Title of Invention

"A PROCESS FOR THE PREPARATION OF MIXTURE OF ALCOHOLS AND KETONES"

Abstract The present invention provides a process for the production of a mixture of alcohols and ketones by the liquid phase oxidation of higher alkanes using a catalyst system consisting of transition group metal such as iron and support such as alumina, silica, carbon, preferably carbon in the presence of alkyl hydroperoxide as oxygen carrier, under stirring conditions at a temperature range of 10°-120°C and at atmospheric pressure in a stirred glass reactor for a period of 1- 30 h. The present invention produces a mixture of alcohols and ketones with high selectivity (preferably 60-90%) along with other byproducts such as diketones and acids.
Full Text FIELD OF INVENTION
This invention relates to a process for the preparation of a mixture of alcohols and ketones. More particularly, the present invention relates to a process for the manufacture of a mixture of alcohols and ketones by liquid phase oxidation of higher alkanes using alkyl hydroperoxide as the oxygen donor in presence of supported iron catalysts. BACKGROUND OF THE INVENTION
The n-alkanes can be considered as feedstock for manufacture of numerous intermediates and finished products, such as alcohols and ketones, having tremendous demand in the manufacture of variety of industrially important products. The alcohols and ketones are either sulfonated or ethoxylated to different types of detergents. Fatty alcohols and their derivatives are of great commercial importance as surfactants, plasticizers, etc. The most widely used are C12-C16 fatty alcohols. A number of studies have been reported in the literature on the oxidations of higher alkanes to alcohols and ketones via air or oxygen as an oxidant. Reactions of alkanes with alkyl hydroperoxide for the manufacture of alcohols and ketones have also been extensively studied in the literature. A very high alcohol to ketone ratio was reported in the oxidation of cyclohexane with t-butyl hydroperoxide (TBHP) over Fe- tris[2-pyridyl methyljamine catalyst. The alcohol: ketone ratio was 18, at an alkane conversion of -30% [J. Kim et. al. J. Mol. Catal. A:Chem., 117, 83, (1997)]. The oxidation of cyclohexane by TBHP in the presence of titanium alkoxide produced the corresponding alcohols and ketones, whereas, other
titanium alkoxide produced the corresponding alcohols and ketones, whereas, other titanium complexes with titanyl or peroxo-titamum groups were not effective [(M Fujiwara et al, J Mol Catal A Chem , 142, 77 (1999)]
Metal porphyrin catalysts are also reported to be active for the oxidation of isobutane and cumene In the presence of oxygen these substrates form the hydroperoxide, which then decomposes to yield the alcohol and ketone products The oxidation of n-dodecane with cumene hydroperoxide or TBHP to detergent grade alcohols has been reported using Fe, Mn, Co porphyrin catalysts and mixture [JR Sanderson et al, US 4,978,799 (1990)] Metal acetylacetonate complexes are reported to be active for the oxidation of isobutane and cumene In the presence of oxygen these substrates form the hydroperoxide, which then decomposes to yield the alcohol/ketone products The production of detergent grade alcohols by the oxidation of n-dodecane with cumene hydroperoxide or TBHP has been reported using Fe, Ru, Cr acetyacetonate catalysts and mixture [J R Sanderson et al, US 4,978,800 (1990)] In the presence of RuCl2(PPh3)3, and TBHP , decane oxidation with 28% conversion has been observed Ketones are the major product formed with 38% selectivity The alcohol formation is about 2% [S I Murahashi, et al, Tetrahedron Lett, 34(8), 1299 (1993)] US 4459427 [Middleton et al ,1984] describes a process for the production of alcohol and ketone derivatives by reacting the linear or branched alkanes (C2 - C20) with TBHP at ambient or elevated temperature and pressure in the presence of iron or manganese phthalocynine or porphyrin square planar complexes having heterocyclic nitrogen donor ligands, and where the complex has either no axial hgands, e g the lower valency or catiomc complex, or has an axial hgand which is non-coordinating or weakly-coordinating D Mansuy et al [AngewChem Intl Ed Engl, 19
(11), 909 (1980)], describe the hydroxylation of cyclohexane and n-heptane by alkyl hydroperoxide using metalloporphynn and in particular iron (111) and manganese (111) porphyrins m the form of Fe(tetraphenyl porphynn)Cl and Mn(TPP)Cl Ru/C has been used for the oxidation of different alkanes (cycloalkanes, n-heptane and n-decane) using TBHP and peracetic acid as the oxidants, to yield 72 - 90% of oxygenates (alcohol + ketones) [S Murahashi, et al, J Org Chem, 65, 9186 (2000)]
The oxidation of cyclohexane, hexane and heptane to alcohols and ketones has also been reported using cis-[Ru(II)(L)2-(OH2)2]2+ complex catalysts (where L = substituted 2,2'-bipyndines or 1,10-phenanthrohnes [T Lau et al, J Chem Soc , Chem Commun, 1406 (1988)]
Numerous heterogeneous catalysts have also been found to be active for the oxidation of alkanes Co/Mn supported on different microporous aluminophosphates were used for the oxidation of dodecane with air at 100°C [R Raja and J M Thomas, Chem Commun, (17), 1841 (1998)] The highest conversion of dodecane reported was 5 5% The products formed were C12 alcohols, ketones and gaseous carbon oxides The selectivity to alcohol and ketone was 35% and 20%, respectively The selectivity for terminal alcohol and aldehyde was 37%
