CATALYSTS AND PROCESS FOR OXIDATION OF OLEFINS TO KETONES

Abstract: An improved process is provided for forming ketones from the corresponding olefins in the vapor phase in the presence of water vapor, and optionally in the additional presence of molecular oxygen, employing a heterogeneous catalyst comprising rhenium compounds and complexes, optionally containing at least one metal compound or complex selected from the group consisting of Group VIB metals and Group VIII noble metals, and mixtures thereof. It has been surprisingly found that these catalysts effect the formation of ketones in high selectivities with minimal selectivities to the undesirable carbon dioxide and carbon monoxide by-products.

Description: CATALYST AND PROCESS FOR OXIDATION OF OLEFINS TO KETONES This invention generally relates to the catalytic vapor phase conversion of olefins to ketones, and to improved catalysts useful therein. DESCRIPTION OF THE PRIOR ART British Patent 1,029,175 to Shell describes a vapor phase olefin oxidation process in which olefins are reacted with 02 at temperatures of less than 3500C in the presence of water vapor and a halogen, using a supported Group VIII noble metal catalyst containing either an Fe, Ni, Co or Group I or VII transition metal compound, optionally to g-efher with an alkali metal compound or one or more trans nation metal compounds of Groups III-VI. While propylene oxidation is said to give acetone as the main reaction product, such halide-containing systems have severe disadvantages such as the high corrosivity of these systems. An early patent (U.S. Patent 2,523,686 to W. F. Engel of Shell) employs catalysts containing (1) an oxide of a metal of Groups II, III, IV or VI of the Periodic Table and (2) a metal or partially reduced oxide of a metal of Group IB, Group VII or Group VIII of the Periodic Table, and prepares saturated open-ended ketones from olefins of at least three carbon atoms per molecule in a vapor phase process in the presence of steam and under defined conditions. The U.S. patent indicates that Mn is preferred over other Group VII metals (Re and Tc) in the patentee's catalysts. The catalysts are prepared by partial reduction of the metal oxide with H2. Catalyst activity decreases over time, and reaeneration of these oxide catalysts are periodically required. Dutch Patent 59,179, also to W. F. Engel, relates to similar catalyst systems. U.S. Patent 3,389,965 to Shell discloses a process for producing E2 by steam reforming of hydrocarbon petroleum fractions over a Re-containing catalyst at 400 to 6000C or higher, which, of course, results in the formation of C02 and CO in very large amounts. The patent, however, does not relate to the selective, partial oxidation of olefins or alcohols or to the production of ketones and other oxygenated products. Manganese, another Group VIIB metal, has been investigated in various catalyst systems as a catalyst promoter. L. Zanderighi, et al., La Chimica E L'Industria, vol. 56, n. 12, 815-820 (Dec., 1964) report, for a series of propylene-oxidations to a product mixture of acrolein, acetone, acetaldehyde, propylene oxide and methanol, using various tungstates (W04-), of a series of cations, that the reactivities of the tested cations was: Cu > > Bi > Pb > Fe > Tl > Mn. Y. Moro Oka, et al., J. Catalysis, vol.23, 183-192 (1971) indicates that no oxygenated products other than carbon oxides were found in propylene oxidation over aMn2O3-MoO3 catalyst. W. H. Davenport et al., advances in Rhenium Catalysis", Ind. & Eng. Chem., vol. 60, no. 11, pp. 10-19 (Nov. 1968).states that the chemical and catalytic properties of Re differ considerably from Mn. For example, whereas metallic Mn is highly reactive, slowly decomposes water and reacts with dilute acids, Re metal is relatively inert and does not react with water or nonoxidizing acids. Re catalysts are said to be highly selective hydrogenation catalysts. In the presence of H2, supported or unsupported Re metal preferentially catalyzes the attack by H2 upon carbonyl functions over olefinic bonds, while Re oxides catalyze the saturation of C=C bonds first. Re-containing hydrogenation catalysts are also disclosed in French Patent 761,632 (1934); H. S. Broadbent et al., J.A.C.S., vol. 76, pp. 1519-1523 (1954); H. S. Broadbent et al., J.A.C.S., vol. 24, pp. 1847-1854 (1959); B. S. Broadbent et al., J.A.C.S., vol. 81, pp. 3587-3589 (1959); H.S. Broadbent et al., J. Org. Chem., vol. 27, pp. 4400-4404 (1962). R. H. Blom et al., Hydrocarbon Proc. vol. 43, no. 10, pp. 132-134 (Oct. 1963). and R. 4. Blom et al., Ind. & Eng. Chem., vol. 54, no. 4, pp. 16-22 (April 1962) discuss the use of certain Re catalysts in the de- hydrogenation of alcohols to aldehydes and ketones. Rhenium dehydrogenation catalysts are prepared in U.S.S.R. Patent 52,780 (1938), as abstracted at 34 Chem. Abs. 5467-7; U.S.S.R. Patent 114,924 (1958), as abstracted at 53 Chem. Abs. 10596f; Belgian Patent 641,143 (1963) added Re to a supported catalyst containing Fe-Sb oxide on silica to catalyze the oxidation of propylene