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WO2006033740A1 - Procede pour reduire la teneur en cyclohexenone d'un melange organique contenant de la cyclohexenone - Google Patents

Procede pour reduire la teneur en cyclohexenone d'un melange organique contenant de la cyclohexenone Download PDF

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Publication number
WO2006033740A1
WO2006033740A1 PCT/US2005/029655 US2005029655W WO2006033740A1 WO 2006033740 A1 WO2006033740 A1 WO 2006033740A1 US 2005029655 W US2005029655 W US 2005029655W WO 2006033740 A1 WO2006033740 A1 WO 2006033740A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic mixture
cyclohexenone
mixture
treated
cyclohexanone
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.)
Ceased
Application number
PCT/US2005/029655
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English (en)
Inventor
Ludovic Fodor
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
INVISTA TECHNOLOGIES Sarl
Invista Technologies SARL USA
Original Assignee
INVISTA TECHNOLOGIES Sarl
Invista Technologies SARL USA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by INVISTA TECHNOLOGIES Sarl, Invista Technologies SARL USA filed Critical INVISTA TECHNOLOGIES Sarl
Priority to EP05788875A priority Critical patent/EP1781584A1/fr
Priority to JP2007529992A priority patent/JP2008513359A/ja
Priority to CN2005800286703A priority patent/CN101010273B/zh
Publication of WO2006033740A1 publication Critical patent/WO2006033740A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/26—Purification; Separation; Stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • Exemplary embodiments of the present invention relate to a method of reducing cyclohexenone concentration in an organic mixture containing cyclohexenone.
  • Caprolactam has extensive commercial use, including its use in making nylon, such as nylon 6 for example, via condensation polymerization.
  • Existing technology for producing caprolactam, particularly ⁇ -caprolactam, on a commercial scale involves the reaction of cyclohexanone with a hydroxylamine salt to form a cyclohexanone oxime intermediate. Cyclohexanone oxime undergoes Beckmann rearrangement upon treatment with concentrated sulfuric acid to form ⁇ -caprolactam.
  • Cyclohexanone is typically produced from cyclohexane that has been air oxidized to make a cyclohexanol-cyclohexanone mixture followed by dehydrogenation of the cyclohexanol in the mixture to produce more cyclohexanone.
  • impurities are normally present in the cyclohexanol-cyclohexanone mixture obtained from air-oxidation of cyclohexane.
  • Such impurities may include esters, carboxylic acids and cyclohexenone, particularly 2-cyclohexene-l-one.
  • Several methods have been proposed for removing esters and carboxylic acids from cyclohexanol-cyclohexanone mixture.
  • DE 2,123,184 relates to a saponification method for decomposing the esters in alcohol, especially cyclohexanol, in the residues remaining after cyclohexanol- cyclohexanone distillation. In this way, additional cyclohexanol is obtained that results in a higher yield.
  • DE 2,650,892 relates to reducing caustic consumption during the treatment of acid and ester by-products by using an alkali hydroxide and carbonate and recycling some of the cyclohexane oxidation off -gas.
  • Japanese patent J08-019019 relates to eliminating esters and carboxylic acids from mixtures obtained during cyclohexane oxidation in presence of boron products with two step saponification.
  • Embodiments of the invention are directed to a method for reducing the cyclohexenone content of a cyclohexenone-containing organic mixture.
  • the method comprises treating the organic mixture with an effective amount of an additive comprising at least one of sulfurous acid, a salt of sulfurous acid, or an alkali hydroxide.
  • Figure 1 is a graphical representation of the effect of a weak acid salt on cyclohexenone concentration added to an organic mixture containing cyclohexenone.
  • Figure 2 is a graphical representation of the amount of cyclohexenone in an organic mixture as a function of time in the presence of an alkali hydroxide.
  • Embodiments of the invention are directed to a method for reducing the cyclohexenone content of a cyclohexenone-containing organic mixture.
  • the method comprises treating the organic mixture with an effective amount of additive comprising at least one of sulfurous acid, a salt of sulfurous acid, or an alkali hydroxide.
  • the additive may comprise a mixture of two or more of these compounds.
  • the additive is added to the organic mixture in an amount effective to reduce the concentration of cyclohexenone in the organic mixture by about 75% of the original concentration of cyclohexenone prior to treatment.
  • references are primarily made to a method for reducing content of cyclohexenone, such as 2-cyclohexene-l-one, in an organic mixture that also comprises cyclohexanone. It should be appreciated however, that the invention may be used to reduce cyclohexenone concentration in other organic mixtures as well.
  • cyclohexanone is typically produced by oxidizing cyclohexane in air to produce an organic mixture that typically includes a mixture of cyclohexanone and cyclohexanol as well as impurities including cyclohexenone, usually 2-cyclohexene-l-one.
