GB2427192A - A process for the oxidation of an alkyl-group containing substrate in the presence of an ionic liquid - Google Patents

A process for the oxidation of an alkyl-group containing substrate in the presence of an ionic liquid Download PDF

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GB2427192A
GB2427192A GB0512345A GB0512345A GB2427192A GB 2427192 A GB2427192 A GB 2427192A GB 0512345 A GB0512345 A GB 0512345A GB 0512345 A GB0512345 A GB 0512345A GB 2427192 A GB2427192 A GB 2427192A
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alkyl
ionic liquid
group containing
oxidant
containing substrate
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Wolfgang Friedrich Hoelderich
Elena Modrogan
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Johnson Matthey PLC
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    • 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
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
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    • B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
    • B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0287—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing atoms other than nitrogen as cationic centre
    • B01J31/0288—Phosphorus
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    • B01J31/0292—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate
    • B01J31/0295—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature immobilised on a substrate by covalent attachment to the substrate, e.g. silica
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    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C27/00—Processes involving the simultaneous production of more than one class of oxygen-containing compounds
    • C07C27/10—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons
    • C07C27/12—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with oxygen
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    • C07C27/16—Processes involving the simultaneous production of more than one class of oxygen-containing compounds by oxidation of hydrocarbons with other oxidising agents
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    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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    • 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
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    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/54—Quaternary phosphonium compounds
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Abstract

A process for the oxidation of an alkyl-group containing substrate comprises contacting the substrate with an oxidant in the presence of an ionic liquid. The substrate may be a cyclic, linear or branched alkane, in particular cyclohexane or n-hexane, and the oxidant may be air, oxygen, oxygen-enriched air, hydrogen peroxide or t-butyl hydroperoxide. The ionic liquid may contain an organic cation, such as quaternary ammonium, imidazolium, pyridinium, phosphonium, guanidinium, picolinium, piperazinium, pyrazolium, pyrrolidinium, triazinium, triazolium or pyridinium, and an anion comprising a halide of at least one metal of Groups 8 to 14 of the Periodic Table, such as aluminium, boron, gallium, manganese, iron, vanadium, chromium, copper, cobalt, zinc, tin, tungsten, palladium, platinum, ruthenium, rhodium or indium. The ionic liquid may be supported on a solid support such as a clay, silica, alumina, aluminosilicate, titanium oxide or born oxide. The substrate and oxidant may be in the gas or liquid phase.

Description

1 2427192 Oxidation Process The present invention concerns processes for
the oxidation of alkane compounds to form alkene oxides, anhydrides, acids, alcohols, aldehydes and ketones.
Alkane oxidation processes are industrially important, for example the oxidation of cyclohexane to cyclohexanol and cyclohexanone forms intermediates for the production of adipic acid and caprolactam, both used in nylon production. Several alkane oxidation processes are practised industrially, using various catalysts. For example, vanadium phosphates and oxides, often with metallic promoters, are used in the oxidation of butane to form maleic anhydride and for other alkane oxidation reactions. Mixed transition metals have also been used. Heteropolyacids are used in US-A-48031 87 as catalysts for the selective oxidation of a variety of organic substrates.
Porous, crystalline molybdenum silicate with a BEA zeolite structure, is used as a catalyst for the selective oxidation of alkane, alkene, ketone, aldehyde or alcohol compounds in DE19828851.
It is an object of the present invention to provide an alternative process for the oxidation of alkanes to oxidised products.
According to the invention, we provide a process for the oxidation of an alkyl-group containing substrate, by contact of said alkyl-group containing substrate with an oxidant, wherein said process is conducted in the presence of an ionic liquid.
The alkyl-group containing substrate may be an alkane or a compound containing a saturated alkyl group. The present process is suitable for the oxidation of C atoms in a hydrocarbon which are bonded to H and/or to another C atom. Said alkyl-group containing substrate therefore preferably comprises a compound of formula CH(CR3)4., where, preferably, each R independently represents H, linear, branched or cyclic alkyl, aryl, alkenyl, carboxyl, amino, hydroxyl, ketone or aldehyde. Each said R group may comprise substituted linear, branched or cyclic alkyl, substituted aryl or substituted alkenyl, where the substituent comprises linear, branched or cyclic alkyl, aryl, alkenyl, carboxyl, amino, hydroxyl or carbonyl. CH(CR3)4 may represent a cyclic or polycyclic structure so that CH(CR3)4 may contain multiple bonds to the same carbon.
