JP2005154393A - Method for treating cycloalkanone oxime - Google Patents
Method for treating cycloalkanone oxime Download PDFInfo
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- JP2005154393A JP2005154393A JP2003399147A JP2003399147A JP2005154393A JP 2005154393 A JP2005154393 A JP 2005154393A JP 2003399147 A JP2003399147 A JP 2003399147A JP 2003399147 A JP2003399147 A JP 2003399147A JP 2005154393 A JP2005154393 A JP 2005154393A
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- Prior art keywords
- oxime
- cycloalkanone
- cycloalkanone oxime
- oxo acid
- boron
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- 150000002923 oximes Chemical class 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 15
- -1 oxo acid salt Chemical class 0.000 claims abstract description 19
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000004715 keto acids Chemical class 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 230000008016 vaporization Effects 0.000 claims abstract description 6
- 229910052810 boron oxide Inorganic materials 0.000 claims description 5
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 5
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 12
- 239000011574 phosphorus Substances 0.000 abstract description 12
- 229910052796 boron Inorganic materials 0.000 abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000009834 vaporization Methods 0.000 abstract description 3
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 25
- 238000004821 distillation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000001412 amines Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000003158 alcohol group Chemical group 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- YGNXYFLJZILPEK-UHFFFAOYSA-N n-cyclopentylidenehydroxylamine Chemical compound ON=C1CCCC1 YGNXYFLJZILPEK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229960002645 boric acid Drugs 0.000 description 2
- 235000010338 boric acid Nutrition 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- MOWNZPNSYMGTMD-UHFFFAOYSA-N oxidoboron Chemical class O=[B] MOWNZPNSYMGTMD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 125000005618 boron oxoacid group Chemical group 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000007769 metal material 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
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- 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加熱する際、例えば貯蔵、移送、気化等の際に好適に用いられる、シクロアルカノンオキシムの処理方法に関する。 The present invention relates to a method for treating a cycloalkanone oxime, which is suitably used for heating a cycloalkanone oxime, for example, during storage, transfer, vaporization and the like.
シクロアルカノンオキシムは比較的、熱に不安定であることから、従来、その熱安定性を向上させる方法が種々提案されている。例えば、特公昭４７−４１９０９号公報（特許文献１）には、シクロアルカノンオキシムの気相接触ベックマン転位の際、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ことが提案されている。また、特開平２−１９３９５７号公報（特許文献２）には、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に保ち、溶融シクロヘキサノンオキシムの貯蔵安定性を改良することが提案されている。さらに、特開平５−１８６４０９号公報（特許文献３）には、アンモニア又は低級アルキルアミンを存在させて、シクロアルカノンオキシムの熱分解を抑制することが提案されている。
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でないことがあった。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 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、シクロアルカノンオキシムの熱安定化剤として、ある種の化合物を用いることにより、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に、ホウ素又はリンの酸化物、オキソ酸、オキソ酸塩、オキソ酸エステル及びオキソ酸アミドから選ばれる化合物を添加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を提供するものである。 As a result of intensive studies, the present inventors have found that the above object can be achieved by using a certain compound as a heat stabilizer for cycloalkanone oxime, and have completed the present invention. That is, the present invention provides a cycloalkanone oxime comprising a compound selected from a boron or phosphorus oxide, an oxo acid, an oxo acid salt, an oxo acid ester, and an oxo acid amide. A processing method is provided.
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。これら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. These cycloalkanone oximes include, for example, a method in which cycloalkanone is reacted with hydroxylamine or a salt thereof, a method in which cycloalkane is photonitrosated, and cycloalkanone is reacted with ammonia in the presence of a catalyst such as titanosilicate. It can be produced by a method of reacting with hydrogen oxide.
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、常圧で沸点以上、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、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、ホウ素若しくはリンの酸化物、ホウ素若しくはリンのオキソ酸、又は該オキソ酸の塩、エステル、若しくはアミドを、熱安定化剤としてシクロアルカノンオキシムに添加する。 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 preparing a raw material gas for subjecting to a gas phase Beckmann rearrangement reaction, 196 if it is cyclopentanone oxime above the boiling point at normal pressure. In the case of cyclohexanone oxime, it may be heated to 206 to 210 ° C. or higher, and may be heated to 150 ° C. or higher, for example, even when decompressed or accompanied by a low boiling point gas. Therefore, in the present invention, in order to improve the thermal stability during heating of such cycloalkanone oxime, boron or phosphorus oxide, boron or phosphorus oxo acid, or salt, ester of the oxo acid, or The amide is added to the cycloalkanone oxime as a heat stabilizer.
ホウ素の酸化物の例としては、三酸化二ホウ素（Ｂ2Ｏ3）等が挙げられ、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）、これらの縮合酸等が挙げられる。なお、これらホウ素の酸化物又はオキソ酸は、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い。 Examples of boron oxides include diboron trioxide (B 2 O 3 ), and examples of boron oxo acids include orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ), Examples thereof include boric acid (H 4 B 2 O 4 ) and condensed acids thereof. Note that these boron oxides or oxo acids may contain elements other than boron and oxygen in the skeleton, if necessary.
