JP2601945B2 - Lactam oil refining method - Google Patents
Lactam oil refining methodInfo
- Publication number
- JP2601945B2 JP2601945B2 JP2314205A JP31420590A JP2601945B2 JP 2601945 B2 JP2601945 B2 JP 2601945B2 JP 2314205 A JP2314205 A JP 2314205A JP 31420590 A JP31420590 A JP 31420590A JP 2601945 B2 JP2601945 B2 JP 2601945B2
- Authority
- JP
- Japan
- Prior art keywords
- lactam
- extraction
- water
- caprolactam
- laurolactam
- 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
- Other In-Based Heterocyclic Compounds (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、ラクタム油の精製方法に関する。詳しく
は、シクロヘキサノンオキシムとシクロドデカノンオキ
シムとの混合物を、ベックマン転位によりカプロラクタ
ムとラウロラクタムを製造する方法において、生成した
ラクタム油の効果的な精製方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for purifying lactam oil. More specifically, the present invention relates to a method for producing a caprolactam and laurolactam from a mixture of cyclohexanone oxime and cyclododecanone oxime by Beckmann rearrangement, and to a method for effectively refining lactam oil produced.
（従来の技術） カプロラクタムとラウロラクタムとを製造する方法
は、シクロヘキサノンとシクロドデカノンとの混合物を
オキシム化し、生成したシクロヘキサノンオキシム又は
その塩とシクロドデカノンオキシム又はその塩との混合
物を硫酸又は発煙硫酸の存在下にベックマン転位し、続
いて、アンモニアガス又はアンモニア水で中和してラク
タム混合物を取得し、そのラクタム混合物を、水と混和
しない有機溶剤で抽出処理するか又はそのラクタム混合
物の層分離によって、硫安水から分離されたラクタム油
層（以下、ラクタム油という）を水と混和しない有機溶
剤で抽出処理して、ラクタム成分を含む抽出液を得、更
に、この抽出液を水で逆抽出処理して、カプロラクタム
を水層に移行させ、ラウロラクタムを有機溶剤層に残存
させる方法（以下、コラクタム化法という）が知られて
いる（例えば、特公昭46−7254号及び同46−10168号各
公報）。(Prior Art) A method for producing caprolactam and laurolactam is to oxime a mixture of cyclohexanone and cyclododecanone, and to produce a mixture of cyclohexanone oxime or a salt thereof and cyclododecanone oxime or a salt thereof with sulfuric acid or fuming. Beckmann rearrangement in the presence of sulfuric acid, followed by neutralization with ammonia gas or aqueous ammonia to obtain a lactam mixture, and then subjecting the lactam mixture to an extraction treatment with a water-immiscible organic solvent or a layer of the lactam mixture The lactam oil layer (hereinafter, referred to as lactam oil) separated from the aqueous ammonium sulfate solution is subjected to extraction treatment with an organic solvent immiscible with water to obtain an extract containing a lactam component, and the extract is back-extracted with water. Process to transfer caprolactam to the aqueous layer and leave laurolactam in the organic solvent layer A method (hereinafter referred to as a collactamation method) is known (for example, JP-B-46-7254 and JP-B-46-10168).
このコラクタム化法によるカプロラクタムとラウロラ
クタムとの同時製造方法においては、従来前記ラクタム
成分を含む抽出液をそのまま水抽出処理していたが、こ
の抽出液中には、原料のシクロドデカノン中に含まれる
直鎖状又は分岐状のアルキルアルコールなどに起因する
アルキル硫酸塩などの陰イオン界面活性物質が存在して
いるために、前記水抽出に際して、エマルジョンを形成
し、有機溶剤層と水層との分離不良等が起こり易く、塔
径の大きな抽出塔が必要となるとともに、水層中に有機
物が同伴して白濁し、カプロラクタムの品質に悪影響を
及ぼしたり、また、有機溶剤層へ水溶性の不純物が同伴
してラウロラクタムの品質にも悪影響を及ぼしていた。In the simultaneous production method of caprolactam and laurolactam by the colactamization method, conventionally, the extract containing the lactam component is subjected to water extraction as it is, but in this extract, it is contained in the raw material cyclododecanone. The presence of an anionic surfactant such as an alkyl sulfate caused by a linear or branched alkyl alcohol, etc., forms an emulsion during the water extraction and forms an emulsion between the organic solvent layer and the aqueous layer. Poor separation is likely to occur, and a large-diameter extraction column is required.Organic substances accompany the aqueous layer, resulting in cloudiness, adversely affecting the quality of caprolactam, and water-soluble impurities in the organic solvent layer. Was also affecting the quality of laurolactam.
