JP4576834B2 - Method for treating cycloalkanone oxime - Google Patents
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Description
本発明は、シクロアルカノンオキシムの熱安定性を向上させる方法に関する。 The present invention relates to a method for improving the thermal stability of a cycloalkanone oxime.
従来、シクロアルカノンオキシムの熱安定性を向上させる方法としては、例えば、アルカリ金属若しくはアルカリ土類金属、又はアルカリ金属、アルカリ土類金属、亜鉛若しくはアルミニウムの酸化物、水酸化物若しくはアルコラートを、シクロアルカノンオキシムの気化帯域に存在させる方法（特許文献１参照）、溶融シクロヘキサノンオキシムを硫酸アンモニウム水溶液で洗浄してｐＨ４．５〜５．８に保つ方法（特許文献２参照）、アンモニア又は低級アルキルアミンを存在させる方法（特許文献３参照）、シクロヘキサノンオキシムの溶液を、水又は塩基水溶液で洗浄する方法や、弱アルカリ性イオン交換樹脂に通す方法（特許文献４参照）等が知られている。
しかしながら、これら従来の方法では、シクロアルカノンオキシムの熱安定性が必ずしも十分にならないことがあった。そこで、本発明の目的は、シクロアルカノンオキシムの熱安定性を効果的に向上させることができる方法を提供することにある。 However, in these conventional methods, the thermal stability of the cycloalkanone oxime may not always be sufficient. Then, the objective of this invention is providing the method which can improve the thermal stability of cycloalkanone oxime effectively.
本発明者等は鋭意研究を行った結果、液状乃至溶液状のシクロアルカノンオキシムを、ある種の水溶液で接触処理することにより、上記目的を達成できることを見出し、本発明を完成するに至った。すなわち、本発明は、シクロアルカノンオキシムを含む液体を、ホウ素若しくはリンのオキソ酸又はその塩の水溶液と接触させることを特徴とするシクロアルカノンオキシムの処理方法を提供するものである。 As a result of diligent research, the present inventors have found that the above object can be achieved by contact treatment of liquid or solution-like cycloalkanone oxime with a certain type of aqueous solution, and the present invention has been completed. . That is, the present invention provides a method for treating cycloalkanone oxime, which comprises contacting a liquid containing cycloalkanone oxime with an aqueous solution of boron or phosphorus oxo acid or a salt thereof.
本発明によれば、シクロアルカノンオキシムの熱安定性を効果的に向上させることができる。 According to the present invention, the thermal stability of cycloalkanone oxime can be effectively improved.
本発明が対象とするシクロアルカノンオキシムとしては、例えば、シクロペンタノンオキシム、シクロヘキサノンオキシム、シクロオクタノンオキシム、シクロドデカノンオキシム等が挙げられ、必要に応じてそれらの２種以上を用いることもできる。シクロアルカノンオキシムは、例えば、シクロアルカノンをヒドロキシルアミン又はその塩と反応させる方法、シクロアルカンを光ニトロソ化する方法、シクロアルカノンをチタノシリケートのような触媒の存在下にアンモニア及び過酸化水素と反応させる方法等により、製造することができる。 Examples of the cycloalkanone oxime targeted by the present invention include cyclopentanone oxime, cyclohexanone oxime, cyclooctanone oxime, cyclododecanone oxime, etc., and two or more of them may be used as necessary. it can. Cycloalkanone oximes include, for example, a method of reacting a cycloalkanone with hydroxylamine or a salt thereof, a method of photonitrosating a cycloalkane, and ammonia and peroxidation in the presence of a catalyst such as titanosilicate. It can be produced by a method of reacting with hydrogen.
