、蒸留等の適当な回収及
び精製方法によりＮ−ビニル−２−ピロリドンを得なけ
ればならない。The N-vinyl-2-pyrrolidone obtained by the above production method contains unreacted raw materials, catalysts, and
Since it contains by-products and the like, N-vinyl-2-pyrrolidone must be obtained by an appropriate recovery and purification method such as distillation.
【０００４】しかしながら、一般的な回収及び精製方法
によって得られるＮ−ビニル−２−ピロリドンには、特
表平８−５０６５８０号公報や特開平９−１６９７２４
号公報に開示されているように、副生成物である不飽和
炭化水素類、塩基性化合物、ビニルエーテル化合物等の
不純物が含有されており、これらは、医薬品や食品添加
剤等の用途にとって好ましくないものであるばかりでな
く、製品の色相や臭気に悪影響を及ぼす。However, N-vinyl-2-pyrrolidone obtained by a general recovery and purification method is disclosed in JP-A-8-506580 and JP-A-9-169724.
As disclosed in Japanese Patent Publication No. JP-A-2003-187, it contains impurities such as unsaturated hydrocarbons, basic compounds, and vinyl ether compounds, which are by-products, and these are not preferable for applications such as pharmaceuticals and food additives. Not only that, but it also adversely affects the hue and odor of the product.
【０００５】そこで、上記問題点の解決法として、例え
ば、米国特許第５０３９８１７号公報では、酸性イオン
交換体で不純物を除去する方法が、また、特開平７−２
５２２２１号公報では、有機カルボン酸の無水物を添加
して処理する方法等が開示されている。しかし、これら
の方法は、イオン交換体の再生や、副原料の使用やその
廃棄が必要であり、商業的に有利な方法ではない。ま
た、特表平８−５０６５８０号公報や特開平９−１６９
７２４号公報には、多段分別結晶法によりＮ−ビニル−
２−ピロリドンを精製する方法が開示されている。しか
し、この方法は、精製に特別な装置が必要であり、工程
も複雑であり、操作が煩雑であるという問題を有してい
る。Therefore, as a solution to the above-mentioned problems, for example, in US Pat. No. 5,039,817, a method of removing impurities with an acidic ion exchanger is also disclosed in JP-A-7-2.
Japanese Patent No. 52221 discloses a method of adding an organic carboxylic acid anhydride for treatment. However, these methods require regeneration of ion exchangers, use of secondary raw materials, and disposal thereof, and are not commercially advantageous methods. In addition, JP-T 8-506580 and JP-A 9-169.
No. 724, N-vinyl-by a multi-stage fractional crystallization method.
A method for purifying 2-pyrrolidone is disclosed. However, this method has a problem that a special apparatus is required for purification, the process is complicated, and the operation is complicated.
【０００６】[0006]
【発明が解決しようとする課題】従って、本発明の目的
は、上記のような従来技術の問題点を改良すること、具
体的には、臭気成分を含む純度９０重量％以上のＮ−ビ
ニル−２−ピロリドンから、臭気成分を含まない精製さ
れたＮ−ビニル−２−ピロリドンを得ることが可能な方
法を提供することにある。SUMMARY OF THE INVENTION Therefore, an object of the present invention is to improve the above-mentioned problems of the prior art, specifically, N-vinyl-containing odor components having a purity of 90% by weight or more. An object of the present invention is to provide a method capable of obtaining purified N-vinyl-2-pyrrolidone containing no odorous component from 2-pyrrolidone.
【０００７】[0007]
【課題を解決するための手段】本発明の上記の目的は、
下記（１）及び（２）のいずれかの態様に従う方法によ
って達成することができる。The above objects of the present invention are as follows.
This can be achieved by the method according to any one of the following (1) and (2).
【０００８】態様（１） 臭気成分を含む純度９０重量
％以上のＮ−ビニル−２−ピロリドンを、蒸留塔を用い
て蒸留することにより、臭気成分を留出液として除去す
ることを特徴とするＮ−ビニル−２−ピロリドンの脱臭
方法。 Aspect (1) The odorous component is removed as a distillate by distilling N-vinyl-2-pyrrolidone containing odorous component and having a purity of 90% by weight or more using a distillation column. A method for deodorizing N-vinyl-2-pyrrolidone.