（発明が解決しようとする課題） 本発明は、上記の問題を解決し、水抽出の際、エマル
ジョンの形成がよく、短時間で容易に静置分離できるラ
クタム油の精製方法を提供することを目的とする。(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems, and provides a method for purifying lactam oil which can form an emulsion well in water extraction and can be easily separated by standing in a short time. Aim.
（課題を解決するための手段） 本発明者らは、このため鋭意検討を重ねた結果、ラク
タム油のpHを特定の値に保って、ラクタムを有機溶剤で
抽出することによって、上記目的が達成できることを見
出し、本発明を完成するに至った。(Means for Solving the Problems) The inventors of the present invention have made intensive studies for this purpose, and as a result, the above-mentioned object was achieved by maintaining the pH of lactam oil at a specific value and extracting lactam with an organic solvent. They have found that they can do this and have completed the present invention.
すなわち、本発明は、シクロヘキサノンオキシムとシ
クロドデカノンオキシムとの混合物を硫酸及び発煙硫酸
の存在下に、ベックマン転位させて、カプロラクタムと
ラウロラクタムを製造する方法において、転位反応で生
成したラクタム油の水層のpHを６〜12に保って、水と混
和しない有機溶剤でカプロラクタムとラウロラクタムを
抽出して、ラクタム成分を含む抽出液を得て、この抽出
液を水で逆抽出処理することを特徴とするラクタム油の
精製方法である。That is, the present invention provides a method for producing a caprolactam and laurolactam by subjecting a mixture of cyclohexanone oxime and cyclododecanone oxime to Beckmann rearrangement in the presence of sulfuric acid and fuming sulfuric acid. Maintaining the pH of the layer at 6 to 12, extracting caprolactam and laurolactam with an organic solvent immiscible with water to obtain an extract containing a lactam component, and subjecting the extract to back extraction with water. Is a method for refining lactam oil.
以下に、本発明を詳しく説明する。 Hereinafter, the present invention will be described in detail.
本発明で、pH調整用に使用するアルカリ性物質として
は、アンモニア若しくはアンモニア水；水酸化ナトリウ
ム、水酸化カリウム等のアルカリ金属水酸化物；炭酸ナ
トリウム、炭酸カリウム等のアルカリ金属炭酸化物；又
はそれらの混合物が例示される。これらの中で、アンモ
ニア若しくはアンモニア水、水酸化ナトリウム又は水酸
化カリウム等が好適である。アンモニア若しくはアンモ
ニア水を使用する場合は、その一部が抽出に用いる有機
溶剤に混入するが、この場合稀硫酸等で水洗して中和
し、pHを４〜８、好ましくは５〜７に再調整することが
望ましい。pHの再調整に使用する酸性物質としては硫
酸、塩酸等が挙げられる。In the present invention, examples of the alkaline substance used for pH adjustment include ammonia or aqueous ammonia; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; Mixtures are exemplified. Among them, ammonia or aqueous ammonia, sodium hydroxide or potassium hydroxide is preferable. When ammonia or aqueous ammonia is used, a part of it is mixed with the organic solvent used for extraction. In this case, the mixture is neutralized by washing with diluted sulfuric acid or the like, and the pH is restored to 4 to 8, preferably 5 to 7. It is desirable to adjust. Examples of the acidic substance used for readjustment of pH include sulfuric acid and hydrochloric acid.
ラクタム油の中和は、水層すなわち重液側のpHを６〜
12とすることが必要で、好ましくは７〜10の範囲に調整
する。Lactam oil is neutralized by increasing the pH of the aqueous layer,
It is necessary to be 12, and it is preferably adjusted to a range of 7 to 10.