シクロアルカノンオキシムは常温で固体のものが多く、その貯蔵や移送の際には、溶融状態にして取り扱いを容易にするため、融点以上、例えばシクロペンタノンオキシムであれば５３〜５５℃以上、シクロヘキサノンオキシムであれば８９〜９１℃以上に加熱されることがある。また、常温で液体のシクロアルカノンオキシムや、溶媒に溶かした溶液状のシクロアルカノンオキシムであっても、その貯蔵や移送の際には、粘度を下げて取り扱いを容易にするため、例えば５０℃以上に加熱されることがある。さらに、シクロアルカノンオキシムを気化させる際、例えば蒸留精製する際や気相ベックマン転位反応に付すための原料ガスを調製する際には、常圧の場合、その沸点以上、例えばシクロペンタノンオキシムであれば１９６℃以上、シクロヘキサノンオキシムであれば２０６〜２１０℃以上に加熱されることがあり、また、減圧の場合や低沸点ガスを同伴させる場合でも、例えば１５０℃以上に加熱されることがある。そこで、本発明では、このようなシクロアルカノンオキシムの加熱時等における熱安定性を向上させるため、ホウ素のオキソ酸若しくはその塩又はリンのオキソ酸若しくはその塩の水溶液を用いて、接触処理を行う。 Many cycloalkanone oximes are solid at room temperature, and when stored or transported, in order to facilitate handling in a molten state, the melting point or higher, for example, 53 to 55 ° C. or higher for cyclopentanone oxime, If it is cyclohexanone oxime, it may be heated to 89-91 degreeC or more. Further, even in the case of cycloalkanone oxime which is liquid at normal temperature or solution-like cycloalkanone oxime dissolved in a solvent, when storing or transferring the cycloalkanone oxime, for example 50 May be heated above ℃. Furthermore, when vaporizing cycloalkanone oxime, for example, when purifying by distillation or when preparing a raw material gas for subjecting to a gas phase Beckmann rearrangement reaction, at normal pressure, above its boiling point, for example, cyclopentanone oxime If it is, it may be heated to 196 ° C. or higher, and if it is cyclohexanone oxime, it may be heated to 206 to 210 ° C. or higher, and even when decompressed or accompanied by a low boiling point gas, it may be heated to 150 ° C. or higher, for example. . Therefore, in the present invention, in order to improve the thermal stability at the time of heating such cycloalkanone oxime, contact treatment is carried out using an aqueous solution of boron oxoacid or salt thereof or phosphorus oxoacid or salt thereof. Do.
上記水溶液に含まれうるホウ素のオキソ酸の例としては、オルトホウ酸（Ｈ3ＢＯ3）、メタホウ酸（ＨＢＯ2）、次ホウ酸（Ｈ4Ｂ2Ｏ4）、これらの縮合酸等を挙げることができる。また、前記水溶液に含まれうるリンのオキソ酸の例としては、オルトリン酸（Ｈ3ＰＯ4）、メタリン酸（ＨＰＯ3）、ホスホン酸（Ｈ3ＰＯ3；亜リン酸ともいう）、ホスフィン酸（Ｈ3ＰＯ2；次亜リン酸ともいう）、これらの縮合酸等を挙げることができる。なお、ホウ素のオキソ酸は、必要に応じて、骨格中にホウ素及び酸素以外の元素を含んでいてもよく、また、リンのオキソ酸は、必要に応じて、骨格中にリン及び酸素以外の元素を含んでいてもよい。 Examples of boron oxo acids that can be contained in the aqueous solution include orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ), hypoboric acid (H 4 B 2 O 4 ), and condensed acids thereof. be able to. Examples of phosphorus oxo acids that can be contained in the aqueous solution include orthophosphoric acid (H 3 PO 4 ), metaphosphoric acid (HPO 3 ), phosphonic acid (H 3 PO 3 ; also referred to as phosphorous acid), phosphinic acid (H 3 PO 2 ; also referred to as hypophosphorous acid) and condensed acids thereof. The oxo acid of boron may contain an element other than boron and oxygen in the skeleton, if necessary. The oxo acid of phosphorus may contain elements other than phosphorus and oxygen in the skeleton, if necessary. It may contain an element.
また、上記水溶液に含まれうるホウ素又はリンのオキソ酸塩は、オキソ酸の全てのプロトンが金属イオンやアンモニウムイオンで置き換わった正塩であってもよいし、一部のプロトンが金属イオンやアンモニウムイオンで置き換わった酸性塩であってもよい。この金属イオンの好適な例としては、ナトリウムやカリウムのような周期表１族（ＩＡ族）、カルシウムやマグネシウムのような周期表２族（ＩＩＡ族）、チタンやジルコニウムのような周期表４族（ＩＶＡ族）、亜鉛のような周期表１２族（ＩＩＢ族）の各金属のイオンが挙げられる。また、アンモニウムイオンは、アンモニアがプロトン化されたものであってもよいし、脂肪族、脂環式又は芳香族の第１、第２又は第３アミンがプロトン化されたものであってもよいし、第４アンモニウムイオンであってもよい。 The boron or phosphorus oxo acid salt that can be contained in the aqueous solution may be a normal salt in which all protons of the oxo acid are replaced with metal ions or ammonium ions, or some protons may be metal ions or ammonium ions. It may be an acid salt replaced with ions. Preferred examples of the metal ion include Group 1 of the periodic table (Group IA) such as sodium and potassium, Group 2 of the periodic table (Group IIA) such as calcium and magnesium, and Group 4 of the periodic table such as titanium and zirconium. (Group IVA), ions of metals of Group 12 (Group IIB) of the periodic table such as zinc. The ammonium ion may be one in which ammonia is protonated, or one in which an aliphatic, alicyclic or aromatic primary, secondary or tertiary amine is protonated. And may be a quaternary ammonium ion.
