JP3002885B2 - Recovery and purification of dimethylformamide - Google Patents
Recovery and purification of dimethylformamideInfo
- Publication number
- JP3002885B2 JP3002885B2 JP1287065A JP28706589A JP3002885B2 JP 3002885 B2 JP3002885 B2 JP 3002885B2 JP 1287065 A JP1287065 A JP 1287065A JP 28706589 A JP28706589 A JP 28706589A JP 3002885 B2 JP3002885 B2 JP 3002885B2
- Authority
- JP
- Japan
- Prior art keywords
- dmf
- formic acid
- content
- water
- bicarbonate
- 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.)
- Expired - Lifetime
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明はギ酸を含有する粗ジメチルホルムアミドから
ジメチルホルムアミド（以下DMFと略記する。）を回収
精製する方法に関する。The present invention relates to a method for recovering and purifying dimethylformamide (hereinafter abbreviated as DMF) from crude dimethylformamide containing formic acid.
DMFはポリアクリロニトリル、ポリウレタン等の溶剤
として賞用されているばかりでなく、農薬、医薬および
香料等の中間体として有用なプロパルギルカルビノール
類を、ハロアリルカルビノール類から脱ハロゲン化水素
反応により得る際の有用な溶媒でもある。DMF is not only awarded as a solvent for polyacrylonitrile, polyurethane, etc., but also obtains propargyl carbinols, which are useful as intermediates for pesticides, medicines and fragrances, by dehydrohalogenation from haloallyl carbinols. It is also a useful solvent in this case.
＜従来の技術＞ DMFを回収再使用する際に特に問題となるのがギ酸の
除去であることは従来よりよく知られている。ギ酸の存
在はそれ自身が触媒となってDMFを分解し、さらにギ酸
を生じることから、DMFの回収率を低下させる。<Related Art> It is well known that formic acid is particularly problematic when DMF is recovered and reused. The presence of formic acid itself acts as a catalyst to decompose DMF and further produce formic acid, thereby reducing the recovery of DMF.
また、ギ酸含有のDMFを使用するとポリアクリロニト
リル、ポリウレタン等の成形物の品質が低下したり、ハ
ロアリルカルビノール類の脱ハロゲン化水素反応が阻害
されたりする。In addition, when formic acid-containing DMF is used, the quality of molded products such as polyacrylonitrile and polyurethane is deteriorated, and the dehydrohalogenation reaction of haloallyl carbinols is inhibited.
ギ酸除去を安価に行う従来の技術としては以下の方法
があげられる。Conventional techniques for inexpensively removing formic acid include the following methods.
DMFを難溶性の無機塩基性物質により中和する方法
（特公昭44−6802号公報）。A method of neutralizing DMF with a poorly soluble inorganic basic substance (JP-B-44-6802).
アルカリ金属もしくはアルカリ土類金属のアルコラー
ト又はそのアルコール溶液により中和する方法（特公昭
54−1684号公報）。Neutralization with an alkali metal or alkaline earth metal alcoholate or its alcohol solution
No. 54-1684).
アミノ化合物により中和する方法（特開昭57−130960
号公報）。A method of neutralizing with an amino compound (JP-A-57-130960)
No.).
＜発明が解決しようとする課題＞ しかしながら、の方法においては過剰の無機塩基性
物質を使用しているにもかかわらず、ギ酸の中和が充分
でなく、回収DMF中のギ酸含量は多く、決して満足でき
るものとは言い難い。<Problems to be Solved by the Invention> However, in the above method, despite the use of an excess of an inorganic basic substance, the neutralization of formic acid is not sufficient, and the formic acid content in the recovered DMF is large. It is hardly satisfactory.
の方法においては、過剰の塩基がDMFを分解させる
ので、中和操作の管理が難しく、実用的とは言い難い。In the above method, since the excess base decomposes DMF, it is difficult to control the neutralization operation and it is not practical.
の方法においては、過剰のアミノ化合物の添加は、
一般にアミノ化合物がDMFより低沸点成分であるため、
回収DMF中に過剰分のアミノ化合物が混入してくる恐れ
があり、好ましいものとは言い難い。In the above method, the addition of the excess amino compound
In general, amino compounds are lower boiling components than DMF,
Excess amino compound may be mixed into the recovered DMF, which is not preferable.