【０００９】態様（２） 臭気成分を含む純度９０重量
％以上のＮ−ビニル−２−ピロリドンにＮ−ビニル−２
−ピロリドンより沸点の低い化合物の少なくとも一種を
添加して得られる液を、蒸留塔を用いて蒸留することに
より、臭気成分を上記化合物と共に留出液として除去す
ることを特徴とするＮ−ビニル−２−ピロリドンの脱臭
方法。 Aspect (2) N-vinyl-2-pyrrolidone having a purity of 90% by weight or more containing an odor component and N-vinyl-2
-N-vinyl-characterized in that a liquid obtained by adding at least one compound having a boiling point lower than that of pyrrolidone is distilled as a distillate using a distillation column to remove the odorous component as a distillate together with the above compound. Method of deodorizing 2-pyrrolidone.
【００１０】[0010]
【発明の実施の形態】以下に、本発明を具体的に説明す
る。なお、以下の記載において、ＮＶＰはＮ−ビニル−
２−ピロリドンの略称である。本発明で蒸留操作の対象となる液
一般的な回収及び精製方法を行って得られる、不飽和炭
化水素類、塩基性化合物、ビニルエーテル化合物等の不
純物、特に、臭気成分を含む純度９０重量％以上のＮＶ
Ｐが、本発明の方法において蒸留操作の対象とされる。
そのようなＮＶＰの具体的な例としては、例えば、レッ
ペ法により工業生産されているＮＶＰや特開平８−１４
１４０２号公報に開示されたＮＶＰの製造方法による反
応生成物を冷却捕集した液を蒸留等の一般的な回収・精
製方法を行って得られるものが挙げられるが、特にこれ
らに限定されるものではない。態様（１）の方法
態様（１）の方法における蒸留操作は、次のような条件
の下で実施される。この蒸留操作は、脱臭効果を上げる
ために、繰り返し実施することができ、その結果として
色相改善の効果も得られる。
塔底液の温度：１８０℃以下、好ましくは、１６５℃以
下である。塔底液の温度が１８０℃より高い場合には、
塔底液に含まれているＮＶＰの重合反応や熱分解が促進
され、ＮＶＰの回収率が低下する。
蒸留塔の操作圧力：蒸留する液の組成にもよるが、通
常、２.６７×１０4Ｐａ（２００ｍｍＨｇ）以下、好ま
しくは、２.００×１０4Ｐａ（１５０ｍｍＨｇ）以下で
ある。
蒸留の形式：特に制限されないが、回分式や連続式の方
法を用いることができる。
連続的に蒸留を行う場合に蒸留する液の供給個所：特に
制限はなく、蒸留塔の任意の個所から行うことができ
る。
蒸留塔の形式：蒸留塔は、その形式に格別の制限はな
く、通常、棚段塔または充填塔などのような精留塔が使
用される。塔の段数は、蒸留する液の組成や還流比に応
じて適宜に選択することができるが、通常、理論段数３
〜３０程度である。態様（２）の方法
態様（２）の方法における蒸留操作は、次のような条件
の下で実施される。この蒸留操作は、脱臭効果を上げる
ために、繰り返し実施することができる。
塔底液の温度：１８０℃以下、好ましくは、１６５℃以
下である。塔底液の温度が１８０℃より高い場合には、
塔底液に含まれているＮＶＰの重合反応や熱分解が促進
され、ＮＶＰの回収率が低下する。
蒸留塔の操作圧力：蒸留する液の組成にもよるが、通
常、２.６７×１０4Ｐａ（２００ｍｍＨｇ）以下、好ま
しくは、２.００×１０4Ｐａ（１５０ｍｍＨｇ）以下で
ある。
蒸留の形式：特に制限されないが、回分式や連続式の方
法を用いることができる。
回分蒸留の場合：ＮＶＰより沸点の低い化合物を臭気成
分を含む純度９０重量％以上のＮＶＰに添加する方法と
しては、臭気成分を含む純度９０重量％以上のＮＶＰと
ＮＶＰより沸点の低い化合物とを予め混合した溶液を塔
底部に仕込む方法あるいは臭気成分を含む純度９０重量
％以上のＮＶＰとＮＶＰより沸点の低い化合物とをそれ
ぞれ別々に塔底部に仕込む方法が通常採られるが、これ
らに限られるものではない。
連続蒸留の場合：蒸留する液の供給個所については特に
制限はなく、蒸留塔の任意の個所から行うことができ
る。蒸留する液の供給方法も特に制限されないが、通
常、臭気成分を含む純度９０重量％以上のＮＶＰとＮＶ
Ｐより沸点の低い化合物との混合溶液を供給する方法あ
るいは臭気成分を含む純度９０重量％以上のＮＶＰとＮ
ＶＰより沸点の低い化合物とをそれぞれ別々に供給する
方法が採られる。ＮＶＰより沸点の低い化合物を添加す
る方法も格別の制限はなく、臭気成分を含む純度９０重
量％以上のＮＶＰとＮＶＰより沸点の低い化合物とを予
め混合する方法あるいは臭気成分を含む純度９０重量％
以上のＮＶＰとＮＶＰより沸点の低い化合物とを連続的
に混合する（混合しながら供給する）方法を採ることが
できる。
蒸留塔の形式：態様（１）に関して前記したと同様の蒸
留塔を使用することができる。
ＮＶＰより沸点の低い化合物：ＮＶＰより沸点の低い化
合物については、特に限定されないが、水酸基を有する
化合物あるいは常圧で１５０℃以下の沸点を有する化合
物が好ましい。水は、取扱い性、経済性及びそれ自体が
無臭であることから、好ましい。ＮＶＰに水酸基を有す
る化合物たとえば水を一定量以上加えた場合、希釈され
ることでＮＶＰそのものの臭気は減少するけれども臭気
成分の臭気が際立って感じられるという現象を本発明者
は観察している（後記の「臭気官能試験」参照）。この
現象は、ＮＶＰとの親和性が、該臭気成分より水の方が
強いために起こるものであろうと推測される。ＮＶＰよ
り沸点の低い化合物として水酸基を有する化合物が好ま
しいとされる理由はここにある。常圧で１５０℃以下の
沸点を有する化合物が好ましいとされる理由は、その蒸
留分離の容易さにある。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. In the following description, NVP is N-vinyl-
Abbreviation for 2-pyrrolidone. Liquid subject to distillation operation in the present invention Impurities such as unsaturated hydrocarbons, basic compounds, vinyl ether compounds, etc., obtained by carrying out general recovery and purification methods, in particular, odor components and purity of 90% by weight or more NV
P is subjected to a distillation operation in the method of the present invention.
Specific examples of such NVP include, for example, NVP industrially produced by the Reppe method and Japanese Unexamined Patent Publication (Kokai) No. 8-14.