上記水溶液には、必要に応じて、ホウ素のオキソ酸、リンのオキソ酸、ホウ素のオキソ酸塩及びリンのオキソ酸塩から選ばれる２種以上の成分が溶解していてもよい。これら成分の水溶液中の濃度は、２種以上用いた場合には合計で、通常０．０１〜３ｍｏｌ／Ｌ、好ましくは０．０５〜２ｍｏｌ／Ｌである。また、前記水溶液の使用量は、シクロアルカノンオキシム１００重量部に対して、通常１０〜１０００重量部、好ましくは５０〜２００重量部である。 Two or more components selected from boron oxoacids, phosphorus oxoacids, boron oxoacid salts and phosphorus oxoacid salts may be dissolved in the aqueous solution as necessary. The concentration of these components in the aqueous solution is generally 0.01 to 3 mol / L, preferably 0.05 to 2 mol / L in total when two or more kinds are used. Moreover, the usage-amount of the said aqueous solution is 10-1000 weight part normally with respect to 100 weight part of cycloalkanone oxime, Preferably it is 50-200 weight part.
上記水溶液による接触処理は、シクロアルカノンオキシムを含む液体に対して行われる。かかる液体は、シクロアルカノンオキシムを有機溶媒に溶解させたものであってもよいし、実質的にシクロアルカノンオキシムのみからなるものであってもよいが、後者の場合、シクロアルカノンオキシムが常温で固体であれば、接触処理の温度をシクロアルカノンオキシムが溶融する温度以上にして、溶融物とする必要がある。 The contact treatment with the aqueous solution is performed on a liquid containing cycloalkanone oxime. Such a liquid may be one in which cycloalkanone oxime is dissolved in an organic solvent, or may be substantially composed only of cycloalkanone oxime. If it is solid at normal temperature, it is necessary to make the temperature of the contact treatment higher than the temperature at which the cycloalkanone oxime melts to obtain a melt.
上記有機溶媒としては、水と分液可能なもの、例えば、ヘキサン、ヘプタン、オクタンのような脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロヘキサンのような脂環式炭化水素；ベンゼン、トルエン、キシレンのような芳香族炭化水素；ジクロロメタン、１，２−ジクロロエタンのようなハロゲン化脂肪族炭化水素；クロロベンゼン、ジクロロベンゼンのようなハロゲン化芳香族炭化水素；エチルメチルケトン、イソブチルメチルケトンのようなケトン；酢酸エチル、酢酸イソプロピルのようなエステル等が挙げられ、必要に応じてそれらの２種以上を用いることもできる。中でも芳香族炭化水素が好ましい。かかる溶媒の使用量は、シクロアルカノンオキシム１００重量部に対し、通常１０〜１０００重量部、好ましくは５０〜２００重量部である。 Examples of the organic solvent include those that can be separated from water, for example, aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane; benzene, toluene, xylene Halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane; Halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Ketones such as ethyl methyl ketone and isobutyl methyl ketone An ester such as ethyl acetate or isopropyl acetate may be used, and two or more of them may be used as necessary. Of these, aromatic hydrocarbons are preferred. The amount of the solvent used is usually 10 to 1000 parts by weight, preferably 50 to 200 parts by weight, per 100 parts by weight of cycloalkanone oxime.
シクロアルカノンオキシムを含む液体と前記水溶液との接触処理は、両者を攪拌や振盪等により混合することにより行うことができる。処理温度は通常２０℃以上、好ましくは２０〜１００℃であるが、実質的にシクロアルカノンオキシムのみからなる溶融物を処理する場合は、前記のとおり、処理温度をその溶融温度以上とする必要がある。なお、この処理中は、シクロアルカノンオキシムが前記水溶液と接触状態にあるので、比較的高い温度であってもよい。 The contact treatment between the liquid containing cycloalkanone oxime and the aqueous solution can be performed by mixing the two together by stirring or shaking. The processing temperature is usually 20 ° C. or higher, preferably 20 to 100 ° C., but when processing a melt consisting essentially of cycloalkanone oxime, the processing temperature needs to be higher than the melting temperature as described above. There is. During this treatment, since the cycloalkanone oxime is in contact with the aqueous solution, a relatively high temperature may be used.