to acrolein. British Patent 1,038,262 (1966) employed Re oxides to promote supported and unsupported Co and Ni molybdates and Cu phosphate to oxidize propylene to acrolein or acrylic acid. British Patent 1,054,864 (1967) obtained significant disproportion of 1-butene (62% butene conversion) over 238 Re207 on A1203 (at 150 C, atm. pressure) and a space velocity of 1600, with a 62% butene conversion chiefly to propylene and pentene, albeit with some by-product C2 and C6 olefins. Olefin metha thesis reactions using 02 and Re oxide/alumina catalysts are discussed in R. Nakamura, et al., J. Molec. Catalysis, vol. 15, pp. 147-156 (1982) (which is not admitted herein to be prior art to our invention). British Patent 876,024 (1961) forms aldehydes and ketones by contacting the corresponding oleo in and oxygen over a catalyst containing 4 strong acid compound of a transition metal of the fifth to eighth group or first sub-group of the Periodic System, in the presence of steam. Illustrated are catalyst compounds containing anions derived from such strong acids as HC1 and EBr. U.S. Patent 2,662,921 (1953) oxidatively converts olefins into unsaturated ketones (e.g., propylene to acrolein).using a catalyst containing at least one oxide of Te and Re, and in the presence of free 02. Other patents disclosing catalyst systems for forming unsaturated such aldehydes using Re-containing catalysts are: U.S. Patents 3,33q,871 and 3,451,946 to C. E. Ziegler, et al. (feed = propylene and 02 and optionally, water vapor, over catalyst containing CoMoO4, TeO2 and a Re compound, to form a mixture of acrolein and acrylic acid); and U.S. Patents 3,369,049 and 3,423,331 to J. S. Eden et al. (acrolein or methacrolein prepared from propylene or isobutylene and 02, with or without water vapor, over a catalyst comprising a mixture of certain Cu, Te and Re compounds). SUMMARY OF THE INVENTION According to the improved process of this invention, ketones are formed in high selectivities in the vapor phase partial oxidation of olefins in the presence of water vapor over a heterogeneous catalyst comprising rhenium and com flexes and compounds thereof, which can be optionally supported with at least one metal selected from the group consisting of Group VIB metals and Group VIII noble metals and compounds and complexes thereof. It has been surprisingly found that the catalysts of this invention can provide ketones in very high selectivities, with minimal selectivity loss to the undesirable CO and C02 by-products. It has been further found that the catalysts of this invention can effect the above results without the formation of substantial amounts of hydrogenation by-products, such as butane from butene feeds, and such olefin saturation by-products have been detected in the gaseous effluents from the process of this invention in only minimal amounts1 if at all. The process of this invention, in which the ketonemaybe formed in an 02- free reaction zone, also -avoids the use of explosive 02-olefin gas mixtures and therefore greatly minimizes the hazards and expense associated with the handling of such 02-olefin gas mixtures. In other respects, an improved process is provided for forming ketones in which molecular oxygen is also fed to the reaction zone. Surprisingly, use of the molecular oxygen containing feed still permits the formation of ketones in high selectivities with minimal selectivities to the un desirable carbon dioxide and carbon monoxide bv-oroducts. of complex In this embodiment of the invention the catalyst comprises a compound/of rl rhenium Catalyst The catalysts of this invention comprise Re and compounds and complexes of Re, preferably in a supported form. The Re can be present in a variety of forms including a compound or complex thereof, alone or in admixture with a suitable promoter for the desired ketone formation reaction. When present as a Re compound, the metal can.be chemically combined with an inorganic anion such as oxygen, sulfur and halide (Br, F, C1 or I). Preferred are non-halide Re catalysts such as those selected from the croup consisting of Re (especially preferred) oxide, Re sulfideland mixtures thereof. Particularly preferred Re oxide and sulfides are Re203, ReO2, ReO3, Re2O5, Re207, Re2S7, ReS2, ReS3 and Re255. The Re catalyst can optionally contain as a promoter a member selected from the group consisting of a metal our metal compound or complex of a Group VI metal, a Group VIII noble metals or a mixture thereof. Thus, also suitable as catalyst for the vapor phase process of this invention are Re catalysts containing, as the metal or as compounds or complexes thereof, any one of Cr, Mo, W, Ru, Rh, Pd, Os, Ir and Pt. These additional elemental components of the catalyst can be present as the metals themselves (that is, in the reduced state) or as compounds or complexes thereof, or as mixtures ofthe foregoing. Any of the inorganic anions discussed above with respect to Re are also suitable as anions with which the additional Group VIB or Group VIII noble metals cat be calcined. As with the