Alkanes which are suitable for oxidation using the process of the invention include cyclic, linear or branched alkanes, preferably containing from 3 to 30 C atoms, more preferably from 6 to 20 C atoms. The alkane substrates may be polycyclic. Substituted alkanes may also be used, in which the substituent is a hydrocarbon moiety, e.g. an alkylbenzene, alkyl naphthalene or other cyclic moiety. Examples of suitable alkanes include butane, hexane, ethyl benzene, cyclohexane, cyclopentadecane, n-decane, cyclododecane amongst many others. Of particular interest industrially is the oxidation of cyclic alkanes to cyclic ketones and alcohols which are of importance as fragrances.
The oxidant may be any known, available oxidant. Typical oxidants include air or oxygen (including oxygen-enriched air), hydrogen peroxide, organic peroxides such as t-butyl hydroperoxide.
The oxidation may be carried out in the liquid phase, the gas phase or in a gas-liquid two-phase reaction mixture, depending upon the nature of the substrate and the oxidant. The conditions are typically mild, e.g. temperatures up to about 150 C and pressures of ambient up to 10 atmospheres. When the oxidation is carried out in the gas phase, the molar ratio of oxygen: substrate is preferably in the range from 1:10 - 10:1. When the process is conducted in the liquid-phase using a liquid- phase oxidant such as H202 then the concentration of the oxidant is such as to provide a molar ratio of oxidant to substrate of from 0.5 to 10: 1, more preferably from 1 - 3: 1. the reaction may be carried out as a gas-liquid two-phase process and in these circumstances the reaction preferably proceeds at elevated pressure and in the presence of excess oxidant. The reaction is approximately stoichiometric so that, when an alkane is to be oxidised to an alcohol, each mole of substrate requires about one mole of oxidant. If the reaction is to produce a ketone a further mole of oxidant is required so the concentration of the oxidant should be increased.
Ionic liquids are ionic compounds, i.e. compounds consisting of a positively charged cation and a negatively charged anion, which are liquid at temperatures less than 120 C, preferably less than C. They are sometimes referred to as "molten salts". Typical ionic liquids have organic cations. Common and useful ionic liquids for the present process have as cations quaternary ammonium, imidazolium, pyridinium, phosphonium, guanidinium, picolinium, piperazinium, pyrazolium, pyrrolidinium, triazinium, triazolium, pyrimidinium. Preferred ionic liquids for use in the process of the invention have phosphonium, imidazolium or quaternary ammonium cations.
The anion may be a simple halide or an inorganic or organic sulphonic acid. Preferred anions are the covalently bonded halides of metals of Groups 8 tol4 of the Periodic Table having a formula MX(-)(fl+l)where n is the valency of the metal M and X is a halogen atom. Preferred metals are aluminium, boron, gallium, manganese, iron, vanadium, chromium, copper, cobalt, zinc, tin, tungsten, palladium, platinum, ruthenium, rhodium and indium. Especially preferred anions comprise halides of iron, cobalt, chromium or vanadium.
More than one type of ionic liquid may be present. For example two or more ionic liquids containing different cations and/or anions may be used. Alternatively more than one type of anion may be used when the cation remains the same.
Conventional ionic liquids are typically formed by combining an inorganic halide and an organic base. As is known in the art, various ratios of inorganic halide to organic base can be used to make the conventional ionic liquids. Stoichiometric amounts of base and inorganic halide are defined such that a neutral ionic liquid is obtained. For use if the process of the invention the ionic liquid is preferably Lewis acidic. Ionic liquids that can be used in the process of the invention include mixed ionic liquids e.g. based on three or more ions, e.g. a cation and two or more anions, or an anion and two or more cations, e.g. ternary ionic liquids derived from FeCl3 and (alkyl)imidazolium chloride and (alkyl)pyridinium chloride, or derived from FeCl3 and a hydrocarbyl substituted quaternary ammonium halide and a hydrocarbyl-substituted phosphonium halide.