The liquid obtained by cooling and collecting the reaction product obtained by the method for producing NVP disclosed in Japanese Patent No. 1402 is obtained by a general recovery / purification method such as distillation, but is not particularly limited to these. is not. Method of Aspect (1) The distillation operation in the method of aspect (1) is carried out under the following conditions. This distillation operation can be repeatedly performed in order to enhance the deodorizing effect, and as a result, the effect of improving the hue can be obtained. Temperature of bottom liquid: 180 ° C. or lower, preferably 165 ° C. or lower. If the temperature of the bottom liquid is higher than 180 ° C,
The polymerization reaction and thermal decomposition of NVP contained in the column bottom liquid are promoted, and the NVP recovery rate is reduced. Operating pressure of the distillation column: It is usually 2.67 × 10 4 Pa (200 mmHg) or less, preferably 2.00 × 10 4 Pa (150 mmHg) or less, though it depends on the composition of the liquid to be distilled. Distillation format: Although not particularly limited, a batch method or a continuous method can be used. Where the liquid to be distilled is supplied in the case where the distillation is continuously carried out: There is no particular limitation, and it can be carried out from any place in the distillation column. Format of distillation column: The format of the distillation column is not particularly limited, and a rectification column such as a plate column or a packed column is usually used. The number of plates in the column can be appropriately selected depending on the composition of the liquid to be distilled and the reflux ratio, but normally, the number of theoretical plates is 3
It is about 30. Distillation in a method aspect the method aspect of (2) (2) is carried out under the following conditions. This distillation operation can be repeatedly performed in order to enhance the deodorizing effect. Temperature of bottom liquid: 180 ° C. or lower, preferably 165 ° C. or lower. If the temperature of the bottom liquid is higher than 180 ° C,
The polymerization reaction and thermal decomposition of NVP contained in the column bottom liquid are promoted, and the NVP recovery rate is reduced. Operating pressure of the distillation column: It is usually 2.67 × 10 4 Pa (200 mmHg) or less, preferably 2.00 × 10 4 Pa (150 mmHg) or less, though it depends on the composition of the liquid to be distilled. Distillation format: Although not particularly limited, a batch method or a continuous method can be used. In the case of batch distillation: As a method of adding a compound having a boiling point lower than that of NVP to NVP containing an odor component and having a purity of 90% by weight or more, NVP containing an odor component and having a purity of 90% by weight or more and a compound having a boiling point lower than that of NVP are used. A method of charging a premixed solution to the bottom of the column or a method of charging NVP having a purity of 90% by weight or more containing an odor component and a compound having a lower boiling point than NVP separately to the bottom of the column is usually adopted, but the method is not limited to these. is not. In the case of continuous distillation: There are no particular restrictions on the supply location of the liquid to be distilled, and it can be performed from any location in the distillation column. The method of supplying the liquid to be distilled is not particularly limited, but normally, NVP and NV containing odorous components and having a purity of 90% by weight or more are used.
