JP2005289827A - Method for handling cycloalkanone oxime - Google Patents
Method for handling cycloalkanone oxime Download PDFInfo
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- JP2005289827A JP2005289827A JP2004103180A JP2004103180A JP2005289827A JP 2005289827 A JP2005289827 A JP 2005289827A JP 2004103180 A JP2004103180 A JP 2004103180A JP 2004103180 A JP2004103180 A JP 2004103180A JP 2005289827 A JP2005289827 A JP 2005289827A
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- cycloalkanone oxime
- oxime
- cycloalkanone
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- 150000002923 oximes Chemical class 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 80
- 229910052742 iron Inorganic materials 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000000155 melt Substances 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 11
- 229910052804 chromium Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 8
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- -1 alicyclic hydrocarbons Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 2
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- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 150000002505 iron Chemical class 0.000 description 2
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- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
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- 238000002411 thermogravimetry Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 229910000831 Steel Inorganic materials 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 239000010949 copper Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 238000004255 ion exchange chromatography Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SCRFXJBEIINMIC-UHFFFAOYSA-N n-cyclododecylidenehydroxylamine Chemical compound ON=C1CCCCCCCCCCC1 SCRFXJBEIINMIC-UHFFFAOYSA-N 0.000 description 1
- KTPUHSVFNHULJH-UHFFFAOYSA-N n-cyclooctylidenehydroxylamine Chemical compound ON=C1CCCCCCC1 KTPUHSVFNHULJH-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
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- 229910052719 titanium Inorganic materials 0.000 description 1
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、シクロアルカノンオキシムを熱的に安定に取り扱う方法に関する。 The present invention relates to a method for thermally handling cycloalkanone oximes stably.
シクロアルカノンオキシムは比較的、熱に不安定な化合物でありながら、貯蔵や移送の際には加熱溶融させて取り扱われることが多く、また、例えば気相ベックマン転位反応の原料ガスとして用いる場合等、加熱気化させて使用される場合もある。このため、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が種々提案されており、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、これら方法を適用しても、シクロアルカノンオキシムの熱安定化効果の再現性が低く、熱安定性が比較的向上することもあれば、熱安定性が殆んど向上しないこともあった。 However, even if these methods are applied, the reproducibility of the thermal stabilization effect of cycloalkanone oxime is low, and the thermal stability may be relatively improved or the thermal stability may be hardly improved. It was.
そこで、本発明者等は、シクロアルカノンオキシムの熱安定性に関する基礎的知見として、上記再現性が得られない原因を解明すべく鋭意研究を行った結果、シクロアルカノンオキシムには、その製造プロセスにおける反応器、タンク、配管等の鉄材料に由来すると思われる鉄分が微量に含まれており、この鉄分が、シクロアルカノンオキシム、特に加熱溶融状態等の加熱液体状態にあるシクロアルカノンオキシムの熱安定性を悪化させるため、組成乃至製法が同じシクロアルカノンオキシムであっても、その鉄含量によって安定性が異なることを見出した。そして、この鉄分の含量を所定値以下に管理することで、加熱液体状のシクロアルカノンオキシムを熱安定性良く取り扱うことができることを見出し、本発明を完成するに至った。 Therefore, as a result of intensive studies to elucidate the cause of the inability to obtain the above reproducibility as basic knowledge about the thermal stability of cycloalkanone oxime, the present inventors have found that cycloalkanone oxime is produced by The process contains a small amount of iron that may be derived from ferrous materials such as reactors, tanks, and pipes. This iron content is cycloalkanone oxime, especially cycloalkanone oxime that is in a heated liquid state such as a heated molten state. In order to deteriorate the thermal stability of the present invention, it was found that even if the cycloalkanone oxime has the same composition or production method, the stability varies depending on the iron content. The inventors have found that by controlling the iron content below a predetermined value, the heated liquid cycloalkanone oxime can be handled with good thermal stability, and the present invention has been completed.
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５０℃以上の温度で取り扱う際、該液体中の鉄含有量を３０重量ｐｐｍ以下に管理することを特徴とするシクロアルカノンオキシムの取り扱い方法を提供するものである。 That is, the present invention relates to a method for handling cycloalkanone oxime, wherein when a liquid containing cycloalkanone oxime is handled at a temperature of 50 ° C. or higher, the iron content in the liquid is controlled to 30 ppm by weight or less. Is to provide.