The ionic liquid may be supported, i.e. absorbed in or on or bonded to a solid support. Suitable supports include solid oxidic materials such as clays, silica, alumina, aluminosilicates, especially zeolites (such as zeolite Y as obtainable from Degussa or Zeolyst International), titanium oxide, boron oxide, or any other metal oxide containing hydroxyl groups on the surface. Such supports include the preferred MCM-types of materials that have a desirable high surface area and include mesoporous materials such as MCM 41, MCM 48 and HMS (hexagonal mesoporous sieve) materials. The process of the invention is most advantageous for making supported ionic liquids on a "regularly ordered" or "structured" support, hereinafter also called a nanosupport, such as zeolites and MCM-type materials. Such structured/ordered supports show sharp peaks in the XRD spectrum, as is known in the art.
Supported ionic liquids made by impregnating the ionic liquid onto a silica or alumina support are known from W099/03163. In impregnating the ionic liquid onto the support the anion, e.g. AId4- may react with hydroxyl groups on the substrate and become bound. As a preferred alternative method of immobilising the ionic liquid through its anion, the (preferably dried and optionally calcined) support material is first treated with the anion or its precursor, e.g. AId3 to form bound anions and then the cation or the ionic liquid is introduced to the supported anion. In this way the Lewis acidity of the supported ionic liquid can be maintained.
Preferred supported ionic liquids are covalently bound to the support through the cation. This may be achieved by grafting the cation or its precursor to the support by known means. The method of making preferred supported ionic liquids is fully disclosed in WOO 1/32308. In this method, using a silica support, for example, an ionic liquid having suitable reactive groups, such as (ethoxy-alkyl)-silyl groups is reacted with the silica-hydroxyl groups present on the surface of the support. The use of appropriate organic compounds, such as (tri-ethoxy-silyl)propylalkyl imidazolium chloride, allows the cationic part of the ionic liquids to be applied to a support in large quantities without the structure of the support material being affected.
Alternatively, suitable organic molecules to form a cation may be incorporated into the support during the synthesis of the support material, for example, amorphous silica or mesoporous materials of the MCM 41 type. Thus supports containing the organic bases needed for the formation of ionic liquids can be synthesised by incorporating a suitable amine in the synthesis of the support.
As a further option, a non-oxidic functionalised support, such as a functionalised polymer which contains the required cations, e.g. as end groups or side chains, or which are provided with the corresponding functions by specific synthesis. Suitable polymeric materials include those based on styrene or other vinylic backbones. The polymer may take the physical form of beads, granules or other forms. A preferred polymeric support comprises a polymeric fibre substrate available commercially from Johnson Matthey as SmopexTM.
The inorganic halide or other anion can be added to the functionalised support containing or carrying the organic cation, or precursor thereto, in various ways. The type of addition depends on the anion used and the desired immobilised ionic liquid. For example, AId3 in solution can be added to an imidazolium chloride immobilised on the support. Reaction with the chloride already present produces the chloroaluminate anion. Selection of the suitable solvent is dependant in each case on the halide used. The reaction conditions must also be selected as a function of the halide used; in general the reaction can take place at room temperature.
Should it not be possible to form the desired anion from a halide already present and a neutral metal halide by simple reaction, the anion can be introduced by an ion exchange. This is the case for example with tetrafluoroborate and hexafluorophosphate anions. Here a simple salt of the anion is added in a suitable solvent and passed over the functionalised support at room temperature until analysis confirms complete exchange of the anions. Selection of the solvent, analysis and conditions of the ion exchange may be specifically selected as a function of the salt used.
For the process of the present invention, the ionic liquid may be unsupported or supported. The use of a supported ionic liquid may be beneficial in facilitating the separation and re-use of the material from the reaction mixture. The supported ionic liquid may be filtered from the reaction mixture, optionally washed in water or in an organic solvent, dried and re-used.
The amount of ionic liquid present in the reaction mixture is preferably in the range from 1 to 50% by weight of the substrate to be oxidised. When the ionic liquid contains a metal-containing anion, the amount of ionic liquid used in the process is preferably in the range from 1 - 20%, more preferably from 1 to 15%, especially from 5 to 10% of metal by weight of the substrate to be oxidised.
The reaction may be carried out in the presence of a solvent for the substrate. Suitable solvents are not susceptible to reaction with any of the reactants. Suitable solvents include toluene, benzene, acetonitrile.
Example 1
Preparation of supported ionic liquid catalyst All metal chlorides were pre-dried under vacuum (101 Pa) at 120 C for 2h. SipernatTM 700 silica was calcined at 550 C for 6 hours and stored under argon.