接触処理後は、油層と水層に分離して、油層としてシクロアルカノンオキシム乃至その溶液を回収することができる。なお、接触処理は必要により複数回行ってもよい。また、接触処理の前、又は後に水洗を行ってもよい。また、接触処理や水洗により不溶物が生じたときには、濾過して除去するのがよい。 After the contact treatment, it can be separated into an oil layer and an aqueous layer, and cycloalkanone oxime or a solution thereof can be recovered as the oil layer. In addition, you may perform a contact process in multiple times as needed. Moreover, you may wash with water before or after a contact process. In addition, when insoluble matter is generated by contact treatment or washing with water, it is preferably filtered off.
本発明の方法は、シクロアルカノンオキシムの熱安定性向上効果に優れることから、貯蔵、移送、気化等、シクロアルカノンオキシムを５０℃以上、さらには９０℃以上の温度条件に付す場合に、その前処理工程として、有利に採用される。特にシクロアルカノンオキシムを気化させる場合は、貯蔵や移送等に比べてより高温条件で操作されることが多いため、その前処理工程として、シクロアルカノンオキシムの熱安定性向上効果に優れる本発明の方法が、有利に採用される。 Since the method of the present invention is excellent in the thermal stability improvement effect of cycloalkanone oxime, when subjecting cycloalkanone oxime to a temperature condition of 50 ° C. or higher, further 90 ° C. or higher, such as storage, transfer, vaporization, The pretreatment process is advantageously employed. In particular, when vaporizing cycloalkanone oxime, since it is often operated at higher temperature conditions than storage and transfer, etc., the pretreatment step is excellent in the effect of improving the thermal stability of cycloalkanone oxime. This method is advantageously employed.
本発明者等は、鉄やニッケル、クロム等の周期表５族〜１１族（ＶＡ〜ＶＩＩＡ族、ＶＩＩＩ族、ＩＢ族）の遷移金属成分、例えば金属乃至その酸化物、塩、錯体等が、シクロアルカノンオキシムの熱安定性を阻害することを見出した。これら遷移金属成分は、シクロアルカノンオキシムの製造プロセスにおいて、反応器、タンク、配管等の材料として使用される金属材料、例えばステンレス等の構成成分であることから、これと接触したシクロアルカノンオキシム中に溶出して、その熱安定性を阻害する。さらにこのシクロアルカノンオキシムを気化させる場合、上記遷移金属成分は、残留シクロアルカノンオキシム中に濃縮されて高濃度で存在することとなり、その熱安定性を一層阻害する。このような熱安定性が阻害されたシクロアルカノンオキシムに対しては、従来の方法では熱安定性を向上させることが困難であったが、本発明の方法によれば、効果的に熱安定性を向上させることができる。なお、シクロアルカノンオキシムの熱安定性をより向上させるためには、反応器、タンク、配管等の材料として、上記遷移金属成分を含まない材料を用いることや、シクロアルカノンオキシムと接触する部分がガラスやフッ素樹脂でライニングされた材料を用いることが望ましい。 The inventors of the present invention have transition metal components of Group 5 to Group 11 (VA to VIIA, Group VIII, Group IB) such as iron, nickel, and chromium, such as metals or oxides, salts, and complexes thereof. It was found to inhibit the thermal stability of cycloalkanone oximes. These transition metal components are metal materials used as materials for reactors, tanks, pipes, etc. in the cycloalkanone oxime production process, such as stainless steel, so that cycloalkanone oximes in contact therewith Elutes in and inhibits its thermal stability. Further, when the cycloalkanone oxime is vaporized, the transition metal component is concentrated in the residual cycloalkanone oxime and is present at a high concentration, further inhibiting the thermal stability. For cycloalkanone oximes whose thermal stability is inhibited, it has been difficult to improve the thermal stability by the conventional method. However, according to the method of the present invention, the thermal stability is effectively improved. Can be improved. In order to further improve the thermal stability of cycloalkanone oxime, a material that does not contain the above transition metal component is used as a material for the reactor, tank, piping, etc. It is desirable to use a material lined with glass or fluororesin.