＜課題を解決するための手段＞ 本発明者らは、上記課題を解決するため、ギ酸の除去
方法につき鋭意検討した結果、ギ酸含有粗DMFをアルカ
リ金属の炭酸塩又は炭酸水素塩により中和する方法にお
いて、系内の水分を11重量％以上で行うことにより、不
純物であるギ酸を充分に中和することができること、及
びこれら塩基性物質を過剰に添加してもDMFの加水分解
が促進されないことを見い出し本発明に至った。<Means for Solving the Problems> In order to solve the above problems, the present inventors have conducted intensive studies on a method for removing formic acid, and as a result, neutralized formic acid-containing crude DMF with an alkali metal carbonate or hydrogencarbonate. In the method, when the water content in the system is adjusted to 11% by weight or more, formic acid as an impurity can be sufficiently neutralized, and the hydrolysis of DMF is not promoted even if these basic substances are added excessively. The present invention has been found.
すなわち、本発明は、ギ酸含有粗DMFをアルカリ金属
の炭酸塩又は炭酸水素塩により中和する方法において、
系内の水分を11重量％以上で行うDMFの回収精製法であ
る。That is, the present invention provides a method for neutralizing formic acid-containing crude DMF with an alkali metal carbonate or bicarbonate,
This is a method for recovering and purifying DMF in which the water content in the system is 11% by weight or more.
本発明で用いる系内の水分とは、（添加したアルカリ
金属の炭酸塩又は炭酸水素塩の重量を除いた中和済溶液
重量）に対する水の重量割合を表わす。The water content in the system used in the present invention refers to the weight ratio of water to (weight of the neutralized solution excluding the weight of the added alkali metal carbonate or bicarbonate).
本発明で用いるアルカリ金属の炭酸塩又は炭酸水素塩
としては、具体的には炭酸リチウム、炭酸水素リチウ
ム、炭酸ナトリウム、炭酸水素ナトリウム、炭酸カリウ
ム、炭酸水素カリウム等が挙げられる。Specific examples of the alkali metal carbonate or bicarbonate used in the present invention include lithium carbonate, lithium bicarbonate, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and the like.
これらアルカリ金属の炭酸塩又は炭酸水素塩を添加す
る際は、系内の水分が11重量％未満の場合には水を添加
して11重量％以上にするか、あるいは、アルカリ金属の
炭酸塩又は炭酸水素塩の水溶液として添加することによ
り上記の含水率の条件を満足するようにする。また、ギ
酸含有粗DMF中の含水率が11重量％以上の場合には、特
に水を添加しなくてもよい。前記系内の水分は11重量％
以上であれば特に制限されないが、通常11〜30重量％で
あり、好ましくは15〜30重量％である。When the alkali metal carbonate or bicarbonate is added, if the water content in the system is less than 11% by weight, water is added to make the content 11% by weight or more, or the alkali metal carbonate or bicarbonate is added. By adding as an aqueous solution of bicarbonate, the above-mentioned condition of the water content is satisfied. In addition, when the water content in the formic acid-containing crude DMF is 11% by weight or more, it is not necessary to particularly add water. 11% by weight of water in the system
The amount is not particularly limited as long as it is above, but is usually 11 to 30% by weight, preferably 15 to 30% by weight.
10重量％以下ではギ酸が充分に除かれず好ましくな
い。If it is less than 10% by weight, formic acid is not sufficiently removed, which is not preferable.
添加するアルカリ金属の炭酸塩又は炭酸水素塩の量
は、粗DMF中のギ酸に対し通常１〜６当量であり、好ま
しくは1.5〜３当量である。The amount of the alkali metal carbonate or bicarbonate to be added is generally 1 to 6 equivalents, preferably 1.5 to 3 equivalents, based on formic acid in crude DMF.
アルカリ金属の炭酸塩又は炭酸水素塩による中和処理
後、系内の水分は、通常、蒸留により脱水することがで
きる。更に単蒸留することにより回収DMFを得ることが
できる。After the neutralization treatment with an alkali metal carbonate or bicarbonate, the water in the system can usually be dehydrated by distillation. Further, the recovered DMF can be obtained by simple distillation.
