JPH07126912A - Purification of aqueous solution of n-methylmorpholine-n-oxide - Google Patents
Purification of aqueous solution of n-methylmorpholine-n-oxideInfo
- Publication number
- JPH07126912A JPH07126912A JP5275821A JP27582193A JPH07126912A JP H07126912 A JPH07126912 A JP H07126912A JP 5275821 A JP5275821 A JP 5275821A JP 27582193 A JP27582193 A JP 27582193A JP H07126912 A JPH07126912 A JP H07126912A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- mmno
- methylmorpholine
- solution
- oxide
- 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.)
- Pending
Links
Landscapes
- Artificial Filaments (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、Ｎ−メチルモルホリン
−Ｎ−オキシド（以下、ＭＭＮＯ）水溶液を溶媒とした
セルロース紡糸液を紡糸する際に用いた凝固浴液及び洗
浄液からＭＭＮＯ水溶液を精製する方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention purifies an aqueous MMNO solution from a coagulation bath solution and a washing solution used in spinning a cellulose spinning solution using an aqueous N-methylmorpholine-N-oxide (hereinafter referred to as MMNO) solution as a solvent. Regarding the method.
【０００２】[0002]
【従来の技術】従来、ＭＭＮＯ水溶液でセルロースを溶
解した紡糸原液を用いて、再生セルロース繊維を製造す
ることが行われている（特開昭５４−９９１４８号公
報）。すなわち、紡糸原液を紡糸ノズルより吐出して、
空気中またはセルロースの貧溶媒中で繊維に賦型・延伸
し、ＭＭＮＯ水溶液または水からなる凝固浴中でセルロ
ースを沈澱凝固した後、ＭＭＮＯ水溶液または水で洗浄
を行い、乾燥をして繊維を得る。2. Description of the Related Art Conventionally, regenerated cellulose fibers have been produced using a spinning dope prepared by dissolving cellulose in an aqueous MMNO solution (Japanese Patent Laid-Open No. 54-99148). That is, the spinning dope is discharged from the spinning nozzle,
The fibers are shaped and stretched in air or in a poor solvent for cellulose, and the cellulose is precipitated and solidified in a coagulation bath consisting of an MMNO aqueous solution or water, then washed with the MMNO aqueous solution or water and dried to obtain fibers. .
【０００３】この時、紡糸原液中のＭＭＮＯ、水、とと
もにＭＭＮＯ由来の不純物やセルロース由来の不純物、
分解物、原液中に添加した安定剤等の添加物が凝固浴
中、洗浄水中に拡散溶解する。これらの不純物等は、凝
固浴中のＭＭＮＯ水溶液また水の褐色着色、濁りの原因
となる。このため、ＭＭＮＯ水溶液及び水を閉循環系で
回収使用すると、その着色濁度が次第にひどくなり、最
終的には、紡糸した繊維へも着色が起こる。したがっ
て、ＭＭＮＯ水溶液、洗浄水は、常に精製を行った清浄
な状態であることが必須である。また、経済的、環境問
題からもＭＭＮＯ水溶液を精製して繰り返し使用するこ
とが望ましい。At this time, MMNO and water in the spinning dope, as well as impurities derived from MMNO and impurities derived from cellulose,
Additives such as decomposed products and stabilizers added to the stock solution diffuse and dissolve in the washing water in the coagulation bath. These impurities and the like cause brown coloring and turbidity of the MMNO aqueous solution or water in the coagulation bath. For this reason, when the MMNO aqueous solution and water are collected and used in a closed circulation system, the turbidity of the coloring gradually becomes worse, and finally the spun fiber is also colored. Therefore, it is essential that the MMNO aqueous solution and the cleaning water are always in a purified and clean state. In addition, it is desirable to purify the MMNO aqueous solution and repeatedly use it from the viewpoint of economic and environmental problems.
【０００４】特開平３−１３７９４３号公報には、ＭＭ
ＮＯ水溶液をアニオン交換体に１または２段階に接触
し、精製する方法が開示されている。Japanese Patent Laid-Open No. 3-17943 discloses a MM.
A method for purifying an aqueous NO solution by contacting it with an anion exchanger in one or two steps is disclosed.