Re component. the metal Group VIII Group VIB/and/or/noble metal will be preferably present in the non-halide form, e.g., an oxide or sulfide. Illustrative of suitable bimetallic catalysts of this invention are Re-Mo, Re-W, Re-Rh, rLCr, Re-Pd, Re-Pt, Re-Ir, Re-Ru and Re-Os oxides and sulfides, and mixtures of the foregoing. Illustrative trimetallic catalysts of this invention are oxides or sulfides of mixtures of each of Re, a group VIB metal and a Group VIII noble metal suchasoxides or sulfides of Re-Cr-Ru, Re-Mo-Rh, Re-W-Rh, Re-Mo-Pd, Re-Mo-Os, Re-Mo-Pt, Re-W-Pd, Re-W-Os and mixtures of the foregoing. Especially preferred are oxides andsulfides of Rh-Re-Mo, Pd-Re-Mo and Rh-Re-W. The Re is preferably present in the promoted catalysts of this invention in a Re:promoter metal weight:weight ratio of from about 0.0001:1 to 10:1, and more preferably from about 0.01:1 to 1:1. Thus, Re-Mo catalyst will preferably contain from about 0.0001 to 10 parts by weight of Re per part by weight of Mo, and more preferably from about 0.01 to 1 part by weight of Re per part by weight of Mo. Similarly, in Re-Rh-Mo catalysts, the weight ratio of Re:(Rh + Mo) will preferably range from about 0.0001 to 10:1, and more preferably from about 0.01 to 1:1. The catalysts which are used in the process of the present invention are solids which can be prepared by any of the methods known in the art. Furthermore, they can be employed in any suitable form, for example, as granules, pellets, powders and the like, and they can be either used as such or supported (as is preferred) on or admixed with an inert material, such as alumina, silica, silica-alumina, zeolites, pumice, any of the activated earths, kieselguhr, clays and the like. The preferred support for the catalyst of this invention is alumina, and most preferably gamma-alumina. Preferred supported bimetallic Re catalysts of this invention are those containing from about 0.1 to 10 wt.% Re together with from about 1 to 30 wt.% of a Group VIB metal (e.g., Mo or W), and more preferably those containing from about 1 to 5 wt.% Re, together with from about 3 to 15 wt.% of a Group VIB metal (e.g., Mo or W), calculated as wt.% of the indicated metals based on the total weight of the supported catalyst. Preferred supported trimetallic Re catalysts of this invention are those containing (based on the total weight of the supported catalyst) from about 0.001 to 5 wt.z of a Group VIII noble metal (e.g., Rh, Pd, Pt or Ru), from about 0.1 to 10 wt.% Re together with from about 1-30 wt.% Mo, and, more preferably, those containing from about 0.1 to 1.0 wt.% of a Group VIII noble metal (e.g., Rh, Pd, Pt or Ru), from about 1 to 5 wt.% Re together with from about 3 to 15 wt.% of a Group VIB metal (e.g., Mo or W), calculated as wt.% of the indicated metals based on the total weight of the supported catalyst. Preferred supported trimetallic Re catalysts of this invention are those containing (based on the total weight of the supported catalyst) from about 0.001 to 5 wit.% Rh, from about 0.1 to 10 wt.% Re together with from about 1-30 wt.% Mo, and, more preferably, those containing from about 0.1-1.0 wt.% Rh, from about 1 to 5 wt.% Re, together with from about 3 to 15 wt.% Mo. Most preferably, the catalyst composition ranges from 1 to 30 wt.% of catalyst metals in relation to the total weight of the supported catalyst. The supports themselves are preferably characterized by a specific surface area of at least about 10 square meters per gram, and more preferably from about 25 to 200 square meters per gram, (as determined by the BET method), and by a pore volume of at least about 0.1 cc./gm, and preferably from about 0.2 to 1.5 cc./gm (as determined by mercury porosimetry). The catalysts can themselves be formed from a thermally decomposable salt so that a suitable solution of the selected rhenium salt, for example, can then be impregnated on to the surface of a catalyst support followed by calcining at a temperature of at least about 4000C for sufficient time to activate the catalyst. Generally, a time of from about 1 to 5 hours will be sufficient at a temperature within the range of 300 to 600 C. This calcining step can be performed in air or in the presence of B2S or an inert gas such as nitrogen, helium and the like. The particular decomposable compound selected will influence the anion associated with the Re and promoter cations in the supported catalyst following the calcining step. Thus, a thio-salt of Re and/or promoter, such as ammonium thiorhenates or ammonium thiomolybdates, will be generally calcined to form 2 Re sulfide catalyst. Non-thio salts, such as the nitrate, carboxylates, carbonate and the like which do not contain S, will generally yield a Re oxide catalyst on decomposition when the decomposable salt itself contains oxygen or when the calcining is conducted in an O2-containing gas (e.g., air). Similarly, calcining the above S-=ree Re and promoter salts in the presence of an H2S, COS, or CS2 atmosphere will also provide a catalyst containing Re sulfides. one techniquefor