Process for the manufacture of 1,2-epoxybutane

Details Process for the manufacture of 1,2-epoxybutane Process for the manufacture of 1,2-epoxybutane

2000-10-30

2001-10-30

Griffin, Steven P. (Department: 1754)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C549S537000, C549S513000

Reexamination Certificate

active

06310223

ABSTRACT:

This invention pertains to certain novel catalysts and catalyst support materials and processes for the preparation of the catalyst support materials and for the selective hydrogenation of 3,4-epoxy-1 -butene (EpB) to 1,2-epoxybutane (butylene oxide—BO). More specifically, this invention pertains to (1) catalyst support materials having micropores filled with one or more inorganic oxides, (2) a process for the preparation of such catalyst support materials, (3) supported catalysts comprising one or more Group VIII metals deposited on the aforesaid support materials and (4) a process for the selective hydrogenation of EpB to BO using a catalyst comprising rhodium deposited of the aforesaid catalyst support materials.
U.S. Pat. No. 4,897,498 describes an efficient process for the preparation of EpB by the selective monoepoxidation of butadiene. Butylene oxide, which is one of many compounds which may be obtained from EpB, is useful in the manufacture of polyethers, alkylene glycols, aminoalkanols, epoxy resins, urethane polyols and nonionic surfactants and as a stabilizer for chlorinated hydrocarbons and fuel additive.
According to Rylander,
Catalytic Hydrogenation Over Platinum Metals
, Academic Press, New York, page 478 (1967), epoxides, with a few exceptions (Berson and Suzuki,
J. Am. Chem. Soc
., 80, 4341 [1958]), readily undergo hydrogenolysis over platinum metal catalysts and the major product is usually an alcohol or mixture of alcohols resulting from cleavage of a carbon-oxygen bond; other products may arise by cleavage of the carbon-carbon bond and by loss of the oxygen function. The catalytic hydrogenation of EpB to butyraldehyde over palladium and to 1-butanol over Raney nickel is described in U.S. Pat. No. 2,561,984. No mention is made of the use of rhodium catalysts nor the observation of BO formation. The hydrogenation of EpB also has been reported by Russian workers in
Zh. Obshch. Khim
., 28, 3046 and 3051 (1958). They hydrogenated EpB in methanol or ethanol with platinum, palladium, and Raney nickel catalysts to give 1-butanol. They state that crotyl alcohol was the principal intermediate in the reduction, although butyraldehyde was also observed. Selective double bond hydrogenation was not observed in any example.
Rhodium has been reported (
J. Am. Chem. Soc
., 83, 3096 [1961]) to be effective for a double bond reduction in the presence of an epoxide group in a fumagillin derivative. In this literature example, however, the epoxide is trisubstituted and less prone to hydrogenolysis due to steric hindrance. Additionally the double bond and epoxide were not conjugated as they are in EpB. By the term “conjugated” is meant that the carbon-carbon double bond and the epoxide group are adjacent, or stated another way, the epoxide oxygen is attached to the allylic carbon atom. The significance of the conjugated system existing in EpB is demonstrated by Raney nickel-catalyzed hydrogenation of EpB and 1,2-epoxy-7-octene under mild conditions of 50° C. and 3.5 bar total pressure. The hydrogenation of EpB gives 40.5% 1,2-epoxybutane and 58.4% 1-butanol whereas the hydrogenation of 1,2-epoxy-7-octene, wherein the double bond and epoxy group are separated by 4 carbon atoms, gives 94.4% 1,2-epoxyoctane.
U.S. Pat. Nos. 5,077,418 and 5,117,013 disclose the preparation of BO by hydrogenating EpB in the presence of a supported rhodium catalyst. Although the supported rhodium catalysts disclosed in the '418 and '013 patents give excellent selectivities to BO, it has been found that the activity of the catalysts decreases substantially when the catalysts are used to hydrogenate EpB over extended periods of time, e.g., hydrogenation periods in excess of 20 hours or greater. This partial but substantial deactivation of the catalysts represents a severe impediment to the use of the supported rhodium catalysts disclosed in the '418 and '013 patents in a commercial (continuous) process.
German Published Patent Application DE 195 32 645 A1 discloses the preparation of BO by catalytic hydrogenation of EpB in the presence of a heterogeneous catalyst comprising one or more catalytically-active elements of Groups 7 to 11 (Cu, Rh, Ru, Co, Ni, Pd and Pt) which are vapor-deposited under vacuum conditions on oxidized, metal mesh supports. Oxidation of the wire mesh support was conducted at 600 to 1100° C. Vacuum deposition of catalytically-active components such as elements of Groups 7 to 11 is very expensive and requires extended periods of time. Furthermore, the catalytically-active component is very inefficiently distributed on the oxidized, wire mesh support which has a very low surface area, e.g. typically 1 square meter per gram (m
2
/g) as compared to 20 to 100 m
2
/g for conventional catalyst supports. These catalysts require very long reaction times for batch processes or very long contact times for continuous operation to achieve acceptable conversions of EpB. Catalysts prepared according to the above-described methodology described in DE 195 32 645 A1 were prepared and used to hydrogenate EpB to BO. At a reaction temperature of 50° C., reaction times of 2 to 8 hours were required to convert EpB to BO in selective yields.
We have discovered that EpB may be selectively hydrogenated at high rates in the presence of certain supported rhodium catalysts whereby the olefinic unsaturation is hydrogenated without significant hydrogenolysis of the conjugated epoxy group to produce BO without substantial loss of activity over extended periods of operation. The rhodium catalysts which exhibit good to excellent catalytic activity over extended periods of operation comprise rhodium deposited on an inert catalyst support material having micropores blocked or filled with an inorganic oxide. The present invention includes a plurality of novel embodiments:
(1) A catalyst support material having or containing micropores blocked or filled with one or more inorganic oxides.
(2) A process for preparing the catalyst support material of embodiment (1) which comprises the steps of (i) contacting a catalyst support material containing micropores with a solution of an inorganic salt and (ii) drying and calcining the material obtained from step (i) under conditions which convert the inorganic salt to an inorganic oxide to block, e.g., cap or fill the micropores of the catalyst support material.
(3) A catalyst comprising a Group VIII metal deposited on the catalyst support material of embodiment (1).
(4) A process for the manufacture of BO which comprises contacting EpB and hydrogen in the presence of a catalyst comprising rhodium metal deposited on the catalyst support material of embodiment (1).
The first embodiment of the present invention comprises a catalyst support material containing micropores blocked or filled with one or more inorganic oxides. These modified catalyst support materials may be obtained from any of the large number of conventional, porous, refractory catalyst carriers or support materials which are essentially inert in the presence of the reactants used and the product or products obtained from the processes in which catalysts prepared from the modified support materials are employed. Such conventional materials may be of natural or synthetic origin and preferably are of a macroporous structure, although even support materials which are considered macroporous always contain a certain and often significant fraction of micropores. These support materials typically have an apparent porosity of greater than 20%. Supports having a siliceous and/or aluminous composition are, in general, preferred.
Specific examples of suitable supports are the aluminum oxides (including the materials sold under the trade name “Alundum”), charcoal, pumice, magnesia, zirconia, kieselguhr, fuller's earth, silicon carbide, porous agglomerates comprising silicon and/or silicon carbide, silica, selected clays, and artificial and natural ceramics. Refractory supports particularly useful in the preparation of catalysts in accordance with this invention comprise materials h

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