A method of supplying a mixed solution with a compound having a boiling point lower than that of P or NVP and N having a purity of 90% by weight or more containing an odorous component
A method of separately supplying a compound having a lower boiling point than VP is adopted. The method of adding a compound having a boiling point lower than that of NVP is not particularly limited, and a method of premixing NVP having a purity of 90% by weight or more containing an odor component and a compound having a boiling point lower than that of NVP or a purity of 90% by weight containing an odor component
A method of continuously mixing (supplying while mixing) the above NVP and a compound having a lower boiling point than NVP can be adopted. Type of distillation column: A distillation column similar to that described above with respect to embodiment (1) can be used. Compound having a lower boiling point than NVP: The compound having a lower boiling point than NVP is not particularly limited, but a compound having a hydroxyl group or a compound having a boiling point of 150 ° C. or lower at normal pressure is preferable. Water is preferable because it is easy to handle, economical, and odorless in itself. The present inventor has observed that when a compound having a hydroxyl group, such as water, is added to NVP in a certain amount or more, the odor of NVP itself is reduced by dilution, but the odor of the odor component is noticeably noticed ( (See "Odor sensory test" below). It is speculated that this phenomenon may occur because water has stronger affinity with NVP than the odorous component. This is the reason why the compound having a hydroxyl group is preferred as the compound having a lower boiling point than NVP. The reason why the compound having a boiling point of 150 ° C. or lower at atmospheric pressure is preferable is that the compound is easily separated by distillation.
【００１１】ＮＶＰよりも沸点が低い化合物の具体例と
しては、ペンタン、ヘキサン、シクロヘキサン、メチル
シクロヘキサン、ヘプタン、オクタン、イソオクタンな
どのような脂肪族炭化水素類；ベンゼン、トルエン、キ
シレン、エチルベンゼンなどのような芳香族炭化水素
類；ジクロロメタン、１,２−ジクロロエタン、クロロ
ホルム、四塩化炭素、クロロベンゼンなどのようなハロ
ゲン化炭化水素類；メタノール、エタノール、１−プロ
パノール、２−プロパノール、１−ブタノール、２−ブ
タノール、イソブタノール、ｔ−ブタノールなどのよう
なアルコール化合物類；ジエチルエーテル、ジイソプロ
ピルエーテル、ジブチルエーテル、テトラヒドロフラ
ン、ジオキソラン、ジオキサン、１,２−ジメトキシエ
タン、１,２−ジエトキシエタンなどのようなエーテル
化合物類；アセトン、メチルエチルケトン、メチルイソ
ブチルケトンなどのようなケトン化合物類；ギ酸メチ
ル、ギ酸エチル、酢酸メチル、酢酸エチルなどのような
エステル化合物類；更には、水、アセトニトリル、ニト
ロメタンなど、が挙げられる。Specific examples of compounds having a lower boiling point than NVP include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, octane and isooctane; benzene, toluene, xylene, ethylbenzene and the like. Aromatic hydrocarbons; halogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, etc .; methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2- Alcohol compounds such as butanol, isobutanol, t-butanol, etc .; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxolane, dioxane, 1,2-dimethoxyethane, 1,2-diethoxy Ether compounds such as tan; ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone; ester compounds such as methyl formate, ethyl formate, methyl acetate, ethyl acetate; further water, acetonitrile, Examples include nitromethane.
【００１２】ＮＶＰより沸点の低い化合物の添加量は、
臭気成分を含むＮＶＰ純度９０重量％以上の液の重量を
基準にして、０.０３〜１.０倍、好ましくは０.０５〜
０.７倍、更に好ましくは０.１〜０.５倍とされる。０.
０３倍より少ない場合には臭気成分の留出除去が十分に
できなくなり、一方、１.０倍より大きい場合には留出
に多大なエネルギーを使用するので経済的に不利とな
る。The addition amount of the compound having a lower boiling point than NVP is
Based on the weight of a liquid containing 90% by weight or more of NVP containing an odorous component, it is 0.03-1.0 times, preferably 0.05-
It is set to 0.7 times, more preferably 0.1 to 0.5 times. 0.
When the amount is less than 03 times, distillative removal of odorous components cannot be sufficiently performed, while when it is more than 1.0 times, a large amount of energy is used for distilling, which is economically disadvantageous.