以下、本発明の実施例を示すが、本発明はこれらによって限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited thereto.
参考例１
シクロヘキサノンオキシム〔純度８９．２重量％（ガスクロマトグラフィーによる測定値）；鉄２４モルｐｐｍを含有（原子吸光分析による測定値）〕１００ｇを、ガラスフラスコ中、フッ素樹脂被覆の攪拌子で攪拌しながら、窒素気流下で２００℃にて５時間加熱した後、０．４Ｔｏｒｒ（５３Ｐａ）、１５８℃にて、減圧蒸留を留出が見られなくなるまで行った。残留液（タール分）の量は５７．１ｇ（仕込量に対し５７．１重量％）であった。
Reference example 1
While stirring 100 g of cyclohexanone oxime [purity 89.2% by weight (measured by gas chromatography); containing 24 mol ppm of iron (measured by atomic absorption analysis)] with a fluororesin-coated stirrer in a glass flask After heating at 200 ° C. for 5 hours under a nitrogen stream, vacuum distillation was performed at 0.4 Torr (53 Pa) and 158 ° C. until no distillation was observed. The amount of the residual liquid (tar content) was 57.1 g (57.1% by weight based on the charged amount).
実施例１
参考例１と同じシクロヘキサノンオキシム１００ｇをトルエン１００ｇに溶解させ、この溶液に濃度１ｍｏｌ／Ｌのオルトリン酸水溶液１００ｇを加え、７５℃にて１時間攪拌した後、油層と水層に分離した。次いで、この油層に水１００ｇを加え、７５℃にて１時間攪拌した後、濾過して微量の不溶物を除去し、油層と水層に分離した。この油層を減圧下に濃縮してトルエンを留去し、シクロヘキサノンオキシム９８ｇを回収した。このシクロヘキサノンオキシムを、参考例１と同様に、加熱、次いで減圧蒸留した。残留液（タール分）の量は１９．４ｇ（仕込量に対し１９．８重量％）であった。
Example 1
100 g of the same cyclohexanone oxime as in Reference Example 1 was dissolved in 100 g of toluene, 100 g of an orthophosphoric acid aqueous solution having a concentration of 1 mol / L was added to this solution, and the mixture was stirred at 75 ° C. for 1 hour, and then separated into an oil layer and an aqueous layer. Next, 100 g of water was added to the oil layer, and the mixture was stirred at 75 ° C. for 1 hour, and then filtered to remove a trace amount of insoluble matter, and the oil layer and the aqueous layer were separated. The oil layer was concentrated under reduced pressure to distill off toluene, and 98 g of cyclohexanone oxime was recovered. This cyclohexanone oxime was heated and then distilled under reduced pressure in the same manner as in Reference Example 1. The amount of the residual liquid (tar content) was 19.4 g (19.8% by weight based on the charged amount).
参考例２
シクロヘキサノンオキシム〔純度９８重量％（ガスクロマトグラフィーによる測定値）；鉄８モルｐｐｍを含有（原子吸光分析による測定値）〕１００ｇを、参考例１と同様に、加熱、次いで減圧蒸留した。残留液（タール分）の量は３５．７ｇ（仕込量に対し３５．７重量％）であった。
Reference example 2
100 g of cyclohexanone oxime [purity 98% by weight (measured by gas chromatography); containing 8 mol ppm of iron (measured by atomic absorption analysis)] was heated and then distilled under reduced pressure in the same manner as in Reference Example 1. The amount of the residual liquid (tar content) was 35.7 g (35.7% by weight based on the charged amount).
実施例２
参考例２と同じシクロヘキサノンオキシム１００ｇをトルエン１００ｇに溶解させ、この溶液に濃度０．１ｍｏｌ／Ｌのオルトホウ酸水溶液１００ｇを加え、７５℃にて１時間攪拌した後、油層と水層に分離した。次いで、この油層に水１００ｇを加え、７５℃にて１時間攪拌した後、濾過して微量の不溶物を除去し、油層と水層に分離した。この油層を減圧下に濃縮してトルエンを留去し、シクロヘキサノンオキシム９８ｇを回収した。このシクロヘキサノンオキシムを、参考例１と同様に、加熱、次いで減圧蒸留した。残留液（タール分）の量は７．３ｇ（仕込量に対し７．４重量％）であった。
Example 2
100 g of the same cyclohexanone oxime as in Reference Example 2 was dissolved in 100 g of toluene, 100 g of a 0.1 mol / L orthoboric acid aqueous solution was added to this solution, and the mixture was stirred at 75 ° C. for 1 hour, and then separated into an oil layer and an aqueous layer. Next, 100 g of water was added to the oil layer, and the mixture was stirred at 75 ° C. for 1 hour, and then filtered to remove a trace amount of insoluble matter, and the oil layer and the aqueous layer were separated. The oil layer was concentrated under reduced pressure to distill off toluene, and 98 g of cyclohexanone oxime was recovered. This cyclohexanone oxime was heated and then distilled under reduced pressure in the same manner as in Reference Example 1. The amount of residual liquid (tar content) was 7.3 g (7.4% by weight based on the charged amount).