本発明で使用する有機溶剤としては、ベンゼン、トル
エン、キシレン、イソプロピルベンゼンなどの芳香族炭
化水素；シクロヘキサン、シクロオクタンなどの脂環式
炭化水素;n−ヘキサン、ｎ−ヘプタン、ｎ−オクタンな
どの炭素数６〜８の脂肪族炭化水素；トリクロルエチレ
ン、四塩化炭素、クロロホルムなどのハロゲン原子で置
換した炭化水素などの抽出温度で液体であり、水と混和
しない溶剤が挙げられるが、中でもベンゼン及びトルエ
ンを最も好適に挙げることができる。もちろん、上記の
溶剤の２種以上の混合物の使用が可能であることは言う
までもない。Examples of the organic solvent used in the present invention include aromatic hydrocarbons such as benzene, toluene, xylene and isopropylbenzene; alicyclic hydrocarbons such as cyclohexane and cyclooctane; n-hexane, n-heptane and n-octane. Aliphatic hydrocarbons having 6 to 8 carbon atoms; solvents which are liquid at the extraction temperature of hydrocarbons substituted with halogen atoms such as trichloroethylene, carbon tetrachloride, and chloroform, and are immiscible with water, among which benzene and Toluene can most preferably be mentioned. Of course, it is needless to say that a mixture of two or more of the above solvents can be used.
前記ラクタム油からのラクタム成分の有機溶剤による
抽出の抽出温度、抽出剤比率及び抽出時間などの抽出操
作条件や抽出装置の型式などの抽出方法は、通常の液−
液抽出において適用される範囲のものであれば、特に限
定されるものではなく、抽出及びそれに続く冷却の結果
得られる前記有機溶液中のカプロラクタム及びラウロラ
クタムの含有量が、共に、前記の10〜20重量％の範囲内
になるように、前記抽出操作条件や抽出方法を決定すれ
ばよい。例えば、抽出温度について言えば、抽出装置内
において、前記ラクタム油や有機溶剤が液体として存在
する温度であり、従って、前記ラクタム油の融点以上、
かつ抽出の結果得られる抽出液や重液の沸点以下の温度
範囲、好ましくは40〜80℃であることが望ましい。ま
た、抽出装置も、工業的には、例えば、充填塔や目皿板
式の塔など、向流式の液−液抽出装置を使用することが
好ましい。The extraction method such as the extraction temperature, extraction agent ratio and extraction time of extraction of the lactam component from the lactam oil with an organic solvent, and the extraction method such as the type of the extraction device, are commonly used for liquid-
The content of caprolactam and laurolactam in the organic solution obtained as a result of extraction and subsequent cooling is not particularly limited as long as it is within the range applicable in liquid extraction, and both of the above-mentioned 10 to 10 The extraction operation conditions and the extraction method may be determined so as to fall within the range of 20% by weight. For example, regarding the extraction temperature, in the extraction device, the temperature at which the lactam oil or the organic solvent is present as a liquid, and therefore, the melting point of the lactam oil or higher,
It is desirable that the temperature be below the boiling point of the extract or heavy liquid obtained as a result of the extraction, preferably 40 to 80 ° C. As the extraction device, it is industrially preferable to use a countercurrent liquid-liquid extraction device such as a packed tower or a perforated plate type tower.
以上述べたpHの調整によって水抽出時のエマルジョン
の発生が大巾に減少するか又は消失し、層分離が短時間
に効果的に実施できるようになる。これはラクタム油に
不純物として含有されていたアルキル硫酸塩等の界面活
性物質が、ラクタム油からのラクタム成分の有機溶剤抽
出の際に、水層側すなわち重液側に移行し易くなるため
である。By adjusting the pH as described above, the generation of emulsion during water extraction is greatly reduced or eliminated, and layer separation can be effectively performed in a short time. This is because surfactants such as alkyl sulfates, which were contained as impurities in lactam oil, easily migrate to the aqueous layer side, that is, the heavy liquid side, when extracting the lactam component from the lactam oil with an organic solvent. .
更に、本発明の大きな利点として、ラクタム油中の着
色性不純物も、pHの調整によって、有機溶剤抽出の際に
重液側に移行するためラクタムの品質が、一段と向上す
るものである。Further, as a great advantage of the present invention, the coloring impurities in the lactam oil are also transferred to the heavy liquid side during the extraction of the organic solvent by adjusting the pH, so that the quality of the lactam is further improved.