(3- chloropropyl)- triethoxysilane (1 5g, 6ommoles) was reacted with a slight excess of trioctylphosphine 90% purity (29g, 7ommoles) in the absence of solvent for 5 days at 90 C. 35g of 1 ium chloride was obtained which was pale- yellow coloured and liquid at room temperature.
20g of the calcined silica support was dispersed in dried toluene (1 OOml) for two hours at 90 C.
The chloride formed in the first step, was then added to the silica slurry dropwise and the stirring was continued for 24 hours. The product silica-supported trioctyiphosphonium chloride ionic liquid was first dried at 110 C under vacuum (101 Pa) and then purified by Soxhlet extraction with boiling CH2CI2.
1 Og of the supported trioctylphosphonium chloride was placed in a round bottomed flask equipped with a condenser and gas inlet valve and dispersed in lOOmI of dried toluene. The mixture was then stirred for 2h at 90 C and then cooled to room temperature. A metal chloride (FeCl3 (8.7g), CrCI3 (8g), CuCI2(7.8g) or CoCI2 (8g)) was added with continuous stirring. After 24h, the reaction was stopped and the compound was dried under vacuum (102Pa). The excess metal salt was removed by Soxhlet extraction with boiling CH2CI2 and then the product was dried at 120 C, under vacuum (101Pa) to remove traces of solvent. The product having a copper chloride anion has the following general structure: C8H17 C13 CH3 For clarity, the above immobilised ionic liquid having the copper chloride anion will be referred to as ICu, the corresponding chromium iron and cobalt chloride versions will be referred to as 1Cr, 1 Fe and 1 Co respectively. The immobilised trioctyiphosphonium chloride (with no metal) will be referred to as 1CI.
Example 2
The supported ionic liquids made in Example 1 were used as catalysts in the oxidation of cyclohexane.
g of cyclohexane was placed in a round-bottomed flask equipped with a reflux condenser and magnetic stirring. The catalyst (either CulL(Phosphonium)/ SiO2or Cr-IL(Phosphonium)/ Si02) was added and the temperature raised to 80 C before the oxidant, tert-butyl hydroperoxide (70% ri water), was added dropwise to give a molar ratio of cyclohexane to catalyst of 1.3: 1. The reaction mixture was sampled and analysed for products by gas chromatography.
The "Run 2' results used catalyst isolated from the first run and dried at 120 C for 3 hours at 10.2 Pa. The results are shown in Table 1. Selectivity is calculated as the total of cyclohexanone and cyclohexanol produced based on cyclohexane consumption.
Table 1
Conversion Conversion Conversion Selectivity Selectivity Selectivity at 6 hours at 22 hours at 6 hours at 6 hours at 22 hours at 6 hours (%) (%) (%) (%) (%) (%) ___________ ____________ IRun 2) ___________ ___________ (Run 2) Cu 4.7 12.2 6.0 82 89 92 [jç 3.1 14.0 11.0 90 90 89
Example 3
l-(tri-ethoxy-silyl).propyI3.methylimidazoium chloride was grafted onto a silica (Grace DavicatTM SP550) substrate by stirring for 16 h at 95 C in toluene/ethanol. The solvent was distilled off at 135 C and the solid was then extracted in a Soxhlet apparatus for 24 h with boiling ethanol before drying in vacuo at 100 C. The loading of ionic liquid on the substrate was estimated at 0.7 mmolg1.
lOg of the supported propyl-3-methyl-imjdazolium chloride was placed in a round bottomed flask equipped with a condenser and gas inlet valve and dispersed in 1 OOml of dried toluene. The mixture was then stirred for 2h at 90 C and then cooled to room temperature. A metal chloride (FeCI3 (8.7g), CrCI3 (8g), WCI6, VCI3 (8g), CoCl2) was added with continuous stirring. After 24h, the reaction was stopped and the compound was dried under vacuum (102Pa). The excess metal salt was removed by Soxhlet extraction with boiling CH2CI2 and then the product was dried at 120 C, under vacuum (101Pa) to remove traces of solvent.
The catalysts were characterised using Inductive Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) as shown in Table 2. the concentration of the anion metal is reported.