本発明によれば、シクロアルカノンオキシムを含む液体を熱安定性良く取り扱うことができる。 According to the present invention, a liquid containing cycloalkanone oxime can be handled with good thermal stability.
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、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℃以上にして加熱溶融させ、液体状で取り扱われることが多い。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、上記溶融物や溶液等の液状シクロアルカノンオキシムが気化器への供給液として用いられ、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。このように加熱液体状態にあるシクロアルカノンオキシムは特に熱安定性に劣り、そこで、本発明は、シクロアルカノンを含む液体を加熱状態で、具体的には５０℃以上、好適には９０℃以上の温度で取り扱う場合の安定性向上を目的としている。 Many cycloalkanone oximes are solid at room temperature, and in order to facilitate handling during storage and transfer, cycloalkanone oximes should be above the melting point, for example, cyclopentanone oxime at 53 to 55 ° C. or higher, cyclohexanone oxime. In many cases, it is heated and melted at 89 to 91 ° C. or higher and handled in a liquid state. 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 preparing a raw material gas for vapor phase Beckmann rearrangement reaction, liquid cycloalkanone oxime such as the above-mentioned melt or solution is vaporized. In the case of normal pressure, it may be heated above its boiling point, for example, 196 ° C. or higher for cyclopentanone oxime, 206 to 210 ° C. or higher for cyclohexanone oxime, Even in the case of entraining with a low boiling point gas, it may be heated to 150 ° C. or higher, for example. Thus, the cycloalkanone oxime in a heated liquid state is particularly inferior in thermal stability. Therefore, the present invention is a liquid containing a cycloalkanone in a heated state, specifically 50 ° C. or higher, preferably 90 ° C. The purpose is to improve stability when handling at the above temperature.
シクロアルカノンオキシムを含む液体は、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、液体とするには、溶融温度以上にして溶融物とする必要がある。 The liquid containing cycloalkanone oxime may be prepared by dissolving cycloalkanone oxime in an organic solvent, or may be substantially composed of only cycloalkanone oxime, but in the latter case, In order to make it into a liquid, it is necessary to make it into a melt above the melting temperature.
上記有機溶媒としては、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；酢酸エチル、酢酸イソプロピルのようなエステル；メタノール、エタノール、イソプロピルアルコールのようなアルコール等が挙げられ、その量は、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５０〜３００重量部である。 Examples of the organic solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; Halogenated aliphatic hydrocarbons such as dichloromethane and 1,2-dichloroethane; Halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Esters such as ethyl acetate and isopropyl acetate; Like methanol, ethanol and isopropyl alcohol Alcohol etc. are mentioned, The quantity is 10-1000 weight part normally with respect to 100 weight part of cycloalkanone oxime, Preferably it is 50-300 weight part.
本発明者等は、シクロアルカノンオキシムには、その製造プロセスにおける反応器、タンク、配管等の材料、具体的には鋼鉄（ＳＳ）やステンレス（ＳＵＳ）等に由来すると思われる鉄分が微量に含まれており、この鉄分が、特にシクロアルカノンオキシムを含む液体が加熱状態にある場合に、その熱安定性を著しく悪化させることを見出した。かかる鉄分は、シクロアルカノンオキシム中に金属、イオン、酸化物、塩、錯体等の状態で存在し得、シクロアルカノンオキシムが鉄材料と接触した時間が長いほど、また、鉄材料と接触した温度が高いほど、多く存在する傾向にあって、熱安定性をさらに悪化させる。 The present inventors have found that cycloalkanone oxime contains a small amount of iron, which is considered to be derived from materials such as reactors, tanks and piping in the production process, specifically steel (SS) and stainless steel (SUS). It has been found that this iron content significantly deteriorates its thermal stability, particularly when the liquid containing cycloalkanone oxime is in a heated state. Such iron can be present in the cycloalkanone oxime in the form of metals, ions, oxides, salts, complexes, etc. The longer the time the cycloalkanone oxime is in contact with the iron material, the more it is in contact with the iron material. The higher the temperature, the more tend to exist, further exacerbating the thermal stability.
