Classifications

• • 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
  • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
  • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
  • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
• • 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
  • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
  • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C407/00—Preparation of peroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C409/00—Peroxy compounds
  • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
  • C07C409/14—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom belonging to a ring other than a six-membered aromatic 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
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
  • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

• the invention relates to a method for the continuous preparation of a mixture of a cycloalkanone, a cycloalkanol and a cycloalkylhydroperoxide, according to which a corresponding cycloalkane is oxidized wherein the cyclic alkane has between 5 and 20 carbon atoms, in a continuous process, with the aid of an oxygen-containing gas, in the absence of a metal catalyst, at a temperature of between 130 and 200°C.
• the aim of this invention is to provide a method with which the selectivity of the cycloalkane oxidation reaction towards desired products is higher.
• the aim of the invention is a method with which the selectivity towards cycloalkylhydroperoxide is higher.
• This aim is achieved because the oxidation is at least partly carried out in the presence of between 0.002 and 2 mmole of a phenolic compound per kg of reaction mixture (mmol/kg).
• a method for obtaining cyclododecylhydroperoxide by oxidation of cyclododecane in the presence of 0.01-30 wt.% of a phenolic compound.
• the experiments are conducted with 1 wt.% (1170 mmol/kg) phenol, 2.5 wt.% (230 mmol/kg) cresol and 0.2 wt.% (18 mmol/kg) resorcinol.
• phenolic or dihydroxybenzene-like compounds during the oxidation of cyclohexane with the aim of increasing the selectivity is described in SU-A-197555.
• the oxidation reaction is catalysed with the aid of a metal catalyst at a temperature of between 200 and 250°C and results in a mixture of cyclohexanol and cyclohexanone.
• a large amount of phenolic compound is used per kg of reaction mixture (90 and 140 mmol/kg). It is hence surprising that the addition of small amounts of phenolic compound to an uncatalysed oxidation and at a lower temperature has a • positive effect with respect to the selectivity at the same degree of conversion.
• the phenolic compound contains one or more groups according to Formula (1)
• Such a phenolic compound is preferably an organic compound having a molecular weight of less than 1000 and having 1-5 aromatic rings.
• a suitable group of phenolic compounds can be represented by Formula (2):
• R 1 through R 5 may, independently of one another, be an -O-R 6 group or an R 7 group, where R 6 and R 7 may, independently of one another, be H or organic groups having between 1 and 30 carbon atoms, whether or not substituted with ether, carbonyl, hydroxyl, amine, amide and ester groups, and/or where R 1 and R 2 or R 2 and R 3 or R 3 and R 4 or R 4 and R 5 can together constitute an aliphatic or aromatic ring having 5, 6, 7, 8, 10 or 12 carbon atoms.
• Suitable phenolic compounds are phenol, 2,6-ditertiary- butylphenol, 2,6-ditertiary-butyl-4-methylphenol, m-cresol, bisphenol-A, biphenol, p-tertiary-butylphenol, 2-hydroxynaphthalene, 2,6-dimethylphenol, 2,4-ditertiary- butylphenol, 2,4,6-tritertiary-butylphenol, 2,4-dimethyl- 6-tertiary-butylphenol, 1-hydroxynaphthalene, hydroquinone, pyrocatechol, resorcinol, p-phenoxyphenol and o-phenylphenol.
• m-cresol 2,4-ditertiary-butylphenol, 2,6-ditertiary-butylphenol and phenol are used.
• Mixtures of the aforementioned phenolic compounds may also be used. Mixtures of phenolic compounds that are prepared during the preparation of a specific phenolic compound can for example be used advantageously because further purification is then not required.
• the concentration of phenolic compound is generally smaller than 2 mmol/kg, preferably smaller than 1 mmol/kg and in particular smaller than 0.9 mmol/kg.
• the concentration of phenolic compound is generally greater than 0.002 mmol/kg, preferably greater than 0.01 mmol/kg and in particular greater than 0.05 mmol/kg.
• the invention also relates to a process wherein the concentration of phenolic compound is less than 0.01 wt.% relative to the reactionmixture.
• the above mentioned concentrations are the concentrations based on the amount of phenolic compound fed to the reaction mixture.
• the actual average concentration during the oxidation reaction shall be lower than the above mentioned concentration because part of the phenolic compound will disappear during the oxidation.
• the invention relates to the oxidation of cyclic alkanes having between 5 and 20 carbon atoms.
• the invention relates to the oxidation of cycloalkanes having between 6 and 12 carbon atoms.
• suitable cyclic alkanes are cyclohexane, cyclooctane and cyclododecane.
• the invention relates to the oxidation of cyclohexane because the oxidation products cyclohexanol, cyclohexanone and cyclohexylhydroperoxide, separately or as a mixture, are used for many applications.
• the invention relates to the oxidation of cyclohexane wherein phenol is used as phenolic compound because phenol is easily obtainable.
• Cyclohexylhydroperoxide can for example be used as an oxidizer in the preparation of alkane epoxide from a corresponding alkene.