【００１３】なお、この態様（２）の場合も、蒸留塔の
缶出液を繰り返し蒸留することによって、色相改善の効
果を得ることができる。Also in the case of this mode (2), the effect of improving the hue can be obtained by repeatedly distilling the bottoms of the distillation column.
【００１４】[0014]
【実施例】［臭気官能試験］臭気成分を含むＮ−ビニル
−２−ピロリドンに水酸基を有する化合物、例えば、水
を一定量以上加えた場合、Ｎ−ビニル−２−ピロリドン
が希釈されることで、Ｎ−ビニル−２−ピロリドンその
ものの臭気が減少し、臭気成分の臭気が際立って感じら
れるという現象を本発明者は観察している。この現象
は、Ｎ−ビニル−２−ピロリドン中の臭気の官能試験に
利用することができる。下記の実施例１における連続蒸
留塔２に供給する臭気成分を含む純度９９.８重量％の
Ｎ−ビニル−２−ピロリドン（連続蒸留塔２への供給
液）について行われた臭気官能試験の例を、以下に示
す。すなわち、実施例１における連続蒸留塔２への供給
液と、その濃度が１０重量％になるように水で希釈した
溶液とを用意し、それぞれの液を１０人の被験者に嗅が
せて、臭気を感じた被験者の数を記録したところ、表１
に示す結果が得られた。Examples [Odor sensory test] A compound having a hydroxyl group, for example, N-vinyl-2-pyrrolidone containing an odor component, is diluted with N-vinyl-2-pyrrolidone when water is added thereto in a certain amount or more. The present inventor has observed a phenomenon in which the odor of N-vinyl-2-pyrrolidone itself is reduced, and the odor of the odor component is noticeable. This phenomenon can be used for sensory test of odor in N-vinyl-2-pyrrolidone. Example of odor sensory test performed on N-vinyl-2-pyrrolidone having a purity of 99.8% by weight (supply liquid to continuous distillation column 2) containing an odor component to be supplied to continuous distillation column 2 in Example 1 below. Is shown below. That is, a supply liquid to the continuous distillation column 2 in Example 1 and a solution diluted with water so that the concentration thereof was 10% by weight were prepared, and 10 liquids of each liquid were smelled by 10 test subjects to give an odor. The number of subjects who felt was recorded in Table 1.
The results shown in are obtained.
【００１５】[0015]
【表１】 [Table 1]
【００１６】上記表１に示したように、水で希釈した溶
液を用いる方が臭気の存在が際立って感じられる。それ
故、下記の実施例における臭気官能試験では、検体とし
て、連続蒸留塔２の缶出液の１０重量％水溶液を用い
た。As shown in Table 1 above, the presence of odor is more noticeable when using a solution diluted with water. Therefore, in the odor sensory test in the examples below, a 10 wt% aqueous solution of the bottom liquid of the continuous distillation column 2 was used as a sample.
【００１７】[0017]
【実施例１】図１に示す装置を用いて、本発明の態様
（１）に従う方法を実施した。臭気成分を含む純度９
９.８重量％のＮ−ビニル−２−ピロリドン（供給液）
を連続的に蒸留した。タンク１からの供給液は連続蒸留
塔２において蒸留され、塔頂から臭気成分が留出されて
導管８を経て排出される。連続蒸留塔２は、内径３５ｍ
ｍのガラス管に充填物として直径３５ｍｍのステンレス
製スルーザーパッキンを濃縮部に４エレメント、回収部
に６エレメント充填したものを用いた。留出タンク３内
の留出液の温度は１０℃に保った。連続蒸留塔２は、操
作圧が１.３３×１０4Ｐａ（１００ｍｍＨｇ）で、還流
比が２となるように留出タンク３から連続蒸留塔２に還
流される留出液量を操作した。タンク１から連続蒸留塔
２に供給する液の単位時間当たりの供給量（以下、供給
速度と記す）、連続蒸留塔２から留出して凝縮器４及び
留出タンク３を経て導管８から抜き出される留出液の単
位時間当たりの留出量（以下、留出速度と記す）、連続
蒸留塔２から導管１０を経て缶出した缶出液の単位時間
当たりの缶出量（以下、缶出速度と記す）を表２に示
す。また、連続蒸留塔２の塔頂温度および塔底液温度を
表３に示す。さらに、連続蒸留塔２の缶出液の臭気官能
試験結果を表４に示す。Example 1 The method according to the embodiment (1) of the present invention was carried out using the apparatus shown in FIG. Purity including odor components 9
9.8% by weight of N-vinyl-2-pyrrolidone (feed solution)
Was continuously distilled. The liquid supplied from the tank 1 is distilled in the continuous distillation column 2, and the odorous components are distilled from the top of the column and discharged via the conduit 8. Continuous distillation column 2 has an inner diameter of 35 m
As a filling material, a glass tube of m having a diameter of 35 mm and a stainless-steel throughzer packing having a diameter of 35 mm was filled in the concentrating portion with 4 elements and the collecting portion with 6 elements. The temperature of the distillate in the distilling tank 3 was kept at 10 ° C. In the continuous distillation column 2, the operating pressure was 1.33 × 10 4 Pa (100 mmHg), and the amount of distillate refluxed from the distillation tank 3 to the continuous distillation column 2 was adjusted so that the reflux ratio was 2. The amount of the liquid supplied from the tank 1 to the continuous distillation column 2 per unit time (hereinafter referred to as the supply rate), the amount of the liquid distilled from the continuous distillation column 2, the condenser 4 and the distillation tank 3, and the withdrawal from the conduit 8. Amount of distillate per unit time (hereinafter referred to as distilling rate) to be collected, amount of bottom liquid per unit time discharged from the continuous distillation column 2 via the conduit 10 (hereinafter referred to as bottom output Table 2 shows the speed). Table 3 shows the column top temperature and column bottom liquid temperature of the continuous distillation column 2. Table 4 shows the results of the odor sensory test of the bottoms of the continuous distillation column 2.