比較例１
参考例２と同じシクロヘキサノンオキシム１００ｇをトルエン１００ｇに溶解させ、この溶液に水１００ｇを加え、７５℃にて１時間攪拌した後、油層と水層に分離した。この油層を減圧下に濃縮してトルエンを留去し、シクロヘキサノンオキシム９８ｇを回収した。このシクロヘキサノンオキシムを、参考例１と同様に、加熱、次いで減圧蒸留した。残留液（タール分）の量は２９．８ｇ（仕込量に対し３０．４重量％）であった。
Comparative Example 1
The same cyclohexanone oxime 100 g as in Reference Example 2 was dissolved in 100 g of toluene, 100 g of water was added to this solution, and the mixture was stirred at 75 ° C. for 1 hour, and then separated into an oil layer and an aqueous layer. The oil layer was concentrated under reduced pressure to distill off toluene, and 98 g of cyclohexanone oxime was recovered. This cyclohexanone oxime was heated and then distilled under reduced pressure in the same manner as in Reference Example 1. The amount of the residual liquid (tar content) was 29.8 g (30.4% by weight based on the charged amount).
比較例２
参考例２と同じシクロヘキサノンオキシム１００ｇをトルエン１００ｇに溶解させ、この溶液に濃度０．１ｍｏｌ／Ｌの水酸化ナトリウム水溶液１００ｇを加え、７５℃にて１時間攪拌した後、油層と水層に分離した。次いで、この油層に水１００ｇを加え、７５℃にて１時間攪拌した後、濾過して微量の不溶物を除去し、油層と水層に分離した。この油層を減圧下に濃縮してトルエンを留去し、シクロヘキサノンオキシム９８ｇを回収した。このシクロヘキサノンオキシムを、参考例１と同様に、加熱、次いで減圧蒸留した。残留液（タール分）の量は１２ｇ（仕込量に対し１２．２重量％）であった。
Comparative Example 2
100 g of the same cyclohexanone oxime as in Reference Example 2 was dissolved in 100 g of toluene, 100 g of a 0.1 mol / L sodium hydroxide aqueous solution was added to this solution, and the mixture was stirred at 75 ° C. for 1 hour, and then separated into an oil layer and an aqueous layer. . Next, 100 g of water was added to the oil layer, and the mixture was stirred at 75 ° C. for 1 hour, and then filtered to remove a trace amount of insoluble matter, and the oil layer and the aqueous layer were separated. The oil layer was concentrated under reduced pressure to distill off toluene, and 98 g of cyclohexanone oxime was recovered. This cyclohexanone oxime was heated and then distilled under reduced pressure in the same manner as in Reference Example 1. The amount of the residual liquid (tar content) was 12 g (12.2% by weight based on the charged amount).
Claims (5)
水溶液と接触させた後、油層と水層に分離し、次いで油層を回収することを特徴とするシクロアルカノンオキシムの処理方法。 A liquid containing oxime, after contact with an aqueous solution of boron or oxo acid or a salt of phosphoric, separated into an oil layer and an aqueous layer, followed by the oxime which is characterized that you recover oil layer Processing method.
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| TW093135364A TWI341830B (en) | 2003-11-28 | 2004-11-18 | Stabilization method of cycloalkanone oxime |
| KR1020040096279A KR101135913B1 (en) | 2003-11-28 | 2004-11-23 | Stabilization method of cycloalkanone oxime |
| US10/995,253 US7232928B2 (en) | 2003-11-28 | 2004-11-24 | Stabilization method of cycloalkanone oxime |
| EP04028124A EP1550652A3 (en) | 2003-11-28 | 2004-11-26 | Stabilization method of cycloalkanone oxime |
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