そこで、本発明では、シクロアルカノンオキシムを含む液体を５０℃以上の温度で取り扱う場合において、該液体中の鉄の含有量を、３０重量ｐｐｍ以下、好ましくは１０重量ｐｐｍ以下、さらに好ましくは５重量ｐｐｍ以下に収まるように管理する。これにより、シクロアルカノンオキシムの熱安定性を改善することができ、安全な取り扱いが可能となる。 Therefore, in the present invention, when a liquid containing cycloalkanone oxime is handled at a temperature of 50 ° C. or higher, the iron content in the liquid is 30 ppm by weight or less, preferably 10 ppm by weight or less, more preferably 5 ppm. The weight is controlled so as to be within ppm. Thereby, the thermal stability of cycloalkanone oxime can be improved and safe handling becomes possible.
さらに、本発明者等は、鉄だけでなく、クロム、モリブデン、タングステン、マンガン、コバルト、ニッケル、銅等の周期表５族〜１１族（ＶＡ族〜ＶＩＩＡ族、ＶＩＩＩ族、ＩＢ族）の遷移金属もシクロアルカノンオキシムの熱安定性を悪化させうることを見出した。例えば、ステンレスのＳＵＳ−３０４は、鉄、ニッケル及びクロムからなるので、これと接触した履歴を持つシクロアルカノンオキシムは、鉄に加えニッケルやクロムも含みうる。また、ステンレスのＳＵＳ−３１６は、鉄、ニッケル、クロム及びモリブデンからなるので、これと接触した履歴を持つシクロアルカノンオキシムは、鉄に加えニッケルやクロム、モリブデンも含みうる。そこで、シクロアルカノンオキシムを含む液体に、鉄分に加えて上記遷移金属成分も混入しうる場合は、鉄含量と共に上記遷移金属の少なくとも１種の含量も、併せて管理してもよい。特に上記ＳＵＳ−３０４やＳＵＳ−３１６の如きステンレスは、鉄材料としてよく用いられるので、鉄と共にニッケルとクロムの含量も併せて管理するのがよい。この場合、シクロアルカノンオキシムを含む液体中の鉄、ニッケル及びクロムの各含有量の合計が、３０重量ｐｐｍ以下、好ましくは１０重量ｐｐｍ以下、さらに好ましくは５重量ｐｐｍ以下に収まるようにするのがよい。 Furthermore, the present inventors not only made iron, but also transitions of groups 5 to 11 (VA group to VIIA group, VIII group, and IB group) of periodic table such as chromium, molybdenum, tungsten, manganese, cobalt, nickel, copper and the like. It has been found that metals can also degrade the thermal stability of cycloalkanone oximes. For example, since stainless steel SUS-304 is made of iron, nickel, and chromium, a cycloalkanone oxime having a history of contact with the stainless steel may contain nickel and chromium in addition to iron. Since stainless steel SUS-316 is made of iron, nickel, chromium, and molybdenum, the cycloalkanone oxime having a history of contact with the stainless steel may contain nickel, chromium, and molybdenum in addition to iron. Therefore, when the transition metal component can be mixed in addition to iron in the liquid containing cycloalkanone oxime, the content of at least one transition metal as well as the iron content may be managed together. In particular, since stainless steel such as SUS-304 and SUS-316 is often used as an iron material, it is preferable to manage the contents of nickel and chromium together with iron. In this case, the total content of iron, nickel and chromium in the liquid containing cycloalkanone oxime should be 30 ppm by weight or less, preferably 10 ppm by weight or less, more preferably 5 ppm by weight or less. Is good.