リンの酸化物の例としては、六酸化四リン（Ｐ4Ｏ6；三酸化リンともいう）、十酸化四リン（Ｐ4Ｏ10；五酸化リンともいう）等が挙げられ、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）、これらの縮合酸等が挙げられる。なお、これらリンの酸化物又はオキソ酸は、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 the oxide of phosphorus include tetraphosphorus hexaoxide (P 4 O 6 ; also referred to as phosphorus trioxide), tetraphosphorus decaoxide (P 4 O 10 ; also referred to as phosphorus pentoxide), and the like. Examples of acids 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 ; hypophosphorous acid) And these condensed acids. Note that these phosphorus oxides or oxoacids may contain elements other than phosphorus and oxygen in the skeleton, if necessary.
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 may be a normal salt in which all protons of the oxo acid are replaced with metal ions or ammonium ions, or an acid salt in which some protons are replaced with metal ions or ammonium ions. May be. 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.
また、ホウ素又はリンのオキソ酸エステルは、オキソ酸の全ての水酸基がアルコール残基（アルコールから酸素原子に結合している水素原子を除いた基）で置き換わったものであってもよいし、一部の水酸基がアルコール残基で置き換わったものであってもよい。同様に、ホウ素又はリンのオキソ酸アミドは、オキソ酸の全ての水酸基がアミン残基（アミンから窒素原子に結合している水素原子を除いた基）で置き換わったものであってもよいし、一部の水酸基がアミン残基で置き換わったものであってもよい。オキソ酸エステルにおけるアルコール残基は、脂肪族、脂環式又は芳香族の第１、第２又は第３アルコールの残基であることができる。また、オキソ酸アミドにおけるアミン残基は、脂肪族、脂環式又は芳香族の第１又は第２アミンの残基であることができる。 Further, the oxo acid ester of boron or phosphorus may be one in which all hydroxyl groups of the oxo acid are replaced with alcohol residues (groups obtained by removing hydrogen atoms bonded to oxygen atoms from alcohols). The hydroxyl group may be replaced with an alcohol residue. Similarly, the oxoacid amide of boron or phosphorus may be one in which all hydroxyl groups of the oxoacid are replaced with amine residues (groups obtained by removing the hydrogen atom bonded to the nitrogen atom from the amine), Some hydroxyl groups may be replaced with amine residues. The alcohol residue in the oxo acid ester can be a residue of an aliphatic, alicyclic or aromatic primary, secondary or tertiary alcohol. Also, the amine residue in the oxoacid amide can be an aliphatic, alicyclic or aromatic primary or secondary amine residue.
上記ホウ素又はリンの化合物の添加量は、シクロアルカノンオキシムに対し、通常０．０００１〜１モル％、好ましくは０．００１〜０．５モル％である。なお、上記ホウ素又はリンの化合物は、必要に応じてそれらの２種以上を用いることもできる。また、上記ホウ素又はリンの化合物は、水や有機溶媒に溶解乃至懸濁させて用いてもよい。 The addition amount of the boron or phosphorus compound is usually 0.0001 to 1 mol%, preferably 0.001 to 0.5 mol% with respect to the cycloalkanone oxime. In addition, the said boron or phosphorus compound can also use those 2 or more types as needed. The boron or phosphorus compound may be dissolved or suspended in water or an organic solvent.
シクロアルカノンオキシムに上記ホウ素又はリンの化合物を添加するタイミングについては、例えばシクロアルカノンオキシムを貯蔵、移送又は気化に付す場合には、貯蔵タンク、移送配管又は気化器等にシクロアルカノンオキシムを導入する前に、予め上記化合物を添加しおいてもよいし、シクロヘキサノンオキシムを導入するに併せて、上記化合物を添加してもよいし、シクロヘキサノンオキシムを導入した後で、上記化合物を添加してもよい。 Regarding the timing of adding the boron or phosphorus compound to the cycloalkanone oxime, for example, when the cycloalkanone oxime is stored, transferred or vaporized, the cycloalkanone oxime is added to the storage tank, transfer pipe or vaporizer. Before the introduction, the above compound may be added in advance, or in addition to the introduction of cyclohexanone oxime, the above compound may be added, or after the introduction of cyclohexanone oxime, the above compound is added. Also good.
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、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、有利に採用される。また、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、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。 The method of the present invention is advantageously employed when the cycloalkanone oxime is subjected to a temperature condition of 50 ° C. or higher, more preferably 90 ° C. or higher because it is excellent in the thermal stability improving effect of cycloalkanone oxime. In addition, when vaporizing cycloalkanone oxime, the method of the present invention, which is excellent in the thermal stability improving effect of cycloalkanone oxime, is often operated at higher temperature conditions than storage and transfer, etc. Adopted.
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。シクロアルカノンオキシムが上記遷移金属成分を含む場合、前記のホウ素又はリンを含む化合物の添加量は、該遷移金属成分の通常１〜１０００モル倍、好ましくは３〜３００モル倍、さらに好ましくは５〜１００モル倍とするのがよい。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 present inventors have disclosed 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, for example, components such as stainless steel. 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 hindering its 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. When the cycloalkanone oxime contains the above transition metal component, the amount of the compound containing boron or phosphorus is usually 1 to 1000 mol times, preferably 3 to 300 mol times, more preferably 5 times that of the transition metal component. It is good to set it to -100 mol times. 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.