preparing the catalyst comprises intimately mewing the selected catalyst components - e.g. rhenium salt such as ammonium perrhenate or a mono- or di-carboxylate of fran 1 to 10 cation atoms (e.g. the acetate, oxalate and the like), caSate or nitrate, alone or in combination with a selected promoter compound (e.g. ammonium permolybdate) - in the presence of a solvent soas to produce a solution or for a flowable paste. Then the selected support may be impregnated with this liquid mixture and evaporation carried out under the selected temperature conditions to obtain a dry solids. Water may be used as the solvent for mixing the catalyst components, but oxygenated organic compounds such as alco hols, ethers, esters, dioxide and the like can also be used. A particularly preferred catalyst of this invention is prepared by first depositing (e.g., by vacuum impregnation) the selected support (e.g., gamma-alumina) with a thermally decomposable molybdenum compound (e.g., am.monium permolyb- date or thiomolybdate), followed by drying and calcining to form solids having molybdenum salts deposited thereon. Thereafter, the selected decomposable rhenium compound (e.g., ammonium perrhenate) is deposited thereon, e.g., by vacuum impregnation, followed by a second drying and calcin ing of the solids. If desired, a Group VIII noble metal promoter compound (e.g., a¯rho ium salt such as rhodium nitrate) can then be deposited on the Mo-Re catalyst, again followed by drying and calcining. Alternatively, the preferred catalyst can be prepared by depositing the selected Group VIII noble metal promoter compound prior to, or simultaneously with, the deposition of the Re compound onto the surface of the solids on which molybdenum has been previously deposited. Each drying step can be performed at tempera- tures within the range of from about 100 to 300it for a time sufficient to remove substantially all water (in the case of use of aqueous solutions of the foregoing Mo, Re and/or Group VIII noble metals salts) or at a temperature above the solvent boiling point to about 300'C, for removal of any other selected solvent used during the impregnation or deposition of the metals, optionally together with passing of an inert gas such as nitrogen over the solids' surface to facilitate the removal of the water or solvent. The calcining temperatures and times are as described above. The supported catalyst thus prepared will generally have a surface area of at least about 5 m2/gm (and preferably at least 40 m2/gm) and can be used in a fixed bed and can also be used in fluidized bed or other conventional means of housing the catalyst particles for ultimate contact with the gaseous reactants. Olefin Conversion Process The olefinic hydrocarbons which can be employed as reactants in the process of this invention are those which contain an aliphatic chain of at least two carbon atoms in which there exists at least one aliphatic double bond, -HC=CH-. Suitable olefinic hydrocarbons are those which are normally gaseous as well as those which are liquids at room temperatures but which can exist in the gaseous form at the elevated temperature and pressure conditions which are employed during the reaction. Representative olefinic reactants which can be employed, either alone or in combination, are propylene, l-butene, 2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, 3-hexene, 3-methyl-1-pentene, cyclobutene, 1-heptene, 2-heptene, 1-octene, 2-octene, 1-nonene, 2-nonene, 1-decene, cyclohexene, cyclooctene, l-douecene, 1-hexadecene, allyl benzene, propenyl benzene, 3-phenyl-1-hexene, 4-o-tolyl-1-butene, and 1,6-di-phenyl-3-hexene. Thus, suitable olefins include (1) linear mono olefins o 2 to 20 carbon atoms, inclusive of terminal olefins, i.e., olefins, having a terminal H2C=CH-group, and internal olefins having the carbon-carbon double bond, as a -HC=CH- group in an internal carbon-carbon bond of the olefin, and (2) cyclic mono-olefins of 4 to 20 carbon atoms having a -EC=CH- group in the cyclic ring. Particularly suitable for this invention are alkenes having from 2 to 10 carbon atoms and cycloalkenes of 4 to 10 carbon atoms, and most preferred are linear alkenes having from 4 to 10 carbon atoms. Illustrative of these preferred classes of olefin feeds are those comprising 1-butene, 2-butene, 1-hexene, 1-pentene, propene, 1-octene, cyclohexene, cyclopentene, cyclobutene and the like, and mixtures thereof. Paraffins (such as alkanes of 2 to 20 carbon atoms) and isoolefins (i.e., olefins having a XC=Cs group in which one or botch carbon atoms are hydrocarbyl substituted, such as 2-methyl-2-butene) can be also present in the gas feed to the oxidation zone in the practice of this invention, but they are essentially unreactive in forming the desired ketones. Preferred olefinic feeds are olefin gas mixtures obtained from the refining of crude oil. Thus, butene cuts from such refineries typically contain n-butenes (1-butene and 2-butene) which will be converted by this process into 2-butanone, and also typically contain butane and