【０００５】また、米国特許第５，１７８，７６４号明
細書は、アルミナ、シリカ、炭素（コークス）といった
吸着剤に接触させた後、セルロースフィルターで濾過す
る方法を開示している。US Pat. No. 5,178,764 discloses a method of contacting with an adsorbent such as alumina, silica and carbon (coke) and then filtering with a cellulose filter.
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、アニオ
ン交換体を用いる方法では、アニオン性以外の不純物を
取り除くことができないし、アニオン交換体を再生する
際に、使用した再生用溶液の排水処理に問題が残る。However, in the method using an anion exchanger, impurities other than anionic cannot be removed, and when regenerating the anion exchanger, there is a problem in wastewater treatment of the regenerating solution used. Remains.
【０００７】また、吸着剤を使用する方法では、吸着能
がなくなるまでの時間（破過時間）が非常に短く、大量
の使用済み吸着剤が生じるため、再生あるいは廃棄に問
題が残る。Further, in the method using an adsorbent, the time (breakthrough time) until the adsorbability is lost is very short, and a large amount of used adsorbent is produced, so that there remains a problem in regeneration or disposal.
【０００８】本発明の目的は、以上の従来の精製方法が
有している問題点を解決し、セルロース紡糸液を紡糸す
る際に用いた凝固浴液及び洗浄液である、不純物を含ん
だＭＭＮＯ水溶液（以下、汚染ＭＭＮＯ水溶液）からＭ
ＭＮＯ水溶液を精製する方法を提供することにある。The object of the present invention is to solve the problems of the conventional purification methods described above, and to prepare an MMNO aqueous solution containing impurities, which is a coagulating bath solution and a washing solution used in spinning a cellulose spinning solution. (Hereinafter, contaminated MMNO aqueous solution) to M
It is to provide a method for purifying an MNO aqueous solution.
【０００９】[0009]
【課題を解決するための手段】本発明の要旨は、Ｎ−メ
チルモルホリン−Ｎ−オキシド水溶液を溶媒としたセル
ロース紡糸原液を紡糸する際に用いた凝固浴液および洗
浄液をアルカリ性に調整し、次いで、活性炭に接触させ
ることを特徴とする、Ｎ−メチルモルホリン−Ｎ−オキ
シド水溶液の精製方法である。SUMMARY OF THE INVENTION The gist of the present invention is to adjust the coagulation bath solution and washing solution used for spinning a cellulose spinning dope using an aqueous solution of N-methylmorpholine-N-oxide as a solvent, and then adjust the alkalinity. A method for purifying an N-methylmorpholine-N-oxide aqueous solution, which comprises contacting with activated carbon.
【００１０】以下、本発明を詳細に説明する。本発明に
いう、セルロースは、精製パルプであればよく、特に限
定しない。セルロース紡糸原液は、公知の方法で調製、
紡糸することができる。The present invention will be described in detail below. The cellulose referred to in the present invention is not particularly limited as long as it is a refined pulp. The cellulose spinning solution is prepared by a known method,
It can be spun.
【００１１】本発明では、汚染ＭＭＮＯ水溶液のｐＨを
１０〜１４に調整することが好ましく、ｐＨ１３以上に
調整することが更に好ましい。ｐＨ１０未満では、濃縮
等で加熱した時に着色しやすい。In the present invention, the pH of the contaminated MMNO aqueous solution is preferably adjusted to 10 to 14, and more preferably adjusted to 13 or more. If the pH is less than 10, coloring tends to occur when heated for concentration.
【００１２】ｐＨ調節のために添加する化合物は、特に
限定しないが、例えば次のようなものが挙げられる。す
なわち、水酸化ナトリウム、水酸化カリウム等のアルカ
リ金属の水酸化物、水酸化マグネシウム、水酸化カルシ
ウム、水酸化バリウム等のアルカリ土類金属の水酸化
物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属の
炭酸塩、アンモニア、アミン等が挙げられる。The compound to be added for pH adjustment is not particularly limited, but examples thereof include the following. That is, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as magnesium hydroxide, calcium hydroxide and barium hydroxide, alkali metal hydroxides such as sodium carbonate and potassium carbonate. Carbonates, ammonia, amines, etc. may be mentioned.