• the cyclohexylhydroperoxide in the mixture can also be decomposed to obtain a mixture of cyclohexanone and cyclohexanol.
• This so-called K/A mixture is a product that is used as such for example in the preparation of adipic acid.
• the decomposition of the cyclohexylhydroperoxide generally takes place after cooling of the mixture, under the influence of a transition-metal catalyst such as cobalt or chromium.
• a transition-metal catalyst such as cobalt or chromium.
• the decomposition of cyclohexylhydroperoxide is carried out with the aid of a method described in EP-A-004105 or EP-A-092867.
• the temperature at which the oxidation is carried out is generally between 130 and 200°C.
• the temperature is preferably higher than 160°C.
• the temperature is preferably lower than 190°C.
• the pressure at which the oxidation is carried out generally lies between 0.1 and 5 MPa.
• the pressure is preferably higher than 0.4 MPa.
• the pressure is preferably lower than 2.5 MPa. In the case that cyclohexane is oxidized the pressure will generally be higher than 0.6 MPa and lower than 2.0 MPa.
• the oxidation is carried out in continuous mode and preferably takes place in a system of reactors connected in series or in a compartmentalized tube reactor.
• the reaction is generally carried out autothermally or by controlling the temperature.
• the temperature is generally controlled by discharging heat of reaction via a stream of gas, via intermediate cooling or via other methods known to a person skilled in the art.
• reactors with an inert inside wall are preferably chosen. To this end use can for example be made of reactors having an inside wall of passivated steel, aluminium, tantalum, glass or enamel.
• the catalysed oxidation - which generally involves the addition of a metal such as cobalt and chromium - yields a reaction mixture with relatively little cycloalkylhydroperoxide relative to cycloalkanone + cycloalkanol.
• the product of the uncatalysed oxidation of cyclohexane comprises at least an amount of cyclohexylhydroperoxide in wt.% that is comparable with the amount of cyclohexanol + cyclohexanone in wt.%.
• the mixture contains more than 2x as much cyclohexylhydroperoxide as cyclohexanol + cyclohexanone after the reaction.
• the catalysed oxidation yields a mixture that contains less than 50% cyclohexylhydroperoxide relative to the amount of cyclohexanol + cyclohexanone in wt.%.
• the concentration of cycloalkylhydroperoxide in the reaction mixture as it leaves the (last) oxidation reactor is generally between 0.1 and 8.0 wt.%.
• the cycloalkanone concentration of this mixture is generally between 0.1 and 10 wt.%.
• the cycloalkanol concentration of this mixture is generally between 0.1 and 15 wt.%.
• the degree of conversion of cycloalkane relative to this reaction mixture is generally between 0.5 and 25 %.
• the degree of conversion of cyclohexane is generally between 2 and 6%.
• the phenolic compound can be supplied separately to each reactor (or compartment). It has been found that it is preferable if the concentration of phenolic compound in the first reactors is relatively lower than the concentration in the last reactor or reactors. It may also be advantageous to supply a phenolic compound to one or more reactors only and not to all of the reactors.
• Oxygen as such air, with increased or reduced oxygen content, or oxygen mixed with nitrogen or another inert gas can be chosen as the oxygen-containing gas. Air is preferable, but the air can be mixed with extra inert gas to prevent the risk of explosions. In general, in order to prevent the risk of explosion, so much oxygen- containing gas is fed to the reactors, in such a manner, that the concentration of oxygen in the offgas remains below the explosion limit.
• the supplied amount of oxygen (calculated as pure oxygen) is generally between 0.1 and 50 Nl per 1 of cycloalkane. This amount is dependent on the reaction rate and oxygen is preferably present in a small excess but this is not critical because the amount of oxygen is generally not limiting.
• Example I Into a double-walled glass reactor (volume equal to a liquid contents consisting of 270 g of cyclododecane (of 170°C)) equipped with 4 baffles, a turbine mixer, coolers, a thermometer and two feed pipes melted cyclododecane was fed through one feed pipe, with the aid of a pump, at a rate of 732 g/h and through the other pipe a solution of the additive in melted cyclododecane, with the aid of a second pump, at a rate of 90 g/h. The residence time was hence 20 minutes. 2,6-ditertiary- butylphenol was used as the additive. The feed rate of the additive was controlled so that the concentration in the reactor was .
• Example I was repeated.
• the feed rate of the additive was controlled so that the concentration in the reactor was 0.094 mmol/kg.
• Analyses of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 61.6, 12.1 and 18.4 mol%, respectively, (total 92.1 mol%) at a degree of conversion of cyclododecane of 4.4 mol%.
• Example I was repeated.
• the feed rate of the additive was controlled so that the concentration in the reactor was 0.48 mmol/kg.
• Analyses of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 68.0, 4.3 and 18.1 mol%, respectively, (total 90.4 mol%) at a degree of conversion of cyclododecane of 5.0 mol%.
• Example I was repeated but no additive was added. Analyses of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 54.6, 13.3 and 18.8 mol%, respectively, at a degree of conversion of cyclododecane of 4.67 mol%. This experiment was repeated.