【００１８】[0018]
【表２】 [Table 2]
【００１９】[0019]
【表３】 [Table 3]
【００２０】[0020]
【表４】 [Table 4]
【００２１】以上のようにして臭気成分の除去されたＮ
−ビニル−２−ピロリドン（連続蒸留塔２の缶出液）の
純度は、９９.９重量％であった。As described above, N from which the odorous component has been removed
The purity of vinyl-2-pyrrolidone (the bottoms of the continuous distillation column 2) was 99.9% by weight.
【００２２】[0022]
【実施例２】図１に示す装置を用いて、本発明の態様
（２）に従う方法を実施した。臭気成分を含む純度９
９.８重量％のＮ−ビニル−２−ピロリドンとその重量
に対して０.３３倍の水を混合した溶液を連続的に蒸留
した。連続蒸留塔２としては実施例１と同様の構成のも
のを使用し、留出タンク３内の留出液の温度を１０℃に
保った。連続蒸留塔２は、操作圧が１.３３×１０4Ｐａ
（１００ｍｍＨｇ）で、還流比が１となるように留出タ
ンク３から連続蒸留塔２に還流される留出液量を操作し
た。連続蒸留塔２の供給速度、留出速度、及び缶出速度
を各液の組成と共に表５に示す。但し、表５中のＮＶＰ
は、Ｎ−ビニル−２−ピロリドンを意味する。また、連
続蒸留塔２の塔頂温度および塔底液温度を表６に示す。
さらに、連続蒸留塔２の缶出液の臭気官能試験結果を表
７に示す。Example 2 A method according to embodiment (2) of the present invention was carried out using the apparatus shown in FIG. Purity including odor components 9
A solution obtained by mixing 9.8% by weight of N-vinyl-2-pyrrolidone and 0.33 times its weight of water was continuously distilled. As the continuous distillation column 2, the one having the same structure as in Example 1 was used, and the temperature of the distillate in the distilling tank 3 was kept at 10 ° C. The operating pressure of the continuous distillation column 2 is 1.33 × 10 4 Pa.
The amount of distillate liquid refluxed from the distilling tank 3 to the continuous distillation column 2 was manipulated so that the reflux ratio was 1 at (100 mmHg). Table 5 shows the feed rate, the distillation rate, and the bottom rate of the continuous distillation column 2 together with the composition of each liquid. However, NVP in Table 5
Means N-vinyl-2-pyrrolidone. Table 6 shows the column top temperature and column bottom liquid temperature of the continuous distillation column 2.
Further, Table 7 shows the results of the odor sensory test of the bottoms of the continuous distillation column 2.
【００２３】[0023]
【表５】 [Table 5]
【００２４】[0024]
【表６】 [Table 6]
【００２５】[0025]
【表７】 [Table 7]
【００２６】以上のようにして臭気成分の除去されたＮ
−ビニル−２−ピロリドン（連続蒸留塔２の缶出液）の
純度は、９９.９重量％であった。As described above, N from which the odorous component has been removed
The purity of vinyl-2-pyrrolidone (the bottoms of the continuous distillation column 2) was 99.9% by weight.