【００１３】本発明に用いる活性炭としては、粉状、粒
状、繊維状のいずれの形態であってもよく、活性炭でア
ルカリ性に調整した汚染ＭＭＮＯ水溶液を処理する方法
は、公知の方法、すなわち、固定床、移動床、流動層
等、が使用できる。処理に使用した活性炭は、脱離再
生、酸化分解、熱再生、生物再生等により再生すること
ができる。The activated carbon used in the present invention may be in the form of powder, granules or fibers, and the method of treating the contaminated MMNO aqueous solution adjusted to alkaline with activated carbon is a known method, that is, fixation. Beds, moving beds, fluidized beds, etc. can be used. The activated carbon used for the treatment can be regenerated by desorption regeneration, oxidative decomposition, heat regeneration, biological regeneration and the like.
【００１４】なお、上記のアルカリ調整、または、活性
炭による濾過に先だって、ＭＭＮＯ水溶液を溶剤で希釈
して粘度を下げると、本発明の効果がより高まる。極性
をもち、ＭＭＮＯとの混合が可能で、ＭＭＮＯと化学反
応を起こさない有機溶剤であれば、使用することがで
き、例えば、ジメチルスルホキシド、Ｎ，Ｎ−ジメチル
ホルムアミド、Ｎ，Ｎ−ジメチルアセトアミド、アセト
ニトリル、スルフォランなどが挙げられる。If the MMNO aqueous solution is diluted with a solvent to reduce the viscosity prior to the above alkali adjustment or filtration with activated carbon, the effect of the present invention is further enhanced. Any organic solvent which is polar and can be mixed with MMNO and does not chemically react with MMNO can be used, and examples thereof include dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, Acetonitrile, sulfolane, etc. are mentioned.
【００１５】本発明により精製されたＭＭＮＯ水溶液
は、公知の方法により濃縮でき、セルロース紡糸液を調
製するのに用いることができる。紡糸原液を調整するた
めには、ｐＨが中性域にあることが望ましいが、このｐ
Ｈの調整は、活性炭による濾過の前に行っても、後で行
ってもよい。The MMNO aqueous solution purified by the present invention can be concentrated by a known method and used for preparing a cellulose spinning solution. In order to adjust the spinning dope, it is desirable that the pH is in the neutral range.
Adjustment of H may be performed before or after filtration with activated carbon.
【００１６】[0016]
【実施例】以下実施例により、本発明を更に具体的に説
明する。 ・精製度評価 精製度の評価は、４１７ｎｍの吸光度を測定して評価し
た。吸光度が低いほど、精製度が高いことを示す。EXAMPLES The present invention will be described in more detail with reference to the following examples. -Evaluation of the degree of purification The degree of purification was evaluated by measuring the absorbance at 417 nm. The lower the absorbance, the higher the degree of purification.
【００１７】・汚染ＭＭＮＯ溶液の採取 セルロース（粘度平均分子量４８０）５１４ｇ、濃度６
０重量％のＭＭＮＯ水溶液３，０００ｇ、没食子酸プロ
ピル（セルロースの安定化剤）１５ｇを混合し、約１０
０℃に加熱攪拌しながら減圧し、約９４０ｇの水を蒸留
脱水して、紡糸原液を調製した。これを１３５℃の紡糸
温度で、孔径２００μｍ、Ｌ／Ｄ＝１５、孔数３６個の
紡糸口金から吐出速度０．１８８ｇ／分・孔で吐出し、
次いで約５０ｃｍの間隙を通過させた後、純水を満たし
た凝固浴中で凝固し糸条を２００ｍ／分で引き取った。Sampling of contaminated MMNO solution 514 g of cellulose (viscosity average molecular weight 480), concentration 6
3,000 g of 0% by weight MMNO aqueous solution and 15 g of propyl gallate (a stabilizer for cellulose) are mixed to obtain about 10
The temperature was reduced to 0 ° C. with heating and stirring, and about 940 g of water was distilled and dehydrated to prepare a spinning dope. This was discharged at a spinning temperature of 135 ° C. from a spinneret having a hole diameter of 200 μm, L / D = 15, and 36 holes at a discharge rate of 0.188 g / min.
