Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1990-09-10
1991-06-04
Reamer, James H.
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568342, 568385, 568815, 568836, 568910, C07C 4528
Patent
active
050216074
DESCRIPTION:
BRIEF SUMMARY
The present invention relates to the oxidation of saturated hydrocarbon chains and in particular to the use of a certain catalyst system which has been found to enable the selective oxidation of aliphatic compounds and alkyl aromatic compounds.
Saturated organic compounds are particularly difficult to oxidise and despite attempts to develop methods and techniques for their controlled or selective oxidation techniques using mild conditions with relatively high yields are only known for the conversion of butane via butenes into maleic anhydride, furthermore the known processes use homogenous and sometimes hazardous catalysts requiring complex separation techniques. An example of such processes are given in Catalysis Today Vol I Nos 5 of October 1987 relative to the selective catalytic oxidation of butane to maleic anhydride involving dehydrogenation and oxidation of the resulting intermediate olefine, the article in Tetrahedron Vol 31 pages 777-784 concerning the oxidation of cyclohexane with molecular oxygen and the article in the Journal of the CHEM SOC CHERM COMMUN 1987 page 1487 and Journal of Molecular Catalysis 44 (1988) pages 73-83. The direct oxidation of saturates to introduce functional groups such as ketones and alcohols using a heterogeneous catalyst system would be extremely attractive.
Surprisingly we have now found that catalysts proposed for the epoxydation of olefins, the hydroxylation of aromatics and the oxidation of alcohols to ketones and aldehydes, as described in US-A-4,410,501; EP-A-200200, EP-B-100119, EP-A-196109, Ep-A-100118 and DE-A-3135559 can be used for the controlled oxidation of saturates under mild conditions enabling direct formation of alcohols and ketones without acid formation. In particular we have found that a synthetic silicon zeolite containing titanium atoms is able to cause saturated hydrocarbon groups and hydrogen peroxide or organic peroxides to react in a heterogeneous catalytic reaction to yield selectively alcohols and ketones.
These catalysts are based on crystalline synthetic material comprisiing silicon and titanium oxides and are characterized by an Infra red absorption band at around 950 cm.sup.-1. They are typically of the general formula:
They are typically prepared from a mixture containing a source of silicon oxide, a source of titanium oxide, a nitrogenated organic base and water as described in United Kingdom Patent 2071071 which is concerned with the catalysts themselves or by the dealumination of ZSM -5 and reaction with titanium tetrachloride vapour as described by B. Kraushaar and J.H.C. Van Hoof in Catalysis Letters 1 (1988) pages 81-84. The catalysts may contain small amounts of other metals such as aluminium, gallium and iron (as described in European Patent Application 0226258).
U.S. Pat. No. 4824976 relates to the use of these types of catalysts for the epoxidation of olefines with H.sub.2 O.sub.2 and in this patent X may be in the range from about 0.0001 to about 0.04. United Kingdom Patents 2083816 and 2116974 relate to the use of similar catalysts for the introduction of hydroxy groups into aromatic substrates by oxidation with H.sub.2 O.sub.2. These patents are incorporated herein by reference for their descriptions of the Infra-red and x ray diffraction analyses of the catalysts, as stated the band intensity at approximately 950 cm.sup.-1 increases as the quantity of titanium present increases.
The invention therefore provides the use for the oxidation of saturated organic groups of a titanium containing silicalite catalyst having an infra red absorption band around 950 cm.sup.-1.
Typically the catalyst is of the general formula
These catalysts may be typically prepared by:
i) heating a reaction mixture comprising:
d) a nitrogen containing organic base, and
e) water,
ii) separating the formed crystals from the reaction mixture and
iii) calcining the separated crystals to form the catalyst.
The catalyst may be agglomerated to form crystal clusters which are also active and readily recovered after the oxidation reaction.
The invention fu
REFERENCES:
patent: 2808442 (1957-10-01), Smith et al.
patent: 4476327 (1984-10-01), Neri et al.
patent: 4480135 (1984-10-01), Esposito et al.
patent: 4824976 (1989-04-01), Clerici et al.
patent: 4943667 (1990-07-01), Hoelderich et al.
Exxon Chemical Patents Inc.
Mahon J. J.
Reamer James H.
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