In the literature, a number of researchers have reported that the detergent grade alcohols were obtained in high selectivity by the oxidation of higher alkanes using bone acid as a catalyst AN Bashikirov, et al [Proc World Pet Cong, Vol 4 175 (1959)] have reported the synthesis of higher aliphatic alcohols by liquid phase oxidation of paraffinic hydrocarbons in the presence of bone acid and found that a high selectivity to alcohols can be achieved by proper selection of reaction conditions Nippon Shokubai in Japan
practices a commercial process for the manufacture of detergent alcohols by alkane oxidation in the presence of boric acid [N Kurata, et al, US 3,660,504 (1972)] Here the diluted oxygen (5% in nitrogen) is used as the oxygen source and the alkyl hydroperoxides are formed in situ These interact with the bone acid to form borate esters, which on hydrolysis yield the detergent alcohols The conversion level for alkane is 31% with a selectivity of 72% to alcohols No metal catalysts are used in this process The bone acid serves as an estenfication agent in the oxidation, which prevents the alcohols from further oxidation by interrupting the oxidative conversion chain at the alcohol stage A similar observation has been reported by N J Stevens and J R Livingston "A New Route for Alcohols" [Chem Eng Progress, 64(7), 62 (1968)] M lam and M Hassan [(Ind Eng Chem Prod Res, 20, 315 (1981)] have reported that the direct oxidation of n-dodecane in the presence of boron compounds like tnbutoxyboroxine, boron tnoxide, dibutoxyborane, etc using dilute oxygen (4% O2 in N2) leads to a mixture of the six possible straight-chain C12 alcohols
Lee et al [Ind Eng Chem Res , 26(10), 1951 (1987)] have reported the phenomena of critical concentration of bone acid and the oxidation reaction kinetics for formation of sec-dodecanol by air oxidation of n-dodecane in the presence of boric acid catalyst US 5,767,320 patent (Raja and Ratnasamy, 1998] describe a process for the oxidation of cyclohexane to a mixture of cyclohexanone and cyclohexanol using Fe, Co, Cu, Cr, Mn complex of phthalocynme or porphynn as catalysts and mixture in which some or all of the hydrogen atoms of the phthalocymne or porphynn have been replaced by electron withdrawing groups
The literature reports indicate that porphyrin, phthalocynine and similar planar complexes
of metal like Fe, Co, Mn, Cu, Ru, Rh are active for the oxidation of alkane in the
presence of alkyl hydroperoxide [TBHP, CHP] There are no reports on the use of
heterogeneous iron metal catalysts for the oxidation of alkanes using alkyl
hydroperoxide
OBJECTIVES OF THE INVENTION
The mam object of the present invention is to provide a process for the preparation of a
mixture of alcohols and ketones
Another object of the present invention is to provide a process for the liquid phase
oxidation of higher alkanes to a mixture of alcohols and ketones in the presence of alkyl
hydroperoxide as an oxidant using supported iron catalyst
Yet another object of the present invention is to develop a process, which will be
environmentally more benign
Yet another object of the invention to provide a process for making mixtures of alcohols
and ketones with minimum by-products formation
Another object of this invention is to use the solid inert support for supporting the
transition metal and which may be selected from alumina, silica, carbon, preferably
carbon
Yet another object of the present invention is to use the linear alkanes, which may be
selected from C8 to C20 paraffins, preferably C10 to C16 paraffins
Yet another object of this invention is to use the alkyl hydroperoxide as an oxidant, which
may be selected from cumene hydroperoxide, t-butyl hydroperoxide, t-amyl
hydroperoxide, preferably t-butyl hydroperoxide
Yet another object of this invention is to provide a process for the production of a mixture
of alcohols and ketones at room or ambient temperature and atmospheric pressure
conditions SUMMARY OF THE INVENTION
The present invention provides a process for the manufacture of a mixture of sec-alcohols and ketones by the liquid phase oxidation of higher alkanes (C8- C20) using a catalyst system consisting of iron metal and support such as alumina, silica, carbon, preferably carbon in the presence of an alkyl hydroperoxide as oxidant.
The reactions were carried out at a temperature ranging between 10°-120°C and at atmospheric pressure in the presence of alkyl hydroperoxide as an oxidant in a stirred glass reactor for a period of 1- 30 h. After the reaction was completed, the reaction mixture was cooled to room temperature, filtered and the reactants and products were analyzed by gas chromatograph (GC). The products were also identified by gas chromatograph - mass spectroscopy (GCMS). The present invention produces a mixture of alcohols and ketones with high selectivity (preferably 60-90%) along with other byproducts such as diketones and acids. DETAILED DESCRIPTION OF THE INVENTION
Accordingly, the present invention provides a process for the preparation of a mixture of alcohols and ketones which comprises; carrying out liquid phase oxidation of higher alkanes (C8-C20) using a supported iron catalyst system in the presence of alkyl hydroperoxide as an oxidant in a solution optionally in presence of solvent, optionally in an inert atmosphere at a temperature range of 10°-120°C at atmospheric pressure for a period of 1- 30 h, cooling the reaction mixture to room temperature, and separating the products by conventional methods such as distillation.