【００２７】[0027]
【実施例３】図１に示す装置を用いて、本発明の態様
（２）に従う方法を実施した。臭気成分を含む純度９
９.８重量％のＮ−ビニル−２−ピロリドンとその重量
に対して０.３３倍のメタノールを混合した溶液を連続
的に蒸留した。連続蒸留塔２としては実施例１と同様の
構成のものを使用し、留出タンク３内の留出液の温度を
１０℃に保った。連続蒸留塔２は、操作圧が１.３３×
１０4Ｐａ（１００ｍｍＨｇ）で、還流比が０.５となる
ように留出タンク３から連続蒸留塔２に還流される留出
液量を操作した。連続蒸留塔２の供給速度、留出速度、
及び缶出速度を各液の組成と共に表８に示す。但し、表
８中のＮＶＰは、Ｎ−ビニル−２−ピロリドンを意味す
る。また、連続蒸留塔２の塔頂温度および塔底液温度を
表９に示す。さらに、連続蒸留塔２の留出液の臭気官能
試験結果を表１０に示す。Example 3 A method according to embodiment (2) of the present invention was carried out using the apparatus shown in FIG. Purity including odor components 9
A solution in which 9.8% by weight of N-vinyl-2-pyrrolidone and 0.33 times its weight of methanol were mixed was continuously distilled. As the continuous distillation column 2, the one having the same structure as in Example 1 was used, and the temperature of the distillate in the distilling tank 3 was kept at 10 ° C. The operating pressure of the continuous distillation column 2 is 1.33 ×
At 10 4 Pa (100 mmHg), the amount of distillate refluxed from the distilling tank 3 to the continuous distillation column 2 was manipulated so that the reflux ratio was 0.5. The feed rate of the continuous distillation column 2, the distillation rate,
The canning speed and the composition of each solution are shown in Table 8. However, NVP in Table 8 means N-vinyl-2-pyrrolidone. Table 9 shows the column top temperature and column bottom liquid temperature of the continuous distillation column 2. Table 10 shows the results of the odor sensory test of the distillate from the continuous distillation column 2.
【００２８】[0028]
【表８】 [Table 8]
【００２９】[0029]
【表９】 [Table 9]
【００３０】[0030]
【表１０】 [Table 10]
【００３１】以上のようにして臭気成分の除去されたＮ
−ビニル−２−ピロリドン（連続蒸留塔２の缶出液）の
純度は、９９.９重量％であった。The N from which the odorous components have been removed as described above
The purity of vinyl-2-pyrrolidone (the bottoms of the continuous distillation column 2) was 99.9% by weight.
【００３２】[0032]
【実施例４】図１に示す装置を用いて、本発明の態様
（２）に従う方法を実施した。臭気成分を含む純度９
９.８重量％のＮ−ビニル−２−ピロリドンとその重量
に対して０.１３倍の水および０.１３倍の１,２−ジメ
トキシエタンを混合した溶液を連続的に蒸留した。連続
蒸留塔２としては実施例１と同様の構成のものを使用
し、留出タンク３内の留出液の温度を１０℃に保った。
そして、連続蒸留塔２は、操作圧が１.３３×１０4Ｐａ
（１００ｍｍＨｇ）で、還流比が０.５となるように留
出タンク３から連続蒸留塔２に還流される留出液量を操
作した。連続蒸留塔２の供給速度、留出速度、及び缶出
速度を各液の組成と共に表１１に示す。但し、表１１中
のＮＶＰは、Ｎ−ビニル−２−ピロリドンを意味する。
また、連続蒸留塔２の塔頂温度および塔底液温度を表１
２に示す。さらに、連続蒸留塔２の缶出液の臭気官能試
験結果を表１３に示す。Example 4 The method according to the embodiment (2) of the present invention was carried out using the apparatus shown in FIG. Purity including odor components 9
A solution prepared by mixing 9.8 wt% N-vinyl-2-pyrrolidone, 0.13 times water and 0.13 times 1,2-dimethoxyethane by weight thereof was continuously distilled. As the continuous distillation column 2, the one having the same structure as in Example 1 was used, and the temperature of the distillate in the distilling tank 3 was kept at 10 ° C.
The continuous distillation column 2 has an operating pressure of 1.33 × 10 4 Pa.
(100 mmHg), the amount of distillate liquid refluxed from the distilling tank 3 to the continuous distillation column 2 was manipulated so that the reflux ratio was 0.5. Table 11 shows the feed rate, distillation rate, and bottom rate of the continuous distillation column 2 together with the composition of each liquid. However, NVP in Table 11 means N-vinyl-2-pyrrolidone.
In addition, the column top temperature and column bottom liquid temperature of the continuous distillation column 2 are shown in Table 1.
2 shows. Further, Table 13 shows the results of the odor sensory test of the bottoms of the continuous distillation column 2.