Then, after passing through a gap of about 50 cm, the yarn was coagulated in a coagulation bath filled with pure water and the yarn was taken out at 200 m / min.
【００１８】凝固浴中のＭＭＮＯ濃度が１０重量％とな
ったとき、試料を採取した。吸光度は、０．４２１であ
った。以下の実施例、比較例には、この試料を用いた。A sample was taken when the MMNO concentration in the coagulation bath reached 10% by weight. The absorbance was 0.421. This sample was used in the following examples and comparative examples.
【００１９】（実施例）上記試料に水酸化ナトリウムを
加え、ｐＨを１３に調整した。次いで、活性炭（Ｔ−Ｓ
Ｂ３２／６０Ｍ：クラレケミカル（株））２００ｍｌの
固定床に空間速度ＳＶ＝６．６で供給した。通過液の吸
光度は、０．００１であった。また、使用した活性炭の
破過時間は、８時間であった。(Example) Sodium hydroxide was added to the above sample to adjust the pH to 13. Then, activated carbon (T-S
B32 / 60M: supplied to a fixed bed of 200 ml of Kuraray Chemical Co., Ltd. at a space velocity SV of 6.6. The absorbance of the passing liquid was 0.001. The breakthrough time of the activated carbon used was 8 hours.
【００２０】（比較例１）活性炭で処理することを除い
て、実施例と同様な処理を行った。得られた処理液の吸
光度は、０．２４５で、精製が不十分であった。(Comparative Example 1) The same treatment as in Example was carried out except that the treatment was carried out with activated carbon. The absorbance of the obtained treatment liquid was 0.245, and purification was insufficient.
【００２１】（比較例２）アルカリ調整はせずに実施例
と同様な処理を行った。活性炭の破過時間は、５０分と
短かった。Comparative Example 2 The same treatment as in Example was carried out without adjusting the alkali. The breakthrough time of activated carbon was as short as 50 minutes.
【００２２】[0022]
【発明の効果】上述の如く構成された本発明によれば、
ＭＭＮＯ水溶液を溶媒としたセルロース紡糸液の紡糸時
に用いた凝固浴液及び洗浄液からＭＭＮＯ水溶液を精製
する際の排水、使用済み吸着剤の処理を大幅に削減でき
る。According to the present invention constructed as described above,
It is possible to greatly reduce the wastewater and the treatment of the used adsorbent when purifying the MMNO aqueous solution from the coagulation bath solution and the washing solution used during the spinning of the cellulose spinning solution using the MMNO aqueous solution as a solvent.
Claims (1)
液を溶媒としたセルロース紡糸原液を紡糸する際に用い
た凝固浴液および洗浄液をｐＨをアルカリ性に調整し、
次いで、活性炭に接触させることを特徴とする、Ｎ−メ
チルモルホリン−Ｎ−オキシド水溶液の精製方法。1. A coagulation bath solution and a washing solution used for spinning a cellulose spinning dope using an aqueous solution of N-methylmorpholine-N-oxide as a solvent are adjusted to have an alkaline pH.
Next, a method for purifying an N-methylmorpholine-N-oxide aqueous solution, which comprises contacting with activated carbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5275821A JPH07126912A (en) | 1993-11-04 | 1993-11-04 | Purification of aqueous solution of n-methylmorpholine-n-oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5275821A JPH07126912A (en) | 1993-11-04 | 1993-11-04 | Purification of aqueous solution of n-methylmorpholine-n-oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07126912A true JPH07126912A (en) | 1995-05-16 |
Family
ID=17560899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5275821A Pending JPH07126912A (en) | 1993-11-04 | 1993-11-04 | Purification of aqueous solution of n-methylmorpholine-n-oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07126912A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110592695A (en) * | 2019-10-12 | 2019-12-20 | 淮安天然丝纺织科技有限公司 | Preparation method of cellulose filament fibers |
-
1993
- 1993-11-04 JP JP5275821A patent/JPH07126912A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110592695A (en) * | 2019-10-12 | 2019-12-20 | 淮安天然丝纺织科技有限公司 | Preparation method of cellulose filament fibers |
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