（実施例） 以下、実施例を挙げ、本発明を更に詳しく説明する
が、本発明は、これによりその範囲が限定されるもので
はない。(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the scope thereof.
実施例１ カプロラクタム40重量％、ラウロラクタム44重量％及
び水分12重量％を含むラクタム油400gを攪拌機を備えた
ガラス容器（容量５）を仕込み、次いで、1580gのト
ルエンを加え、温度68℃で攪拌しながら、pHが８となる
ようにアンモニアガスを吹き込み、そのまま10分間攪拌
した後静置分離すると、19.3重量％のカプロラクタムと
1.6重量％のラウロラクタムを含む分離重液38gと、8.0
重量％のカプロラクタムと9.2重量％のラウロラクタム
を含むトルエン溶液（以下、「トルエン溶液−１」とい
う）1926gが得られた。Example 1 A glass container (capacity 5) equipped with a stirrer was charged with 400 g of lactam oil containing 40% by weight of caprolactam, 44% by weight of laurolactam and 12% by weight of water, and then 1580 g of toluene was added, followed by stirring at a temperature of 68 ° C. Then, ammonia gas was blown into the mixture so that the pH became 8, and the mixture was stirred for 10 minutes and allowed to stand still for separation to obtain 19.3% by weight of caprolactam.
38 g of separated heavy liquid containing 1.6% by weight laurolactam, 8.0 g
As a result, 1926 g of a toluene solution containing caprolactam by weight and 9.2 wt% laurolactam (hereinafter referred to as "toluene solution-1") was obtained.
この重液を分離した「トルエン溶液−１」の一部800g
に、更に水510gを加えて58〜62℃で攪拌混合し、カプロ
ラクタムを水層側へ逆抽出したところ、エマルジョンの
生成もなく短時間の静置分離で容易に分離し、9.9重量
％のラウロラクタムを含む有機層（トルエン層）733g
と、9.8重量％のカプロラクタムを含む水層566gとが得
られた。800 g of a part of "toluene solution-1" from which this heavy liquid was separated
Was further added with 510 g of water, and the mixture was stirred and mixed at 58 to 62 ° C., and caprolactam was back-extracted into the aqueous layer side. 733g of organic layer containing lactam (toluene layer)
And 566 g of an aqueous layer containing 9.8% by weight of caprolactam.
実施例２ 実施例１で得た「トルエン溶液−１」1000gに、更に1
9gの水を加え、攪拌しながら75％硫酸を添加してpH6に
調整した。そのまま66〜68℃で10分間攪拌した後、静置
分離すると、17.7重量％のカプロラクタムと0.9重量％
のラウロラクタムとを含む分離重液29gと、7.6重量％の
カプロラクタムと9.3重量％のラウロラクタムとを含む
トルエン抽出液988gが得られた。Example 2 To 1000 g of the “toluene solution-1” obtained in Example 1,
9 g of water was added, and the pH was adjusted to 6 by adding 75% sulfuric acid with stirring. After stirring at 66-68 ° C for 10 minutes as it is, the mixture is allowed to stand and separated, and 17.7% by weight of caprolactam and 0.9% by weight
Was obtained, and 988 g of a toluene extract containing 7.6% by weight of caprolactam and 9.3% by weight of laurolactam were obtained.
得られたトルエン抽出液に、さらに600gの水を加えて
58〜62℃で攪拌混合し、カプロラクタムを水層側へ逆抽
出したところエマルジョンの生成もなく、短時間の静置
で容易に分離した。To the obtained toluene extract, further add 600 g of water.
The mixture was stirred and mixed at 58 to 62 ° C., and caprolactam was back-extracted into the aqueous layer side. As a result, no emulsion was formed and the caprolactam was easily separated by standing for a short time.