Example 4
l-(tri-ethoxy-silyl)-propyl-3-butyljmidazolium chloride grafted onto a silica (Grace DavicatTM SP550) to 0.65mmol/g was used to prepare supported ionic liquids having Fe, Cr, cobalt and rhodium chloride anions using the procedure described in Example 3. The samples were characterised as before with the results shown in Table 2.
Table 2
Example Catalyst Si metal _________ _____________________________________________ (mg/g) (mmoles/g) 3Cl Silica- propyl-3-methyl-imidazolium chloride 403 3Cr Silica-(propyl-3-methyl-imidazolium)(+) CrCI4(-) 375 0.38 (Cr) 3Fe Silica-(propyl-3-methyl-imidazolium)(+) FeCl4(-) 370 0.56 (Fe) 3Co Silica-(propyl-3-methyl-imidazolium)(+) C0CI3(-) 383 0.34 (Co) 3V Silica-(propyl-3-methylimidazolium)(+) VCI4(-) 0.27 (V) 3W Silica-(propyl-3-methyl-imidazolium)(+) WCI7(-) 12.5 (W) 4Cl Silica-(propyl-3-butyl-imiciazolium) chloride 391 4Cr Silica-(propyl-3-butylimidazolium)( ) CrCI4(-) 354 0.85 (Cr) 4Fe Silica-(propyl-3-butyl-imidazoljum)(+) FeCI4(-) 377 0.60 (Fe) L 4Co Silica-(propyl-3-butyl-imidazolium)(+) C0CI3(-) 377 0.33 (Co)
Example 5
1 g of cyclohexane and 1 Og of acetonitrile solvent was placed in a roundbottomed flask equipped with a reflux condenser and magnetic stirring. The catalyst (10%wt of metal based on cyclohexane or 25%wt of catalyst if no metal anion is present) was added and the temperature raised to 90 C before the hydrogen peroxide oxidant (30% aqueous solution), was added dropwise to give a molar ratio of cyclohexane to hydrogen peroxide of 1:2. The reaction mixture was sampled and analysed for products by gas chromatography. The results are shown in Table 3.
Example 6
5g of calcined silica (FK 700) support was placed in a round bottom flask, equipped with a magnetic stirrer. The flask was immersed in an oil bath. 5g of ionic liquid trihexyl(tetradecyl) phosphonium irontetrachloride was added at 50 C and the stirring continued for 24h. The excess of ionic liquid was then removed by extraction with boiling CH2CI2 (150 ml) in a Soxhlet apparatus for 24 hours. Then the catalyst (denoted 6Fe) was dried at 120 C under vacuum and stored under argon.
The procedure was repeated using trihexyl(tetradecyl) phosphonium chromiumtetrachloride to form supported catalyst 6Cr and with trihexyl(tetradecyl) phosphonium cobalttrichloride to form supported catalyst 6Co and with trihexyl(tetradecyl) phosphonium borontetrafluoride to form supported catalyst 6B.
Table 3
Catalyst Conversion (%) Selectivity to Selectivity to Reaction time cyclohexanone cyclohexanol (%) (hours) ________ __________ (%) 3C1 18 73 4 18 3Cr 55 81 1 18 3Fe 70 76 2 18 4C1 22 70 7 18 4Cr 83 80 2 18 4Fe 81 91 1 18 4Cr 90 63 5 24 3Cr 75 72 3 24 1Cr 78 81 3 6 1Cr 80 88 2 10 1Cr 83 70 2 24 1CI 31 78 11 31
Example 7
The impregnation procedure of Example 6 was followed using a calcined titania (Degussa P25) support instead of the silica. The resulting supported catalysts are denoted as 7Fe (irontetrachloride anion), 7Cr(chromiumtetrachloride anion) and 7B (borontetrafluoride anion).
Example 8
The impregnation procedure of Example 6 was followed using MCM-41 mesoporous silica support. The resulting supported catalyst is denoted as 8Cr (chromiumtetrachloride anion).
Example 9
The oxidation of cyclohexane with hydrogen peroxide, as described in Example 5, was repeated using the impregnated catalysts of Examples 6 - 8. Unsupported ionic liquids were also used:- trihexyl(tetradecyl) phosphonium chromiumtetrachloride (designated catalyst 9Cr) and trihexyl(tetradecyf) phosphonium irontetrachloride (designated catalyst 9Fe). All catalysts were used at a concentration of 1 0%wt of metal based on cyclohexane. The results are shown in Table 4. Where the catalyst is marked as "2" run", the experiment uses a regenerated catalyst from the first run, which has been separated from the first reaction mixture, washed and dried at 120 "C for 3 hours at 102 Pa.