isobutene. The process of this invention is effected by passing the selected olefin and water vapor and (optionally) molecular oxygen over the surface of a catalyst of this invention under conditions such as to maintain a vaporous olefin in the reaction zone. The conditions of temperature and pressure under which this can be performed can vary widely depending on such factors as the particular olefin selected for use, the space velocity of gases through the reactor and other factors. Generally, however, a temperature of from about 125 to 6000C, preferably from about 200 to less than about 400 C, will be entirely suitable. Most preferably, where the alkene comprises butene-l or butene-2, the temperature within the catalyst reactor is maintained within the range of from about 250 to 3750C. Similarly, for cycloalkenes such as cyclohexene, a temperature range of about 125 to about 2000C is most preferable. The pressures are in no way critical and will generally range from about 0 to 2000 psig, preferably from about 5 to 150 psig, although higher or lower pressures are also suitable. The space velocity of the total gases through the oxidation reactor are also not critical and can range from 100 to 10,000 v/v/hr., and preferably from about 200 to 6,000 v/v/hr., where tvn represents a unit of volume (e.g., nCCn), The reaction can be carried out either batcbwise, continuously, or semi-continuously. In batch operations, the gaseous reactants may be placed, together with the catalyst, in a suitable pressure vessel and allowed to remain there under the desired reaction conditions for a suitable reaction interval, which will generally range from about 0.01 to 10 hours or more, depending on the degree of reaction completeness sought. In continuous operation, the gaseous reactants are passed'through a body of the catalyst supported within a reactor vessel, which can be any of the conventional equipment employed by the industry for such reactions. The water vapor (and 02, where employed) can be combined and premixed with, or introduced separately from, the olefin feed, or they can bypassed to the reaction vessel via separate conduits. The manner of contacting the water vapor and olefin is not critical and anv of the conventional gas-gas contacting methods employed in the industry may be used. The ratio of olefin:water vapor can also vary widely. Generally, the molar ratio of olefin:water vapor introduced to the reactor will range from about 2:1 to 1:20, preferably from about 1:1 to 1:10. Where O2 is employed, the olefin: oxygen molar ratio in the total gases fed to the reactor will generally range from about 0.5:1 to 10:1, and most typically from about 1:1 to 5:1. However, ratios outside the foregoing ranges can also be employed. An inert gaseous diluent such as nitrogen or paraffin can also be introduced together with the other gaseous feeds to the reactor in order to achieve a desired high space velocity and to minimize hot spots which could result in an over-oxidation of the feed and/or reactants during the exothermic ketone formation using an O2-containing feed. Preferably, the olefin, water vapor, and 02 (where employed), are contacted with a non-halide catalyst of this invention and in the substantial absence of free halide (that is a molar ratio of free halide:olefin of less than about lx10 :1) in order to minimize corrosion difficulties. The reaction zone, in which the desired reaction between the olefin and water vapor to form the selected ketone is effected, is preferably oxygen-free, that is, contains a molar ratio of added molecular oxygen to olefin of less than about 0.01:1. Molecular oxygen, therefore, is not a desired component of the gas feed to tne process and its presence serves to increase the amount of oxygenated by-products, including carbon dioxide and carbon monoxide, as will be illustrated in the examples which follow. The gas feed is preferably substantially free of H2S, e.g., contains less than about 0.01 vol.% H2S, to avoid complicating the task of product recovery and purification. The ketones which are formed will depend, of course, on the particular olefin(s) employed in the feed. Thus, use of alone as the olefin will result in forming the corresponding alkanone having the same number of carbon atoms as the alkene fed (acetone from propylene; methyl ethyl ketone from 1-butene, 2-butene, or mixtures thereof; cyclohexanone from cyclohexene). The process is particularly suitable for forming alkanones having from 4 to 10 carbon atoms. The major alcohol product formed in the process of this invention will correspond to the carbon skeleton of the ketone product, e.g., secondary butyl alcohol corresponding to methyl ethyl ketone. The ketones and alcohols produced by the process of this invention can be recovered from the reaction mixture in any desired manner, such as by distillation or by extraction with water or other solvents followed by distillation. Preferably, at least a portion of the unreacted gases are recovered and recycled to the reactor in addition to fresh feed gases in order