  • the physical properties of cyclohexenone are similar to those of cyclohexanol and cyclohexanone, making separation of cyclohexenone from cyclohexanol and/or cyclohexanone by distillation difficult.
  • the cyclohexenone concentration in the organic mixture is reduced by chemical treatment of the cyclohexenone in the mixture.
  • the cyclohexenone concentration is reduced by at least about 75%, preferably by about 90% or greater, of the original concentration of cyclohexenone in the organic mixture.
  • the organic mixture is treated with an effective amount of an additive or combination of additives including sulfurous acid, a salt of sulfurous acid, or an alkali hydroxide.
  • a salt of sulfurous acid is meant to include a salt of pyrosulfurous acid, such as a metabisulfite.
  • the treatment is typically conducted at a temperature in the range of about 60 to about 160 degrees C and may last for about 10 to about 90 minutes, typically greater than 30 minutes.
  • the organic mixture should be stirred during treatment to facilitate good mixing of the additive(s) with the cyclohexenone.
  • cyclohexenone Reducing the concentration of the cyclohexenone in the organic mixture provides a mixture that may then be used in caprolactam production that decreases competition for hydroxylamine during the caprolactam production process, resulting in fewer side reactions consuming raw material.
  • exemplary salts of sulfurous acid that may used include sodium metabisulfite, sodium hydrogen sulfite and sodium sulfite.
  • Alkali hydroxides typically include sodium hydroxide, potassium hydroxide, or a mixture of the two.
  • sodium hydroxide is added to treat the organic mixture and reduce the concentration of cyclohexenone.
  • the amount of cyclohexanone added may be enough to make the organic mixture about 1% to about 5% by weight cyclohexanone, although greater amounts of cyclohexanone may be added.
  • sodium hydrogen sulfite or sodium metabisulfite may be particularly effective when the organic mixture does not contain any ⁇ cyclohexanone.
  • sulfurous acid salts are used, more effective treatment may be achieved by adding sodium carbonate.
  • the sodium carbonate is believed to stabilize the organic mixture and reduce reformation of cyclohexenone.
  • a mixture of sodium hydrogen sulfite and sodium carbonate or a mixture of sodium metabisulfite and sodium carbonate may advantageously be used in the treatment of the organic mixture.
  • the organic mixture may be a cyclohexenone-containing cyclohexanol- cyclohexanone mixture obtained from a process of cyclohexane oxidation.
  • the oxidation may occur in any oxygenated environment, such as pure oxygen or air. In either case, distillation may be required to remove the oxidation products from unreacted cyclohexane.
  • the cyclohexenone depleted cyclohexanol- cyclohexanone mixture may then be dehydrogenated. This dehydrogenation converts the cyclohexanol to cyclohexanone, resulting in a feed particularly suitable for caprolactam production that is primarily cyclohexanone.
  • the treatment and/or any distillation may occur either before or after dehydrogenating the cyclohexanol.
  • the cyclohexenone containing organic mixture to be treated may already be predominantly cyclohexanone if treatment follows, rather than precedes, dehydrogenation of the cyclohexanol-cyclohexanone mixture.
  • Another example of an organic mixture from which it may be desirable to remove cyclohexenone includes cyclohexanol obtained from a process of making cyclohexanol from phenol, which typically results in an organic mixture of cyclohexanol with cyclohexenone impurities.
  • the cyclohexenone-depleted cyclohexanone produced by the method of the invention is suitable for caprolactam production.
  • a 200 mL solution of KA oil containing 55.82 wt% cyclohexanone, 43.96 wt% cyclohexanol, and 0.22 wt% 2-cyclohexene-l-one was added to a 500 mL glass reactor provided with a heating mantle, stirring bar, temperature control, reflux condenser, and containing sample addition/withdrawing ports.
  • the mixture was treated with O.lg of sodium hydrogen sulfite for 30 minutes at about 95 degrees C under constant stirring.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé pour réduire la concentration en cyclohexénone d'un mélange organique contenant de la cyclohexénone. Le procédé comprend la mise en contact d'un mélange organique contenant de la cyclohexénone, avec une quantité efficace d'acide sulfureux et/ou d'un sel d'acide sulfureux et/ou d'un hydroxyde alcalin, ou d'un mélange d'au moins deux de ces composés.
PCT/US2005/029655 2004-08-24 2005-08-19 Procede pour reduire la teneur en cyclohexenone d'un melange organique contenant de la cyclohexenone Ceased WO2006033740A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP05788875A EP1781584A1 (fr) 2004-08-24 2005-08-19 Procede pour reduire la teneur en cyclohexenone d'un melange organique contenant de la cyclohexenone
JP2007529992A JP2008513359A (ja) 2004-08-24 2005-08-19 シクロヘキセノン含有有機混合物のシクロヘキセノン含量を低減するための方法
CN2005800286703A CN101010273B (zh) 2004-08-24 2005-08-19 减少含有环己烯酮的有机混合物中的环己烯酮含量的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US92510304A 2004-08-24 2004-08-24
US10/925,103 2004-08-24