実施例１
シクロヘキサノンオキシム〔純度９８．９重量％（ガスクロマトグラフィーによる測定値）；鉄８モルｐｐｍ、クロム０．４モルｐｐｍ及びニッケル０．８モルｐｐｍを含有（原子吸光分析による測定値）〕１００．１ｇに、１重量％オルトホウ酸水溶液０．５ｇを添加して、ガラスフラスコ中、窒素気流下で２００℃にて５時間加熱した後、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５．８９ｇ（仕込量に対し５．９重量％）であった。
Example 1
Cyclohexanone oxime [purity 98.9% by weight (measured by gas chromatography); iron 8 mol ppm, chromium 0.4 mol ppm and nickel 0.8 mol ppm (measured by atomic absorption analysis)] 100.1 g Then, 0.5 g of a 1% by weight aqueous solution of orthoboric acid was added and heated in a glass flask under a nitrogen stream at 200 ° C. for 5 hours, followed by vacuum distillation until no distillation was observed. The amount of the residual liquid (tar content) was 5.89 g (5.9% by weight based on the charged amount).
実施例２
実施例１と同じシクロヘキサノンオキシム１００．１ｇに、１重量％オルトリン酸水溶液０．５ｇを添加して、実施例１と同様に加熱、次いで蒸留を行った。残留液（タール分）の量は３．８９ｇ（仕込量に対し３．９重量％）であった。
Example 2
To 100.1 g of the same cyclohexanone oxime as in Example 1, 0.5 g of a 1% by weight aqueous orthophosphoric acid solution was added and heated in the same manner as in Example 1, followed by distillation. The amount of the residual liquid (tar content) was 3.89 g (3.9% by weight based on the charged amount).
実施例３
実施例１と同じシクロヘキサノンオキシム１００．１ｇに、１重量％亜リン酸水溶液０．５ｇを添加して、実施例１と同様に加熱、次いで蒸留を行った。残留液（タール分）の量は４．２８ｇ（仕込量に対し４．３重量％）であった。
Example 3
To 100.1 g of the same cyclohexanone oxime as in Example 1, 0.5 g of a 1% by weight aqueous phosphorous acid solution was added, followed by heating and distillation as in Example 1. The amount of the residual liquid (tar content) was 4.28 g (4.3% by weight based on the charged amount).
実施例４
実施例１と同じシクロヘキサノンオキシム１００．０８ｇに、１重量％のオルトホウ酸トリメチルを含むメタノール溶液０．６７ｇを添加して、実施例１と同様に加熱、次いで蒸留を行った。残留液（タール分）の量は７．４２ｇ（仕込量に対し７．４重量％）であった。
Example 4
To 100.08 g of the same cyclohexanone oxime as in Example 1, 0.67 g of a methanol solution containing 1% by weight of trimethyl orthoborate was added, followed by heating and distillation as in Example 1. The amount of the residual liquid (tar content) was 7.42 g (7.4% by weight based on the charged amount).
比較例１
実施例１と同じシクロヘキサノンオキシム１１０ｇに、１重量％水酸化ナトリウム水溶液０．５ｇを添加して、実施例１と同様に加熱、次いで蒸留を行った。残留液（タール分）の量は３７．７ｇ（仕込量に対し３４．３重量％）であった。
Comparative Example 1
To 110 g of the same cyclohexanone oxime as in Example 1, 0.5 g of a 1% by weight aqueous sodium hydroxide solution was added and heated in the same manner as in Example 1, followed by distillation. The amount of the residual liquid (tar content) was 37.7 g (34.3% by weight based on the charged amount).
比較例２
実施例１と同じシクロヘキサノンオキシム１００．２９ｇに、添加剤を加えることなく、実施例１と同様に加熱、次いで蒸留を行った。残留液（タール分）の量は２８．０１ｇ（仕込量に対し２７．９重量％）であった。
Comparative Example 2
To 100.29 g of the same cyclohexanone oxime as in Example 1, heating was carried out in the same manner as in Example 1 and then distillation without adding an additive. The amount of the residual liquid (tar content) was 28.01 g (27.9% by weight based on the charged amount).
Claims (3)
The method according to claim 1 or 2, which is carried out when vaporizing 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 |
| CN2004101038394A CN1660786B (en) | 2003-11-28 | 2004-11-26 | Stabilization method of cycloalkanone oxime |
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| JPS541295B1 (en) * | 1967-04-06 | 1979-01-23 | ||
| JPH05186409A (en) * | 1992-01-10 | 1993-07-27 | Sumitomo Chem Co Ltd | Method for suppressing thermal decomposition of cycloalkanone oxime |
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| JPS541295B1 (en) * | 1967-04-06 | 1979-01-23 | ||
| JPH05186409A (en) * | 1992-01-10 | 1993-07-27 | Sumitomo Chem Co Ltd | Method for suppressing thermal decomposition of cycloalkanone oxime |
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