In one of the embodiments of the present invention, the support used for the catalyst is an
inert solid support and may be selected from alumina, silica and carbon, preferably
carbon.
In another embodiment the precursors of iron used in the preparation of catalyst may be
selected from acetates, bromides, chlorides, fluorides, iodide, carbonates, nitrates,
sulfates, phosphates, preferably nitrates.
In still another embodiment the concentration of iron in the catalyst is in the range of 0.3
- 10 % of support.
In yet another embodiment the mole ratio of alkanes to iron is in the range of 1 - 5000.
In yet another embodiment the mole ratio of alkanes to the alkyl hydroperoxide is in the
range of 0.2 - 5.0.
In yet another embodiment the reactions are carried out at a temperature in the range of
10°-120°C.
In yet another embodiment the reaction is conducted at atmospheric pressure in air or
inert atmosphere.
In still another embodiment the solvent used is a primary alcohol, alkyl nitrile or dialkyl
ketone.
In yet another embodiment the alkyl hydroperoxide is used as a solution in primary
alcohols, alkanes, dialkyl peroxide, aromatic solvents.
In still another embodiments the said process is environmentally more benign.
The process of the invention is described in detail in the following illustrative but non-hmitative examples
Example 1 This example illustrates the preparation of carbon supported Fe catalyst First the 1 809 g of iron nitrate is dissolved in 20 ml of distilled water followed by addition of 2 g of activated carbon The mixture was heated to 60°C for 30 mm then cooled to room temperature The pH of the solution was adjusted to 10 by the addition of ammonia, and stirred for 30 mm The mixture was then dried in an evaporator The dried catalyst was then calcined at 300°C m the flow of nitrogen for 4 hours, cooled to room temperature and then reduced in the flow of hydrogen at 300°C for 10 hours This catalyst had a Fe content of 5 % of total weight The likewise manner Fe/C catalysts with Fe content 1%, 2%, 3% and 4% were prepared using appropriate quantities of Fe salts
Example 2 A mixture of 3 123 g n-decane in 4 957 g TBHP, 0 13 g 5% Fe/C catalyst was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was earned at 80°C at atmospheric pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 12 5 % conversion of n-decane with 51 8 % and 25 4 % selectivity to decanones and decanols, respectively