比較例１ ラクタム油をトルエンで抽出する時に、アンモニアガ
スでのpH調整をしなかった他は、実施例１と同様に行
い、「トルエン溶液−１」を得た。この際、ラクタム油
をトルエンで抽出したときのpH値は4.8であった。得ら
れた「トルエン溶液−１」水1230gを加え逆抽出したと
ころ、エマルジョンが生成し、攪拌停止後30分間静置し
ても、有機層と水層の分離ができなかった。Comparative Example 1 A "toluene solution-1" was obtained in the same manner as in Example 1, except that the pH of the lactam oil was not adjusted with ammonia gas when the lactam oil was extracted with toluene. At this time, the pH value when the lactam oil was extracted with toluene was 4.8. When 1230 g of the obtained “toluene solution-1” water was added and back-extracted, an emulsion was formed, and even if the stirring was stopped and allowed to stand for 30 minutes, the organic layer and the aqueous layer could not be separated.
（発明の効果） 以上のように、本発明によれば、コラクタム油の精製
における水抽出の際、エマルジョンを形成することな
く、極めて効率的に抽出液を分離することができる。(Effects of the Invention) As described above, according to the present invention, an extract can be separated extremely efficiently without forming an emulsion during water extraction in the purification of colactam oil.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 下村 秀雄 山口県宇部市大字小串1978番地の10 宇 部興産株式会社宇部ケミカル工場内 (56)参考文献 特開 昭52−62289（ＪＰ，Ａ) 特開 昭53−147085（ＪＰ，Ａ) 特開 昭60−199873（ＪＰ，Ａ) 特開 昭48−52785（ＪＰ，Ａ) 特公 昭46−10168（ＪＰ，Ｂ１) 特公 昭46−7254（ＪＰ，Ｂ１) ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideo Shimomura 10 Ube Kogushi Co., Ltd., 1978 Kogushi, Ube City, Ube City, Yamaguchi Prefecture (56) References JP-A-52-62289 (JP, A) JP-A-53-147085 (JP, A) JP-A-60-199873 (JP, A) JP-A-48-52785 (JP, A) JP-B-46-10168 (JP, B1) JP-B-46-7254 ( JP, B1)
Claims (1)
ノンオキシムとの混合物を、硫酸及び発煙硫酸の存在下
に、ベックマン転位させて、カプロラクタムとラウロラ
クタムを製造する方法において、転位反応で生成したラ
クタム油の水層のpHを６〜12に保って、水と混和しない
有機溶剤でカプロラクタムとラウロラクタムを抽出し
て、ラクタム成分を含む抽出液を得て、この抽出液を水
で逆抽出処理することを特徴とするラクタム油の精製方
法。1. A method for producing caprolactam and laurolactam by subjecting a mixture of cyclohexanone oxime and cyclododecanone oxime to Beckmann rearrangement in the presence of sulfuric acid and fuming sulfuric acid, wherein water of lactam oil produced by the rearrangement reaction is produced. Maintaining the pH of the layer at 6 to 12, extracting caprolactam and laurolactam with an organic solvent immiscible with water to obtain an extract containing a lactam component, and subjecting the extract to back extraction with water. Lactam oil refining method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2314205A JP2601945B2 (en) | 1990-11-21 | 1990-11-21 | Lactam oil refining method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2314205A JP2601945B2 (en) | 1990-11-21 | 1990-11-21 | Lactam oil refining method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04187671A JPH04187671A (en) | 1992-07-06 |
| JP2601945B2 true JP2601945B2 (en) | 1997-04-23 |
Family
ID=18050541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2314205A Expired - Lifetime JP2601945B2 (en) | 1990-11-21 | 1990-11-21 | Lactam oil refining method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2601945B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3498758A1 (en) * | 2017-12-13 | 2019-06-19 | Evonik Degussa GmbH | Method for the preparation of polymers from monomers comprising laurolactam |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE790692A (en) * | 1971-10-29 | 1973-04-27 | Stamicarbon | PROCESS FOR OBTAINING PURE MILK |
| DE2550934C3 (en) * | 1975-11-13 | 1980-06-12 | Bayer Ag, 5090 Leverkusen | Purification of caprolactam |
| DE2724361A1 (en) * | 1977-05-28 | 1978-11-30 | Bayer Ag | CLEANING CAPROLACTAM |
| JPS60199873A (en) * | 1984-03-23 | 1985-10-09 | Ube Ind Ltd | Recovery of epsilon-caprolactam |
-
1990
- 1990-11-21 JP JP2314205A patent/JP2601945B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04187671A (en) | 1992-07-06 |
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