Table 4
Catalyst Conversion (%) Selectivity to Selectivity to Reaction time cyclohexanone (%) cyclohexanol (%) (hours) 6Cr 41 48 44 24 6Fe 31 35 33 24 7Cr 34 49 44 24 7Cr(2run) 33 50 44 24 7Fe 16 42 46 24 8Cr 60 45 44 24 9Cr 55 40 38 24 9Fe 48 31 28 24
Example 10
Cyclohexane was oxidised with oxygen in the gas phase in an autoclave at a temperature of 135 C, a pressure of 6 atmospheres using 0.1 gram of catalyst at a cyclohexane: 02 ratio of 9: 4. the conversion and selectivity (to cyclohexanone + cyclohexanol) after 1 hour is shown in Table 5. Where the catalyst is marked as "run 2", the experiment uses a regenerated catalyst from the first run, which has been separated from the first reaction mixture, washed and dried at 120 C for 3 hours at 102 Pa.
Table 5
Catalyst Conversion (%) Selectivity (%) iCo 4.6 88 lCo (run 2) 3.7 88 iFe 3.0 93 4Co 3.6 89 4Fe 2.8 88 4Rh 4.0 95 6B 3.2 82 6Co 3.7 84 7B 2.7 86 8Cr 4.0 89 8Cr (run 2) 3.7 92
Example 11
The oxidation of n-hexane with hydrogen peroxide was carried out using the procedure described in Example 5. Unsupported ionic liquids were also used:- trihexyl(tetradecyl) phosphonium irontetrachioride (designated catalyst 9Fe), methyl-imidazolium tungstenheptachloride (designated catalyst 11W) and trihexyl(tetradecyl) phosphonium boronpentachloride (designated catalyst 11 B). All catalysts were used at a concentration of 1 0%wt of metal based on cyclohexane.
The conversion and total yield of products are shown in Table 6. The products included 3- hexanol, 2-hexanol, 1,6-hexanediol, 2,5-hexanedione, adipic acid, 1- hexanol.
Table 6
Catalyst solvent Conversion (%) Yield (%) 9Fe toluene 15 5 11B toluene 11 5 11W toluene 23 6 8Cr toluene 5 3 8Cr - 18 12 6B toluene 9 7 3V acetonitrile 9 - 3Co acetonitrile 8 6 3W acetonitrile 18 16

Claims (18)

  1. Claims 1. A process for the oxidation of an alkyl-group containing
    substrate, by contact of said alkyl- group containing substrate with an oxidant, wherein said process is conducted in the presence of an ionic liquid.
  2. 2. A process as claimed in claim 1, wherein said alkyl-group containing substrate comprises a cyclic, linear or branched alkane.
  3. 3. A process as claimed in claim 2, wherein said cyclic, linear or branched alkane containins from 3 to 30 C atoms.
  4. 4. A process as claimed in claim 1, wherein said alkyl-group containing substrate comprises a compound of formula CHX(CR3)4X, where each R independently represents H, linear, branched or cyclic alkyl, aryl, alkenyl, carboxyl, amino, hydroxyl or carbonyl.
  5. 5. A process as claimed in claim 4, wherein at least one said R group comprises substituted linear, branched or cyclic alkyl, substituted aryl or substituted alkenyl, where the substituent comprises linear, branched or cyclic alkyl, aryl, alkenyl, carboxyl, amino, hydroxyl, ketone or aldehyde.
  6. 6. A process as claimed in claim 1, wherein said alkyl-group containing substrate comprises butane, hexane, ethyl benzene, cyclohexane, cyclopentaciecane, n-decane, cyclododecane.
  7. 7. A process as claimed in any one of the preceding claims, wherein the oxidant comprises air, oxygen, oxygen-enriched air, hydrogen peroxide or t-butyl hydroperoxide.
  8. 8. A process as claimed in any one of the preceding claims, wherein the ionic liquid contains an organic cation selected from the group consisting of quaternary ammonium, imidazolium, pyridinium, phosphonium, guanidinium, picolinium, piperazinium, pyrazolium, pyrrolidinium, triazinium, triazolium or pyrimidinium.