Diketones and acids are formed as side products with 91 % and 1 2 % selectivity, respectively
Example 3 A mixture of 3 942 g decane, 3 12 g TBHP (in DTBP), 0 5 g 5 % Fe/C catalysts and 8 91 g t-butanol was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was earned at 80°C at atmospheric pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 11 8 % conversion of n-decane with 10 0 % and 5 6 % selectivity to decanones, decanols, respectively Diketones are formed as side products with 1 6 % selectivity
Example 4 A mixture of 5 015 g n-dodecane, 2 995 g TBHP (in DTBP), 0 25 g 3 % Fe/C catalyst was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was earned at 80°C at atmosphenc pressure under constant stirring for a penod of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide m the reaction mixture was
estimated by lodometric titration method The GC analysis of reaction mixture showed
6 9 % conversion of n-dodecane with 55 1 % and 33 8 % selectivity to dodecanones and
dodecanols, respectively Diketones are formed as side products with 8 1 % selectivity
Example 5 A mixture of 5 038 g n-dodecane, 3 024 g TBHP (in DTBP), 0 25 g 4 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was carried at 80°C at atmospheric pressure under constant stirring for a penod of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed
7 3 % conversion of n-dodecane with 53 4 % and 31 9 % selectivity to dodecanones,
dodecanols, respectively Diketones and acids are formed as side products with 4 9 % and
3 4 % selectivity, respectively
Example 6 A mixture of 5 0 g n-dodecane, 2 981 g TBHP (in DTBP), 0 25 g 5 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was earned at 80°C at atmosphenc pressure under constant stirnng for a penod of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas
chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 8 4% conversion of n-dodecane with 54 1 % and 29 2 % selectivity to dodecanones, dodecanols, respectively Diketones and acids are formed as side products with 5 1 % and 1 1 % selectivity, respectively
Example 7 A mixture of 5 0 g n-dodecane, 2 981 g TBHP in di-t-butylperoxide (DTBP), a 0 25 g 5 % Fe/C catalyst was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was earned at 25°C at atmospheric pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 0 5% conversion of n-dodecane with 64 5 % and 354 % selectivity to dodecanones, dodecanols, respectively
Example 8 A mixture of 5 0 g n-dodecane, 2 981 g TBHP (in DTBP), 0 1 g 5 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was carried at 80°C at atmospheric pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At
the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 5 7% conversion of n-dodecane with 59 0 % and 35 9 % selectivity to dodecanones, dodecanols, respectively Diketones are formed as side products with 4 9 % selectivity
Example 9 A mixture of 5 004 g n-dodecane, 2 995 g TBHP (in DTBP), 0 5 g 5 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was carried at 80°C at atmosphenc pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 9 9 % conversion of n-dodecane with 56 3 % and 27 2 % selectivity to dodecanones, dodecanols, respectively Diketones and acids are formed as side products with 4 7 % and 3 0 % selectivity, respectively
Example 10 A mixture of 5 0 g n-dodecane, 2 981 g TBHP (in DTBP), 0 75 g 5 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction
was carried at 80°C at atmospheric pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 10 7 % conversion of n-dodecane with 59 1 % and 27 3 % selectivity to dodecanones, dodecanols, respectively Diketones are formed as side products with 10 3 % selectivity
Example 11 A mixture of 5 017 g n-dodecane, 6 009 g TBHP (in DTBP) (C12 TBHP mole ratio = 1 2), 0 25 g 5 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was carried at 80°C at atmosphenc pressure under constant stirring for a penod of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 11 7 % conversion of n-dodecane with 60 8 % and 24 3 % selectivity to dodecanones, dodecanols, respectively Diketones and acids are formed as side products with 7 3 % and 5 6 % selectivity, respectively
Example 12
A mixture of 3 788 g TBHP in 4 219 g n-dodecane (TBHP C12 ratio = 2 1), 0 25 g 5 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was carried at 80°C at atmospheric pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 14 6 % conversion of n-dodecane with 42 5 % and 24 8 % selectivity to dodecanones, dodecanols, respectively Diketones are formed as side products with 7 2 % selectivity
Example 13 A mixture of 3 771 g TBHP in 4 20 g n-dodecane, 0 25 g 3 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was earned at 80°C at atmospheric pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 12 5 % conversion of n-
dodecane with 47 7 % and 27 8 % selectivity to dodecanones, dodecanols, respectively Diketones are formed as side products with 6 6% selectivity
Example 14 A mixture of 3 77 g TBHP in 4 199 g n-dodecane, 0 25 g 4 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was earned at 80°C at atmospheric pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 14 3 % conversion of n-dodecane with 42 8 % and 23 8 % selectivity to dodecanones, dodecanols, respectively Diketones are formed as side products with 6 3 % selectivity
Example 15 A mixture of 3 598 g TBHP in 4 349 g n-dodecane, 0 5 g 5 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was carried at 80°C at atmospheric pressure under constant stirring for a period of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc
titration method The GC analysis of reaction mixture showed 15 8 % conversion of n-dodecane with 40 7 % and 17 7 % selectivity to dodecanones, dodecanols, respectively Diketones formed as side products with 10 1 % selectivity
Example 16 A mixture of 5 04 g n-hexadecane, 2 487 g TBHP (in DTBP), 0 25 g 5 % Fe/C catalysts was charged to the glass reactor of 50 ml capacity fitted with a water condenser The reaction was carried at 80°C at atmospheric pressure under constant stirring for a penod of 6 hours The temperature was maintained by the use of circulated high temperature bath At the end of the reaction, the reaction mixture was cooled to room temperature, filtered to separate the catalyst, and then weighed The reactants and products were analyzed by gas chromatograph and the products were also identified by gas chromatography mass spectomerty The hydroperoxide in the reaction mixture was estimated by lodometnc titration method The GC analysis of reaction mixture showed 99 % conversion of hexadecane with 60 4 % and 13 1 % selectivity to hexadecanones, hexadecanols, respectively The advantages of the present invention are
1 The present invention provides a process for the production of a mixture of secondary alcohols and ketones by oxidation of higher alkanes using alkyl hydroperoxide as an oxidant at moderate reaction temperature ( 2 The present invention provides a process by the use of a heterogeneous catalysts system, which can be separated from the reaction mixture with ease and reused for the reaction
3 The present invention provides a process that is environmentally more benign
4 The invention produces ketones and alcohols as major products with high selectivity (60-90 %), with a higher proportion of ketone
5 The catalyst system reported in the present invention works at a lower temperature and hence the formation of carbon dioxide is negligible