Publications (1)

Publication Number Publication Date
WO2006033740A1 true WO2006033740A1 (fr) 2006-03-30

Family

ID=35789225

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2005/029655 Ceased WO2006033740A1 (fr) 2004-08-24 2005-08-19 Procede pour reduire la teneur en cyclohexenone d'un melange organique contenant de la cyclohexenone

Country Status (5)

Country Link
EP (1) EP1781584A1 (fr)
JP (1) JP2008513359A (fr)
KR (1) KR20070045270A (fr)
CN (1) CN101010273B (fr)
WO (1) WO2006033740A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813905A (en) * 1955-06-06 1957-11-19 Phillips Petroleum Co Process for recovering cyclohexanone by formation of a bisulfite adduct
DE2650892A1 (de) * 1976-11-06 1978-06-01 Basf Ag Verfahren zur aufarbeitung von cyclohexanol und cyclohexanon enthaltenden reaktionsgemischen
EP0260076A2 (fr) * 1986-09-05 1988-03-16 E.I. Du Pont De Nemours And Company Préparation de cyclohexanone et de cyclohexanol
EP0659726A1 (fr) * 1993-12-23 1995-06-28 Dsm N.V. Procédé pour la préparation d'une alcanone et/ou d'un alcanol
EP0768292A1 (fr) * 1995-10-13 1997-04-16 Dsm N.V. Procédé pour la décomposition de l'hydroperoxyde de cycloalkyle
US6075169A (en) * 1996-10-18 2000-06-13 Basf Aktiengesellshcaft Process for preparing oxidation products from cyclohexane in counterflow
EP1433774A1 (fr) * 2002-12-27 2004-06-30 Koninklijke DSM N.V. Procédé pour la réduction de la concentration d' aldéhyde dans un mélange comprenant de la cyclohexanone et un ou plusieurs aldéhydes

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3806527A (en) * 1972-06-21 1974-04-23 Continental Oil Co Process for the addition of bisulfite to unsaturated compounds
NL7802125A (nl) * 1978-02-25 1979-08-28 Stamicarbon Werkwijze voor het bereiden van cycloalkanolen en cycloalkanonen.
JPS5692262A (en) * 1979-12-25 1981-07-25 Koei Chem Co Ltd Production of 2,2-bishydroxymethylalkanesulfonate salt
JPS57169438A (en) * 1981-04-14 1982-10-19 Ube Ind Ltd Preparation of cyclohexanol and cyclohexanone
JPH0819019B2 (ja) * 1991-07-16 1996-02-28 三菱化学株式会社 シクロヘキサンの酸化反応混合物の処理法
JP2500977B2 (ja) * 1992-03-24 1996-05-29 三菱化学株式会社 シクロヘキサノンの製造方法
JP2001114758A (ja) * 1999-10-15 2001-04-24 Sumitomo Chem Co Ltd カプロラクタムの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813905A (en) * 1955-06-06 1957-11-19 Phillips Petroleum Co Process for recovering cyclohexanone by formation of a bisulfite adduct
DE2650892A1 (de) * 1976-11-06 1978-06-01 Basf Ag Verfahren zur aufarbeitung von cyclohexanol und cyclohexanon enthaltenden reaktionsgemischen
EP0260076A2 (fr) * 1986-09-05 1988-03-16 E.I. Du Pont De Nemours And Company Préparation de cyclohexanone et de cyclohexanol
EP0659726A1 (fr) * 1993-12-23 1995-06-28 Dsm N.V. Procédé pour la préparation d'une alcanone et/ou d'un alcanol
EP0768292A1 (fr) * 1995-10-13 1997-04-16 Dsm N.V. Procédé pour la décomposition de l'hydroperoxyde de cycloalkyle
US6075169A (en) * 1996-10-18 2000-06-13 Basf Aktiengesellshcaft Process for preparing oxidation products from cyclohexane in counterflow
EP1433774A1 (fr) * 2002-12-27 2004-06-30 Koninklijke DSM N.V. Procédé pour la réduction de la concentration d' aldéhyde dans un mélange comprenant de la cyclohexanone et un ou plusieurs aldéhydes

Also Published As

Publication number Publication date
JP2008513359A (ja) 2008-05-01
CN101010273B (zh) 2010-06-30
EP1781584A1 (fr) 2007-05-09
CN101010273A (zh) 2007-08-01
KR20070045270A (ko) 2007-05-02

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