to maximize olefin conversion. Alternatively, a series of reactor vessels can be employed and the unreacted gases from the first vessel can then be passed as feed to the second vessel, together with make-up gaseous olefin and water vapor as required. Gaseous H2, which is also formed in the overall reaction, ilustrated by equation (I) below, can be readily recovered from the reaction effluents. catalyst EMI13.1 Molecular oxygen is an optional, additional component of the feed to the reaction zone for conversion of the olefin to the desired ketone. When employed, the olefin:oxygen molar ratio in the total gases fed to the reactor will generally range from about 0.5:1 to 10:1, and more typically from about 1:1 to 5:1. However, ratios outside the foregoing ranges can also be employed. However, the reaction zone, in which the desired reaction between the olefin and water vapor to form the selected ketone is effected, is preferably oxygen-free, that is, contains a molar ratio of added molecular oxygen to olefin of less than about 0.01:1. Molecular oxygen, therefore, is. not a required component of the gas feed to the process and its presence serves to increase the amount of oxygenated by-products, including carbon dioxide and carbon monoxide, as will be illustrated in the examples which follow. The choice of whether or not to employ 2 in the gas feed to the reaction may be made based on a variety of process parameters. The O2-containing feeds will yield a more exothermic reaction, and hence provide an opportunity for higher level heat recovery from the reaction effluent. On the other hand, use of 2 in the feed generally results in an increase in the amount of undesired by-products which are made, such as CO and CO2, although olefin conversions are somewhat increased over comparative reactions in which 2 is excluded from the reaction zone. Of course, the precise balance of these potential benefits and disadvantages of O2-containing feeds must be made on a case-by-case basis. while not wishing to be limited thereby, it is believed that the ketone product formed by the process of this invention proceeds by way of an alcohol intermediate corresponding to the skeleton structure of the ketone product. It is believed that this is the explanation for the quantity of alcohol product which is also formed and detected in the examples that follow. For example, butene is converted to a mixture of ketone and secondary butyl alcohol. Accordingly, our invention also provides a process for contacting such an. alcohol with water vapor and 2 (where employed) in the presence of a catalyst of this invention to form a corresponding ketone. Process parameters include feed ratios, reaction times, space velocities, temperatures, pressures and the like, which are discussed above for the use of olefin-containing feeds, are also useful in the embodiment of this invention in which the alcohol is employed as the feed. The molar ratio of alcohol:water vapor is generally from about 0.01:1 to 100:1, and preferably from about 0.01:1 to 10:1. Alcohols which are suitable as feeds correspond to any of the above-discussed product alcohols of this invention. Therefore, particularly suitable are alkanols, and especially secondary alkanols, having from 3 to 10 carbon atoms per molecule. The utility of the catalysts of this invention for conversion of alcohols to ketones can be readily seen from the following examples, and it will also be apparent to one skilled in the art that recycle of recovered alcohol by-product to an olefin-reaction zone using a catalyst of this invention will provide improved overall utilization of an olef in-containing feed as a result of the further reaction of the thus-recycled alcohol by-product. The process of this invention can be further illustrated by reference to the following examples wherein percent conversions and selectivities are mole percent. Product selectivities in the examples were determined by gas chromatographic analysis after steady-state conditions were observed. Products formed were methyl ethyl ketone, CO, CO2, secondary butyl alcohol, butyl mercaptan and the balance unknown. In the Examples 1-41 and 46-50, the gaseous effluents from the reactor were analyzed for butene consumed, using isobutane as a standard and employing response factors determined for the GC by calibration with a known gas mixture. In Examples 42-45, the gaseous reactor effluent was passed through a series of four traps partially filled with water. The solutions in each trap were analyzed by gas chromatography using dioxane as internal standard. No internal standard was employed in Example 46. To illustrate the surprisingly improved selectivities to methyl ethyl ketone which are achieved in the process of this invention and the substantial absence of oxygen, a trimetallic rhenium-rhodium-molybdenum sulfide catalyst of this invention was prepared and then tested in oxide form in the presence of molecular oxygen to establish a base line of activity. Thereafter, this oxide catalyst was converted to a sulfide form and