We Claim:
1. A process for the preparation of a mixture of alcohols and ketoneswhich comprises; carrying out liquid phase oxidation of higher alkanes (C8-C20) using a supported iron catalyst system in the presence of alkyl hydroperoxide as an oxidant in a solution optionally in presence of solvent, optionally in an inert atmosphere at a temperature range of 10°-120°C at atmospheric pressure for a period of 1- 30 h, cooling the reaction mixture to room temperature, and separating the products by conventional methods such as distillation.
2. A process as claimed in claim 1, wherein the support used for the catalyst is inert solid support and selected from alumina, silica, carbon, preferably carbon.
3. A process as claimed in claim 1, wherein the concentration of iron in the catalyst is in the range of 0.3-10 % of support.
4. A process as claimed in claim 1, wherein the mole ratio of alkanes to iron is in the range of 1 - 5000.
5. A process as claimed in claim 1, wherein the mole ratio of alkanes to alkyl hydroperoxide is in the range of 0.2 - 5.0.
6. A process as claimed in claim 1, wherein the solvent used is a primary alcohol, alkyl nitrile or dialkyl ketone.
7. A process as claimed in claim 1, where the alkyl hydroperoxide is used as a solution in primary alcohols, alkanes, dialkyl peroxide, aromatic solvents.
8. A process for the preparation of a mixture of alcohols and ketones substantially as herein described with reference to the examples accompanying the specification.

Documents:

1754-DEL-2004-Abstract-(18-02-2011).pdf

1754-del-2004-abstract.pdf

1754-DEL-2004-Claims-(18-02-2011).pdf

1754-del-2004-claims.pdf

1754-DEL-2004-Correspondence-Others-(18-02-2011).pdf

1754-del-2004-correspondence-others.pdf

1754-DEL-2004-Description (Complete)-(18-02-2011).pdf

1754-del-2004-description (complete).pdf

1754-del-2004-form-1.pdf

1754-del-2004-form-18.pdf

1754-del-2004-form-2.pdf

1754-DEL-2004-Form-3-(18-02-2011).pdf

1754-del-2004-form-3.pdf

1754-del-2004-form-5.pdf


Patent Number 247410
Indian Patent Application Number 1754/DEL/2004
PG Journal Number 14/2011
Publication Date 08-Apr-2011
Grant Date 05-Apr-2011
Date of Filing 17-Sep-2004
Name of Patentee COUNCIL OF SCIENTIFIC & INDUSTRIAL RESEARCH
Applicant Address RAFI MARG, NEW DELHI-110 001, INDIA.
Inventors:
# Inventor's Name Inventor's Address
1 VILAS HARI RANE NATIONAL CHEMICAL LABORATORY PUNE-411008, MAHARASHTRA, INDIA.
2 RAJ MADHUKAR DESHPANDE NATIONAL CHEMICAL LABORATORY PUNE-411008, MAHARASHTRA, INDIA.
3 RAGHUNATH VITTHAL CHAUDHARI NATIONAL CHEMICAL LABORATORY PUNE-411008, MAHARASHTRA, INDIA.
PCT International Classification Number C07C 51/16
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 NA