また、脱水後析出したギ酸のアルカリ金属塩及び過剰
量のアルカリ金属の炭酸塩又は炭酸水素塩を濾別した場
合、最初の粗DMF中にギ酸、水以外の高沸点成分が不純
物として含まれていない場合には、そのまま回収DMFと
して再使用することもできる。しかし、高沸点成分を含
んでいる場合には、通常、単蒸留することにより回収DM
Fを得ることができる。In addition, when the alkali metal salt of formic acid precipitated after dehydration and an excessive amount of a carbonate or bicarbonate of an alkali metal are separated by filtration, high boiling components other than formic acid and water are contained as impurities in the first crude DMF. If not, it can be reused as recovered DMF. However, when high boiling components are contained, the recovered DM is usually recovered by simple distillation.
You can get F.
＜発明の効果＞ 本発明によれば安価なアルカリ金属の炭酸塩又は炭酸
水素塩の添加と水分の調整を行うことにより、ギ酸含有
DMF中のギ酸がほぼ完全に除かれた高純度のDMFが回収で
きる。この回収DMFは、ポリアクリロニトリル、ポリウ
レタン等の溶剤として再使用でき、また、農薬、医薬及
び香料等の中間体として有用なプロパルギルカルビノー
ル類をハロアリルカルビノール類の脱ハロゲン化水素反
応により得る際の溶媒にも再使用できる。<Effects of the Invention> According to the present invention, the addition of inexpensive alkali metal carbonates or bicarbonates and the adjustment of water content allow formic acid
High purity DMF from which formic acid in DMF has been almost completely removed can be recovered. This recovered DMF can be reused as a solvent for polyacrylonitrile, polyurethane, etc., and is also useful for obtaining propargyl carbinols useful as intermediates for pesticides, medicines, fragrances, etc. by the dehydrohalogenation reaction of haloallyl carbinols. Can also be reused.
＜実施例＞ 以下、実施例により本発明を説明するが、本発明はこ
れら実施例に限定されるものではない。<Examples> Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
実施例１ 粗DMF300.00g（DMF含量89.56％、水含量6.92％、ギ酸
含量1.10％）に室温下15％炭酸ナトリウム水溶液66.86g
を加え、30分間撹拌した。このスラリーを精留脱水後、
不溶物を濾去し、得られた濾液を単蒸留して回収DMF26
1.17g（DMF含量99.79％、水含量0.20％、ギ酸含量12pp
m）を得た。Example 1 66.86 g of a 15% aqueous sodium carbonate solution at room temperature in 300.00 g of crude DMF (89.56% DMF content, 6.92% water content, 1.10% formic acid content)
Was added and stirred for 30 minutes. After rectifying and dewatering this slurry,
The insoluble material was removed by filtration, and the obtained filtrate was subjected to simple distillation to recover DMF26.
1.17g (DMF content 99.79%, water content 0.20%, formic acid content 12pp
m).
DMF回収率 97.0％ 実施例２ 粗DMF300.00g（DMF含量89.56％、水含量6.92％、ギ酸
含量1.10％）に室温下水13.75g及び炭酸水素カリウム1
4.32gを加え、30分撹拌した。このスラリーを精留脱水
後、不溶物を濾去し、得られた濾液を単蒸留して回収DM
F260.92g（DMF含量99.78％、水含量0.20％、ギ酸含量26
ppm）を得た。DMF recovery rate 97.0% Example 2 Crude DMF 300.00g (DMF content 89.56%, water content 6.92%, formic acid content 1.10%) 13.75g water and potassium hydrogen carbonate 1 at room temperature
4.32 g was added and stirred for 30 minutes. After rectifying and dewatering this slurry, the insoluble matter was removed by filtration, and the obtained filtrate was subjected to simple distillation to recover DM.
F260.92g (DMF content 99.78%, water content 0.20%, formic acid content 26
ppm).
DMF回収率 96.9％ 実施例３ 粗DMF300.00g（DMF含量89.56％、水含量6.92％、ギ酸
含量1.10％）に室温下水28.52g及び炭酸リチウム7.98g
を加え、30分撹拌した。このスラリーを精留脱水後単蒸
留して回収DMF259.79g（DMF含量99.80％、水含量0.18
％、ギ酸含量10ppm）を得た。DMF recovery rate 96.9% Example 3 Crude DMF 300.00g (DMF content 89.56%, water content 6.92%, formic acid content 1.10%) 28.52g water and 7.98g lithium carbonate at room temperature
Was added and stirred for 30 minutes. This slurry was subjected to simple distillation after rectification and dewatering, and recovered by simple distillation. 259.79 g of DMF (99.80% DMF content, 0.18
%, Formic acid content 10 ppm).