then tested in the presence of molecular oxygen for a butene feed to determine a base line of activity. Thereafter, a series of subsequent runs were conducted in which molecular oxygen was not employed as a component of the gas feed. EXAMPLE 1 Gamma-alumina (15 cc.; 12-20 mesh; 100 m2/gm surface area; 0.45 cc./gm pore volume; Alfa Products) was dried in air in a Linberg furnace at 500iC for 3 hours to give a dry weight of 12.89 grams. Ammonium perrhenate [NH4ReO4] (1.30 grams) was dissolved in distilled water to form a 5.5 cc. aqueous solution and transferred into a 60 cc. dropping funnel. The catalyst support was placed in a 125 cc. glass filtering flask equipped with a side arm for pulling a vacuum, and the filtering flask was attached to a dropping funnel using a rubber stopper. After evacuation to a pressure of -15 in Hg, the ammonium perrhenate solution was added dropwise to the catalyst support to achieve complete wetness. The impregnated wet catalyst was placed in -a stainless steel gauze boat and dried in air at 125it for 1.25 hour, 250it for 0.75 hour and 350it for 1 hour, and finally calcined in air by raising the furnace temperature to 5000C (at a rate of about 100C/min.), which was maintained for 3 hours. After the drying and calcining procedure, the resulting catalyst was found to comprise rhenium oxide on gamma-alumina and to contain 7.1 wt.% Re, calculated as the metal, based on the weight of the catalyst support. Ten cc. of the foregoing oxide catalyst and 20 cc. of fused ceramic inerts (12-20 mesh) were well mixed and loaded into a test reactor which comprised a 24-inch (0.38 inch ID) stainless steel tubular reactor equipped with gas inlets and gas outlets at opposing ends of the tubular reactor. The reactor was then heated to a temperature of 303'C (which was maintained by means of electric heating tape and a Gardsman temperature control). Temperatures in the reactor were determined by means of a thermocouple positioned in the - center of the catalyst bed. A gaseous mixture containing butene-1, oxygen, nitrogen and water vapor was passed to the reactor, the oxygen and nitrogen being employed as a 10:90 vol:vol mixture of oxygen and nitrogen. The feed rates for these gaseous components and the reaction temperature were 60 cc. per minute of.butene, 730 cc. per minute of the oxygen:nitrogen mixture, and 224 cc. per minute of water vapor. The total gas hourly space velocity of the gaseous mixture through this reactor was 6084 cc/cc/hr. A gaseous inlet pressure of 7.1 psig was employed throughout the reaction (0.4 hrs.). A gaseous effluent was continuously withdrawn from the reactor and was sampled and analyzed by means of an on-line gas chromatograph. After achieving steady conditions, methyl ethyl ketone was found to have been formed in a selectivity of about 86.6% at a butene conversion of 5.6%. Selectivity to carbon dioxide was 3.6 and no carbon monoxide was found. EXAMPLE 2 In a separate run, the catalyst used in Example 1 was contacted with a butene feed under the same conditions except that the gaseous feed to the reactor (2980C) was 102 cc. per minute of butene-l, 730 cc. per minute of the oxyg en nitrogen mixture, and 224 cc. per minute of water vapor, providing a gas hourly space velocity of 6336 cc/cc/hr. Methyl ethyl ketone was found to have been formed in a selectivity of 87.4%, as determined by sampling after 3.0 hours of reaction. (Butene conversion in this run was not determined.) No selectivity loss to carbon dioxide and carbon monoxide was detected. EXAMPLE 3 The rhenium oxide catalyst employed in Example 2 above (still mixed with the inerts) was sulfided in the reactor by contacting the oxide catalyst with a gas mixture of hydrogen sulfide (190 cc./min.; charged as 6 vol.% H2S in N2) and H2 (230 cc./min.) at a temperature of 325C and a gas inlet pressure of 9 psig, for 3 hours. The resulting solids were then contacted under the same flow conditions with B2 (520 cc./min) to strip out any absorbed, unreacted d2S. The catalyst was then determined to comprise rhenium sulfide, and to contain rhenium in an amount of about 7.1 wt.%, calculated as the element, based on the total weight of the catalyst support. The rhenium sulfide catalyst was then contacted with a butene feed of the following composition employed the pro cedure of Example 1 employing a gas inlet pressure of about 8.5 psig and a reaction temperature of 298it: 60 cc. per minute of butene, 380 cc. per minute of the oxygen:nitrogen mixture and 224 cc. per minute of water vapor. The total gas hourly space velocity during the run (2.0 hrs.) was 3984 cc/cc/hr. At a 4;8% conversion methyl ethyl ketone was found to be formed in a selectivity of 83.3%. Carbon dioxide selectivity was 3.68 and secondary butyl alcohol selectivity was 2.9%. No selectivity loss to carbon monoxide was observed. EXAMPLE 4 The rhenium sulfide catalyst of Example 3 was employed in a second such run at a reaction temperature of 294it and a gas inlet pressure of 8.5 psig for 4.5 hours. In this Example, the gaseous feed to the reactor