【００３３】[0033]
【表１１】 [Table 11]
【００３４】[0034]
【表１２】 [Table 12]
【００３５】[0035]
【表１３】 [Table 13]
【００３６】以上のようにして臭気成分の除去されたＮ
−ビニル−２−ピロリドン（連続蒸留塔２の缶出液）の
純度は、９９.９重量％であった。As described above, N from which odorous components have been removed
The purity of vinyl-2-pyrrolidone (the bottoms of the continuous distillation column 2) was 99.9% by weight.
【図１】実施例１〜４において用いられた蒸留装置の概
略の構成を示すブロック図である。FIG. 1 is a block diagram showing a schematic configuration of a distillation apparatus used in Examples 1 to 4.
【符号の説明】 １・・・タンク ２・・・連続蒸留塔 ３・・・留出タンク ４・・・凝縮器 ８・・・導管 １０・・導管[Explanation of symbols] 1 ... tank 2 ... Continuous distillation column 3 Distillation tank 4 ... condenser 8 ... Conduit 10 ... Conduit
───────────────────────────────────────────────────── フロントページの続き (72)発明者 矢野 斉 大阪府吹田市西御旅町５番８号 株式会社 日本触媒内 Ｆターム(参考） 4C069 AB12 BA03 BC12 CC24 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hitoshi Yano 5-8 Nishiomitabicho Suita City, Osaka Prefecture Within Nippon Shokubai F-term (reference) 4C069 AB12 BA03 BC12 CC24
Claims (2)
−ビニル−２−ピロリドンを、蒸留塔を用いて蒸留する
ことにより、臭気成分を留出液として除去することを特
徴とするＮ−ビニル−２−ピロリドンの脱臭方法。1. N containing an odorous component and having a purity of 90% by weight or more.
A method for deodorizing N-vinyl-2-pyrrolidone, characterized in that odorous components are removed as a distillate by distilling vinyl-2-pyrrolidone using a distillation column.
−ビニル−２−ピロリドンにＮ−ビニル−２−ピロリド
ンより沸点の低い化合物の少なくとも一種を添加して得
られる液を、蒸留塔を用いて蒸留することにより、臭気
成分を上記化合物と共に留出液として除去することを特
徴とするＮ−ビニル−２−ピロリドンの脱臭方法。2. N having an odor component and a purity of 90% by weight or more
-Vinyl-2-pyrrolidone by adding at least one compound having a lower boiling point than N-vinyl-2-pyrrolidone to a liquid obtained by distillation using a distillation column to distill odorous components together with the above compounds. A method for deodorizing N-vinyl-2-pyrrolidone, characterized in that
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002043174A JP2003238533A (en) | 2002-02-20 | 2002-02-20 | Method for deodorizing n-vinyl-2-pyrrolidone |
| DE10306948A DE10306948A1 (en) | 2002-02-20 | 2003-02-19 | Simplified deodorization of N-vinyl-2-pyrrolidone, useful as a starting monomer for poly(N-vinyl-2-pyrrolidone), comprises column distillation in the presence of an added low boiling point compound |
| CNB031060196A CN1244557C (en) | 2002-02-20 | 2003-02-20 | Deodorant N-vinyl-2-pyrrolidone production |
| TW92103477A TW572895B (en) | 2002-02-20 | 2003-02-20 | Method for preparing deodorized N-vinyl-2-pyrrolidone |
| US10/368,411 US7037412B2 (en) | 2002-02-20 | 2003-02-20 | Method for preparing deodorized N-vinyl-2-pyrrolidone |
| KR1020030010784A KR100776960B1 (en) | 2002-02-20 | 2003-02-20 | Method for preparing deodorized n-vinyl-2-pyrrolidone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002043174A JP2003238533A (en) | 2002-02-20 | 2002-02-20 | Method for deodorizing n-vinyl-2-pyrrolidone |
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| Publication Number | Publication Date |
|---|---|
| JP2003238533A true JP2003238533A (en) | 2003-08-27 |
Family
ID=27783045
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002043174A Pending JP2003238533A (en) | 2002-02-20 | 2002-02-20 | Method for deodorizing n-vinyl-2-pyrrolidone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012510440A (en) * | 2008-11-28 | 2012-05-10 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for removing by-products from N-vinylamide |
-
2002
- 2002-02-20 JP JP2002043174A patent/JP2003238533A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012510440A (en) * | 2008-11-28 | 2012-05-10 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for removing by-products from N-vinylamide |
| JP2015083600A (en) * | 2008-11-28 | 2015-04-30 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Method for removing by-product from n-vinylamide |
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