DMF回収率 96.5％ 比較例１ 粗DMF300.00g（DMF含量89.56％、水含量6.92％、ギ酸
含量1.10％）に室温下無水炭酸ナトリウム10.03gを加
え、６時間撹拌した。このスラリーを精留脱水後、不溶
物を濾去し、得られた濾液を単蒸留して回収DMF255.04g
（DMF含量98.82％、水含量0.21％、ギ酸含量0.52％）を
得た。DMF recovery rate 96.5% Comparative Example 1 Anhydrous sodium carbonate 10.03 g was added to crude DMF 300.00 g (DMF content 89.56%, water content 6.92%, formic acid content 1.10%) at room temperature and stirred for 6 hours. After rectifying and dewatering the slurry, insolubles were removed by filtration, and the obtained filtrate was subjected to simple distillation to recover DMF 255.04 g.
(98.82% DMF content, 0.21% water content, 0.52% formic acid content).
DMF回収率 93.8％ 比較例２ 粗DMF300.00g（DMF含量89.56％、水含量6.92％、ギ酸
含量1.10％）に室温下水10.27g及び無水炭酸ナトリウム
10.03gを加え、６時間撹拌した。このスラリーを精留脱
水後、不溶物を濾去し、得られた濾液を単蒸留して回収
DMF255.00g（DMF含量99.36％、水含量0.21％、ギ酸含量
0.23％）を得た。DMF recovery rate 93.8% Comparative Example 2 Crude DMF 300.00g (DMF content 89.56%, water content 6.92%, formic acid content 1.10%) at room temperature 10.27g water and anhydrous sodium carbonate
10.03 g was added and stirred for 6 hours. After rectifying and dewatering this slurry, the insoluble matter was removed by filtration, and the obtained filtrate was recovered by simple distillation.
DMF 255.00g (DMF content 99.36%, water content 0.21%, formic acid content
0.23%).
DMF回収率 94.3％ DMF recovery rate 94.3%
───────────────────────────────────────────────────── フロントページの続き (72)発明者 早田 聡宏 大阪府大阪市此花区春日出中３丁目１番 98号 住友化学工業株式会社内 (72)発明者 齋藤 憲治 大阪府大阪市此花区春日出中３丁目１番 98号 住友化学工業株式会社内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshihiro Hayata 3-1-198, Kasuganaka, Konohana-ku, Osaka-shi Inside Sumitomo Chemical Co., Ltd. (72) Inventor Kenji Saito Kasuga, Konohana-ku, Osaka-shi, Osaka No. 3-chome No. 98, Sumitomo Chemical Co., Ltd.
Claims (1)
リ金属の炭酸塩又は炭酸水素塩により中和する方法にお
いて、系内の水分を11〜30重量％で行うことを特徴とす
るジメチルホルムアミドの回収精製法。1. A method for neutralizing formic acid-containing crude dimethylformamide with an alkali metal carbonate or bicarbonate, wherein the water content in the system is adjusted to 11 to 30% by weight. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1287065A JP3002885B2 (en) | 1989-11-02 | 1989-11-02 | Recovery and purification of dimethylformamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1287065A JP3002885B2 (en) | 1989-11-02 | 1989-11-02 | Recovery and purification of dimethylformamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03148244A JPH03148244A (en) | 1991-06-25 |
| JP3002885B2 true JP3002885B2 (en) | 2000-01-24 |
Family
ID=17712599
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1287065A Expired - Lifetime JP3002885B2 (en) | 1989-11-02 | 1989-11-02 | Recovery and purification of dimethylformamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3002885B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8258291B2 (en) | 2006-10-25 | 2012-09-04 | Mamtek International Limited | Process for the preparation of sucralose by the chlorination of sugar with triphosgene (BTC) |
| US7862744B2 (en) * | 2008-07-23 | 2011-01-04 | Mamtek International Limited | Methods and systems for preparing materials for sucralose production |
| CN110655476A (en) * | 2019-11-08 | 2020-01-07 | 无锡诚尔鑫环保装备科技有限公司 | System for retrieve DMF and dimethylamine in follow DMF waste liquid |
| CN111606822A (en) * | 2020-05-25 | 2020-09-01 | 安徽金禾实业股份有限公司 | Method for recovering acidic DMF (dimethyl formamide) in sucralose production |
-
1989
- 1989-11-02 JP JP1287065A patent/JP3002885B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03148244A (en) | 1991-06-25 |
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