  9. 9. A process as claimed in any one of the preceding claims, wherein the ionic liquid contains an anion comprising a halide of at least one metal of Groups 8 tol4 of the Periodic Table having a formula MX- (n+1) where n is the valency of the metal M and X is a halogen atom.
  10. 10. A process as claimed in claim 9, wherein said metal is selected from the group consisting of aluminium, boron, gallium, manganese, iron, vanadium, chromium, copper, cobalt, zinc, tin, tungsten, palladium, platinum, ruthenium, rhodium and indium.
  11. 11. A process as claimed in claim 10, wherein said metal is selected from iron, cobalt, chromium or vanadium.
  12. 12. A process as claimed in any one of the preceding claims, wherein the ionic liquid is supported on a solid support.
  13. 13. A process as claimed in claim 12, wherein said support is selected from clays, silica, alumina, aluminosilicates, titanium oxide, boron oxide.
  14. 14. A process as claimed in any one of claims 12 or 13, wherein the anion of said ionic liquid is covalently bound to said support.
  15. 15. A process as claimed in any one of claims 12 or 13, wherein the cation of said ionic liquid is covalently bound to said support.
  16. 16. A process as claimed in any one of the preceding claims, wherein said alkyl-group containing substrate and said oxidant are in the gas phase.
  17. 17. A process as claimed in any one of the preceding claims, wherein said alkyl-group containing substrate is in the liquid phase and said oxidant is in the gas phase.
  18. 18. A process as claimed in any one of the preceding claims, wherein said alkyl-group containing substrate and said oxidant are in the liquid phase.
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EP1829852A1 (en) * 2006-02-27 2007-09-05 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone
WO2008022233A1 (en) * 2006-08-18 2008-02-21 Invista Technologies S.A.R.L. Extraction process using an ionic liquid
WO2009114970A1 (en) * 2008-03-21 2009-09-24 北京化工大学 Process for preparing hydroperoxide by catalytic oxidation of arenes containing isopropyls
WO2012066296A3 (en) * 2010-11-19 2012-07-19 Invista Technologies S.A.R. L. Nitrous oxide-containing ionic liquids as chemical reagents
CN104588111A (en) * 2014-12-24 2015-05-06 东华大学 Preparation method and application of silicon oxide/palladium hybridized material with surface grafted with ionic liquid
US20180141813A1 (en) * 2016-11-18 2018-05-24 Goodrich Lighting Systems Gmbh Methods Using Ionic Liquids for Decomposing Peroxides
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CN111056665B (en) * 2019-10-11 2022-08-26 华南理工大学 Method for cooperatively treating organic matter sewage by using ionic liquid and hydrogen peroxide

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
EP1829852A1 (en) * 2006-02-27 2007-09-05 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone
US7541500B2 (en) 2006-02-27 2009-06-02 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone
WO2008022233A1 (en) * 2006-08-18 2008-02-21 Invista Technologies S.A.R.L. Extraction process using an ionic liquid
WO2009114970A1 (en) * 2008-03-21 2009-09-24 北京化工大学 Process for preparing hydroperoxide by catalytic oxidation of arenes containing isopropyls
WO2012066296A3 (en) * 2010-11-19 2012-07-19 Invista Technologies S.A.R. L. Nitrous oxide-containing ionic liquids as chemical reagents
CN104588111A (en) * 2014-12-24 2015-05-06 东华大学 Preparation method and application of silicon oxide/palladium hybridized material with surface grafted with ionic liquid
US10059700B2 (en) * 2015-06-01 2018-08-28 Sekisui Chemical Co., Ltd. Supported catalyst for aldehyde coupling reaction , method for performing aldehyde coupling reaction, and method for regenerating supported catalyst for aldehyde coupling reaction
RU2694829C2 (en) * 2016-09-06 2019-07-17 Общество с ограниченной ответственностью ОКСО Method for catalytic oxidation of n-hexane
US20180141813A1 (en) * 2016-11-18 2018-05-24 Goodrich Lighting Systems Gmbh Methods Using Ionic Liquids for Decomposing Peroxides
US10589995B2 (en) * 2016-11-18 2020-03-17 Diehl Aviation Gilching Gmbh Methods using ionic liquids for decomposing peroxides

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