シクロアルカノンオキシムを含む液体中の鉄含量は、例えば、原子吸光分析、誘導結合高周波プラズマ（ＩＣＰ）分光分析、イオンクロマトグラフィー、比色法等により測定することができる。また、上記液体の態様により、鉄含量と相関のあるパラメータが存在する場合は、これを鉄含量の分析値に代用してもよい。かかるパラメータとしては、例えば、熱重量測定（ＴＧ）、示差熱分析（ＤＴＡ）、示差走査熱量測定（ＤＳＣ）、加速速度熱量測定（ＡＲＣ）等の各熱分析のパラメータを挙げることができる。なお、鉄含量だけでなく上記遷移金属の含量も併せて管理する場合、その測定法には上記鉄含量と同様の測定法を採用することができる。 The iron content in the liquid containing cycloalkanone oxime can be measured by, for example, atomic absorption analysis, inductively coupled plasma (ICP) spectroscopic analysis, ion chromatography, colorimetric method or the like. Further, when there is a parameter having a correlation with the iron content according to the aspect of the liquid, it may be substituted for the analytical value of the iron content. Examples of such parameters include thermal analysis parameters such as thermogravimetry (TG), differential thermal analysis (DTA), differential scanning calorimetry (DSC), and accelerated velocity calorimetry (ARC). In addition, when managing not only the iron content but also the content of the transition metal, a measurement method similar to the iron content can be adopted as the measurement method.
シクロアルカノンオキシム含有液中の鉄含量を所定値以下にするためには、該液体が鉄材料と接触する時間をなるべく短くし、鉄材料と接触するときの温度をなるべく低くするのがよい。また、鉄材料に代えて、鉄不含の材料、例えば、亜鉛、錫、アルミニウム、チタンのような金属からなる材料、ガラス、樹脂等を用いることや、鉄材料がこれら金属、ガラス、フッ素樹脂等でライニングされた材料を用いることも、有効である。 In order to reduce the iron content in the cycloalkanone oxime-containing liquid to a predetermined value or less, it is preferable to shorten the time during which the liquid is in contact with the iron material as much as possible and to reduce the temperature at which the liquid is in contact with the iron material as low as possible. Also, instead of iron materials, iron-free materials, for example, materials made of metals such as zinc, tin, aluminum, titanium, glass, resins, etc. are used, and iron materials are made of these metals, glasses, fluororesins. It is also effective to use a material lined with, for example.
特にシクロアルカノンオキシムを気化させる場合、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、通常、シクロアルカノンオキシム含有液がフィード原料として用いられ、これが高温条件に付されるので、特に本発明の方法を適用するのが有効である。この場合、通常、シクロアルカノンオキシム含有ガスと共に、蒸留塔塔底液等の缶液（濃縮液）が発生するが、この缶液中に鉄分が濃縮されて高含量になるので、この管理が特に重要となる。この缶液中の鉄含量を所定値以下に保つには、フィード原料であるシクロアルカノンオキシム含有液中の鉄含量を分析し、この分析値に基づいて濃縮率の上限を定めるのがよい。また、該フィード原料中の鉄分が微量過ぎて測定できない場合は、適宜、缶液中の鉄含量を分析して、所定値を超えないように運転を行うのがよい。 In particular, when vaporizing cycloalkanone oxime, for example, when purifying by distillation or preparing a raw material gas for gas phase Beckmann rearrangement reaction, a cycloalkanone oxime-containing liquid is usually used as a feed raw material. Since it is subjected to high temperature conditions, it is particularly effective to apply the method of the present invention. In this case, a canal liquid (concentrated liquid) such as a distillation tower bottom liquid is usually generated together with the cycloalkanone oxime-containing gas. Especially important. In order to keep the iron content in the can liquid below a predetermined value, it is preferable to analyze the iron content in the cycloalkanone oxime-containing liquid as a feed material and to set the upper limit of the concentration rate based on the analysis value. In addition, when the iron content in the feed material is too small to be measured, it is preferable to appropriately analyze the iron content in the can and operate so as not to exceed a predetermined value.
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。なお、例中、鉄、ニッケル及びクロムの含量は原子吸光分析による測定値であり、検出下限値は鉄が０．１重量ｐｐｍ、ニッケルが０．２重量ｐｐｍ、クロムが０．４重量ｐｐｍである。 Examples of the present invention will be described below, but the present invention is not limited thereto. In the examples, the contents of iron, nickel and chromium are measured by atomic absorption analysis, and the detection lower limit values are 0.1 ppm by weight for iron, 0.2 ppm by weight for nickel and 0.4 ppm by weight for chromium. is there.