• Example IV Example I was repeated only now phenol was used as the additive.
• the feed rate of the additive was controlled so that the concentration in the reactor was 1.0 mmol/kg.
• Analyses of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 59.6, 14.8 and 18.7 mol%, respectively, (total 93.1 mol%) at a degree of conversion of cyclododecane of 4.4 mol%.
• Example IV was repeated only now the feed rate of the additive was controlled so that the concentration in the reactor was 0.8 mmol/kg and the cyclododecane feed was lowered in such an amount that the degree of conversion of cyclododecane was 4.7 mol%.
• Analyses of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 58.0, 12.5 and 17.8 mol%, respectively, (total 92.0 mol%).
• Example V was repeated only now the feed rate of the additive was controlled so that the concentration in the reactor was 0.48 mmol/kg. and the cyclododecane conversion was 5.1 mol%. Analysis of the effluent of the reactor showed that the selectivity towards cyclododecyl ⁇ hydroperoxide, cyclododecanol and cyclododecanone was 61.4, 6.3 and 15.3 mol%, respectively, (total 91.1 mol%).
• Example VI was repeated but no additive was added.
• the degree of conversion of cyclododecane was 5.1 mol% as in Example VI.
• Analysis of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanone and cyclododecanol was 48.6, 11.7 and 17.4 mol%, respectively (total 77.6 mol%) .
• Example VII Example I was repeated only now 2,6-ditertiary- butyl-4-methylphenol was used as the additive.
• the feed rate of the additive was controlled so that the concentration in the reactor was 0.94 mmol/kg.
• Analysis of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 59.2, 13.2 and 18.5 mol%, respectively, (total 91.9 mol%) at a degree of conversion of cyclododecane of 4.5 mol%.
• Example VII was repeated.
• the feed rate of the additive was controlled so that the concentration in the reactor was 1.9 mmol/kg.
• Analysis of the effluent of the reactor showed that the selectivity towards cyclododecyl- hydroperoxide, cyclododecanol and cyclododecanone was
• Example I was repeated only now m-cresol was used as the additive.
• the feed rate of the additive was controlled so that the concentration in the reactor was 1.1 mmol/kg.
• Analyses of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 65.0, 8.1 and 18.5, respectively, (total 91.6 mol%) at a degree of conversion of cyclododecane of 4.3 mol%.
• Example I was repeated only now 4-methoxyphenol was used as the additive.
• the feed rate of the additive was controlled so that the concentration in the reactor was 1.0 mmol/kg.
• Analysis of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 60.7, 13.2 and 17.8 mol%, respectively, (total 91.7 mol%) at a degree of conversion of cyclododecane of 4.4 mol%.
• Example I was repeated only now 2,4,6- tritertiary-butylphenol was used as the additive.
• the feed rate of the additive was controlled so that the concentration in the reactor was 1.0 mmol/kg.
• Analyses of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 65.7, 9.9 and 16.4 mol%, respectively, (total 92.0 mol%) at a degree of conversion of cyclododecane of 4.5 mol%.
• Example XII Example I was repeated only now 2,4-ditertiary- butylphenol was used as the additive. The feed rate of the additive was controlled so that the concentration in the reactor was 1.1 mmol/kg. Analysis of the effluent of the reactor showed that the selectivity towards cyclododecylhydroperoxide, cyclododecanol and cyclododecanone was 67.4, 5.4 and 18.3 mol%, respectively, (total 91.1 mol%) at a degree of conversion of cyclododecane of 4.5 mol%.
• Example XII was repeated only now phenol was used as the additive.
• the feed rate of the additive was chosen so that the concentration in the reactor was 0.6 mmol/kg.
• Analyses of the effluent of the reactor showed that the selectivity towards cyclohexylhydroperoxide, cyclohexanol and cyclohexanone was 91.5 mol% at a degree of conversion of cyclohexane of 3.4 mol%.
• Example XV Example XIV was repeated.
• the phenol concentration was 0.3 mmol/kg and the total selectivity was 91.9 mol% at a degree of conversion of cyclohexane of 3.5 mol%. Comparative experiment D
• Example XII was repeated only now without the addition of an additive. Analyses of the effluent of the reactor showed that the selectivity towards cyclohexylhydroperoxide, cyclohexanol and cyclohexanone was 89.4 mol% at a degree of conversion of cyclohexane of 3.4 mol%.

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• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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• 1992
  • 1992-12-16 BE BE9201101A patent/BE1006451A3/nl not_active IP Right Cessation
• 1993
  • 1993-11-29 TW TW082110062A patent/TW277055B/zh active
  • 1993-12-02 KR KR1019950702515A patent/KR100299587B1/ko not_active Expired - Fee Related
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  • 1993-12-02 JP JP6514007A patent/JPH08504437A/ja active Pending
  • 1993-12-02 UA UA95062797A patent/UA35602C2/uk unknown
  • 1993-12-02 RU RU95114380A patent/RU2116290C1/ru active
  • 1993-12-02 WO PCT/NL1993/000259 patent/WO1994013613A1/en not_active Ceased
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