Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-04-16
2002-02-19
Trinh, Ba K. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S532000, C549S533000, C549S536000
Reexamination Certificate
active
06348607
ABSTRACT:
The present invention relates to a process for oxidizing an organic compound containing at least one C—C double bond, or a mixture of two or more thereof, in which the organic compound or the mixture of two or more thereof is reacted with a medium comprising molecular oxygen and carbon monoxide in the presence of a heterogeneous catalyst. In addition, the present invention also relates to an integrated process of the abovementioned type in which the used catalyst is regenerated and any components which have not been consumed are separated off and returned to the reaction.
Processes for oxidizing an organic compound containing at least one C—C double bond, in particular olefins and among these preferably propylene, are known. Thus, U.S. Pat. No. 5,625,084 describes the reaction of propylene to form propylene oxide. There, propene is reacted with oxygen over silver-containing catalysts to give propylene oxide. However, selectivities of propene to propylene oxide of only from 50 to 60% at low conversions are achieved in this reaction. A large amount of the expensive propene cannot be converted into the target product propylene oxide.
EP-A 0 709 360 and WO 98/00413 describe the preparation of propylene oxide from propylene using an explosive gas mixture of oxygen and hydrogen over Au/Ti catalysts. However, such processes demand elaborate and costly safety measures.
An integrated process for preparing epoxides from alkanes is described in EP-A 0 850 936. The epoxidation is carried out by bringing a gas comprising the alkene, hydrogen and unreacted alkane into contact with oxygen in the presence of an Au-containing cataylst.
It is an object of the present invention to provide a simple process of the above-described type which, without suffering from the disadvantages of the use of explosive oxygen/hydrogen mixtures, is able to convert olefins into the corresponding epoxides with selectivities significantly above 60%.
We have found that this object is achieved by a process for oxidizing an organic compound containing at least one C—C double bond, or a mixture of two or more thereof, which comprises the step (II) below:
(II) reaction of the organic compound or the mixture of two or more thereof with a medium comprising molecular oxygen in the presence of a heterogeneous catalyst, wherein the medium further comprises carbon monoxide (CO).
The molecular oxygen used according to the present invention for the oxidation is subject to no restrictions of any sort. Accordingly, it is possible to use air, essentially pure molecular oxygen or oxygen which originates from other sources, e.g. ozone and nitrogen oxides, although preference is given to molecular oxygen.
Furthermore, it is essential according to the present invention for the medium to comprise carbon monoxide (CO). This too can originate from any source. The CO used preferably comes from a synthesis gas process.
Further processes from which the CO can originate are described, for example, in K. Weissermel, H. J. Arpe, Industrial Organic Chemistry, 2
nd
edition (1993), VCH Verlag Weinheim, p.14 ff., the full scope of which is hereby incorporated by reference into the present application.
In addition, the medium may comprise hydrogen or water, preferably in the form of water vapor, or else hydrogen and water. The source of hydrogen and water is likewise subject to no restrictions of any sort, although the hydrogen is particularly preferably prepared in situ by, for example, dehydrogenation of alkanes which are then used as starting materials.
Furthermore, the medium used according to the present invention may further comprise a gaseous or liquid diluent such as helium, nitrogen, argon, methane, carbon dioxide, water vapor or a mixture thereof, preferably water vapor and/or carbon dioxide (in the gas phase). When carrying out the reaction in the liquid phase or supercritically, it can be carried out in the presence of an oxidation-stable and thermally stable liquid, e.g. chlorinated aliphatic alcohols such as chloropropanol, chlorinated aromatics such as chlorobenzene or dichlorobenzene and also liquid polyethers, polyesters and polyalcohols.
The ratio of the essential components in the process of the present invention, i.e. the ratio of organic compound to oxygen to CO, can be selected freely. It is preferably 1:0.1-10:0.1-10, more preferably 1:1.5-5:0.3-3 and in particular 1:2:0.5 (in each case organic compound:O
2
:CO).
There are also, in principle, no restrictions of any sort in respect of the organic compounds containing at least one C—C double bond which can be used for the purposes of the present invention. The term “organic compound containing a C—C double bond” used in the context of the present invention encompasses all organic compounds which contain at least one C—C double bond. The compound can be a low molecular weight organic compound, i.e. a compound which has a molecular weight of up to about 500, or a polymer, i.e. a compound which has a molecular weight of more than 500. However, the process of the present invention is preferably employed for low molecular weight organic compounds of the above-described type. Suitable organic compounds include linear, branched or cyclic compounds which can have aromatic, aliphatic, cycloaliphatic groups or a combination of two or more thereof. The organic compound used preferably has from 2 to 30 carbon atoms, more preferably from 2 to 10 carbon atoms. It is preferably an aliphatic monoolefin. However, it is also possible for the organic compound used to have more than one ethylenically unsaturated double bond, as is the case for, for example, dienes or trienes. It can contain additional functional groups, e.g. a halogen atom, a carboxyl group, an ester group, a hydroxyl group, an ether bridge, a sulfide bridge, a carbonyl group, a cyano group, a nitro group, an amino group or a combination of two or more thereof. The double bond can be terminal or internal. Furthermore, it can be a constituent of a cyclic structure as is the case for, for example, cyclohexene. It is also possible to use a mixture of two or more compounds of this type.
Further examples of suitable organic compounds include unsaturated fatty acids or their derivatives, e.g. esters and glycerides of such unsaturated fatty acids, and also oligomers or polymers of unsaturated organic compounds, e.g. polybutadiene.
Examples of such organic compounds include the following: ethylene, propylene, 1-butene, cis- and trans-2-butene, isobutylene, butadiene, pentenes, isoprene, 1-hexene, 3-hexene, 1-heptene, 1-octene, diisobutylene, 1-nonene. 1-decene, camphene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, dimers, trimers or tetramers of propylene, styrene and other vinylaromatic organic compounds having at least one C—C double bond, diphenylethylene, polybutadiene, polyisoprene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, cyclododecatriene, dicyclopentadiene, methylenecyclopropane, methylene-cyclopentane, methylenecyclohexane, vinylcyclohexane, vinylcyclohexene, methallyl ketone, allyl chloride, allyl bromide, acrylic acid, methacrylic acid, crotonic acid, vinylacetic acid, crotyl chloride, methallyl chloride, dichlorobutenes, allyl alcohol, allyl carbonate, allyl acetate, alkyl acrylates and methacrylates, diallyl maleate, diallyl phthalate, unsaturated triglycerides such as soya oil, unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, ricinoleic acid and also their esters including the monoglyceryl, diglyceryl and triglyceryl esters.
It is also possible to use mixtures of two or more compounds of this type, in particular mixtures of the compounds mentioned above by way of example.
Accordingly, the present invention particularly preferably provides a process of the type spoken of here in which the organic compound containing at least one C—C double bond is selected from the group consisting of linear or branched aliphatic olefins, linear or branched aromatic olefins, linear
Grosch Georg Heinrich
Möller Ulrich
Rieber Norbert
Stein Bernd
BASF - Aktiengesellschaft
Trinh Ba K.
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