実施例１〜４、比較例１
検出下限値未満の鉄、ニッケル及びクロムを含むシクロヘキサノンオキシム（シクロヘキサノンのアンモキシム化反応により調製）の溶融物を供給原料として用い、メタノール及び窒素と共に、濡れ壁蒸発器にシクロアルカノンオキシム／メタノール／窒素＝５／９／１（重量比）の割合で連続的に供給して、シクロヘキサノンオキシム、メタノール及び窒素を含むガスを連続的に生成させると共に、缶液を連続的に抜き出した。蒸発圧力９５０ｔｏｒｒ（０．１２５ＭＰａ）以下、蒸発温度１４０〜１６０℃の範囲で供給量を調整して、表１に示す鉄含量、ニッケル含量及びクロム含量の各缶液を得た。各缶液について、加速速度熱量測定（ＡＲＣ）〔「住友化学 １９８９−Ｉ」（住友化学工業株式会社、１９８９年発行）第６１〜８１頁参照〕を行い、自己発熱速度が０．０２℃／分以上になるときの温度である発熱開始温度を求めると共に、１５０℃における自己発熱速度が最大値になるまでの時間であるＴＭＲ（Time to Maximum Rate）を求めた。結果を表１に示す。
Examples 1-4, Comparative Example 1
Using a melt of cyclohexanone oxime (prepared by ammoximation reaction of cyclohexanone) containing iron, nickel and chromium below the lower detection limit as feedstock, along with methanol and nitrogen, cycloalkanone oxime / methanol / nitrogen in the wet wall evaporator = 5/9/1 (weight ratio) was continuously supplied to continuously generate a gas containing cyclohexanone oxime, methanol and nitrogen, and the can liquid was continuously extracted. The supply amount was adjusted in an evaporation pressure range of 950 torr (0.125 MPa) or less and an evaporation temperature range of 140 to 160 ° C. to obtain cans of iron content, nickel content and chromium content shown in Table 1. Each can solution is subjected to accelerated rate calorimetry (ARC) ["Sumitomo Chemical 1989-I" (Sumitomo Chemical Co., Ltd., 1989), pages 61-81], and the self-heating rate is 0.02 ° C / A heat generation start temperature, which is a temperature when the temperature becomes equal to or higher than a minute, was obtained, and a TMR (Time to Maximum Rate), which was a time until the self-heating rate at 150 ° C. reached the maximum value, was obtained. The results are shown in Table 1.
Claims (5)
The method according to any one of claims 1 to 3, wherein the liquid containing cycloalkanone oxime is a melt substantially consisting only of cycloalkanone oxime.
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| 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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| JPS4742517Y1 (en) * | 1964-01-08 | 1972-12-22 | ||
| JPS541295B1 (en) * | 1967-04-06 | 1979-01-23 | ||
| JPS541294B1 (en) * | 1967-04-06 | 1979-01-23 | ||
| JPH02193957A (en) * | 1988-11-23 | 1990-07-31 | Basf Ag | Method for improving storage stability of fused cyclohexanone oxime |
| JPH05186409A (en) * | 1992-01-10 | 1993-07-27 | Sumitomo Chem Co Ltd | Method for suppressing thermal decomposition of cycloalkanone oxime |
| JP2003034674A (en) * | 2001-06-28 | 2003-02-07 | Enichem Spa | Method for purifying cyclohexanone-oxime |
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| JPS4742517Y1 (en) * | 1964-01-08 | 1972-12-22 | ||
| JPS541295B1 (en) * | 1967-04-06 | 1979-01-23 | ||
| JPS541294B1 (en) * | 1967-04-06 | 1979-01-23 | ||
| JPH02193957A (en) * | 1988-11-23 | 1990-07-31 | Basf Ag | Method for improving storage stability of fused cyclohexanone oxime |
| JPH05186409A (en) * | 1992-01-10 | 1993-07-27 | Sumitomo Chem Co Ltd | Method for suppressing thermal decomposition of cycloalkanone oxime |
| JP2003034674A (en) * | 2001-06-28 | 2003-02-07 | Enichem Spa | Method for purifying cyclohexanone-oxime |
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