comprised 60 cc. per minute of butene, 730 cc. per minute of the oxygen:nitrogen mixture and 224 cc. per minute of water vapor. The total gas hourly space velocity was therefore 6084 cc/cc/hr. At a 3.4% butene conversion, methyl ethyl ketone selectivity was 88.4%. No selectivity loss to carbon dioxide or carbon monoxide was observed. Secondary butyl alcohol selectivity was observed to be 1.8%. EXAMPLE 5 Gamma-alumina (25 cc.; 12-20 mesh; Alfa Products) was dried in a Lynberg furnace at 500C for 3 hours in air to give a dry weight of 21.0 grams. Ammonia perrhenate (1.52 grams) was dissolved in distilled water to provide 24 cc. of an aqueous solution. Following the procedure of Example 1, the support was vacuum impregnated three times, each impregnation employing 8.0 cc. of the above aqueous ammonium perrhenate solution. After each impregnation, the impregnated solids were dried in nitrogen for one-half hour at 125*C, followed by one-half hour at 250it and then calcined in air at 5000C for 3 hours. After the third impregnation, the solids were allowed to cool to room temperature and the material was divided into two equal parts. The first one half of the impregnated solids was then impregnated twice with an aqueous solution of rhodium trinitrate using the drying and calcining procedure described in Example 1. The rhodium trinitrate solution comprised, in each impregnation 4.0 cc. of an-aqueous solution containing 0.521 gram of rhodium trinitrate. After each impregnation with the rhodium salt, the solids were dried and calcined as described above. The mixed rhenium oxide:rhodium oxide on alumina catalyst was then mixed with inerts and sulfided with hydrogen sulfide gas using the procedure described above in Example 3. The catalyst thereby obtained was found to comprise 1.5 wt.% rhodium and 5.0 wt.% rhenium, calculated as the metals, based on the weight of the catalyst support. Following the procedure of Example 1, a series of runs were conducted using a reaction temperature of 300'C, and a gas inlet pressure of about 7 psig, with varying compositions of gaseous feed to the reactor. Water vapor feed in each run was 224 cc. per minute. The data thereby obtained are set forth in Table I below. Run 3 shows that H2S is not a desired component of the feed to the process using a Rh-Re sulfide catalyst. TABLE I: Rh-Re Sulfide Catalyst Butene O2/N2(1) H2S % Selectivity Run Time Feed Feed Feed GHSV(2) Butene MEK SBA C4SH No. (hrs.) (cc/min) (cc/min) (cc/min) cc/cc/hr Conv.(%) (3) CO2 CO (4) (5) 1 1.0 31 380 0 3138 43.6 50.7 18.9 5.6 ND 9.8 2 2.0 60 730 0 6084 14.6 51.9 23.0 6.1 ND 3.1 3 2.5 60 730 65 6474 39.5 6.0 13.9 10.8 ND 58.8 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. COMPARATIVE EXAMPLE 6 Employing the catalyst preparation procedure of Example 1, a rhodium oxide on gamma-alumina catalyst was prepared by vacuum impregnation of the gamma-alumina support with a 9.0 ml. aqueous solution containing 1.0 grams of rhodium trinitrate, followed by drying in nitrogen at 150'C for 1 hour, 250iC for 1 hour, and 350'C for 2 hours, and by calcining in air at 5000C for 3 hours. The rhodium oxide catalyst was then mixed with inerts and subjected to the H2S sulfiding/H2 stripping procedure of Example 3. The rhodium sulfide on gemma-alumina catalyst thereby obtained was found to contain 1.5 wt.% rhodium, calculated as the metal, based on the weight of the catalyst support. This catalyst was employed in Runs A and B, to be described in more detail below. A second rhodium on gamma-alumina catalyst containing 1.0 wt.% rhodium (calculated as the metal) was prepared from RhCl3.3B20 and ammonium sulfide by vacuum' impregnation of an aqueous rhodium chloride solution (8 cc.; containing 0.565 grams -of the hydrated rhodium trichloride), following the procedure of Example 1. The impregnated solids were dried in the oven at 125'C for 3 hours under nitrogen and 25 cc. of the resulting solids was then reacted with an aqueous solution containing 0.70 gram of ammonium sulfide [(NH4)2S] by contacting for 30 minutes at 25'C in a glass flask. The resulting solids were then washed with distilled water (3 equal portions of 10 cc.) to remove any excess unreacted ammonium sulfide, followed by drying of the solids under nitrogen in the furnace at 1250C for 1 hour, 2000C for 1 hour, and 350iC for 1 hour. The dried solids were then calcined in the furnace by raising the furnace temperature to 500*C (at a rate of 100C per minute) which was then main- tained for 3 hours, under N2. This rhodium sulfide catalyst .mixed with inerts and employed in Runs C to E, to be described below. The selected rhodium sulfide catalyst prepared as above were then employed in separate runs for butene oxidation using the procedure described above for Example 3, employing the conditions of reaction set forth in Table IT below. The reaction temperature in Run A was 303'C and in Runs B to E was 300'C. The gas inlet pressure in each run was about 7 psig, and the water vapor injection rate in Run D was 112 cc. per minute and in all other runs was 224 cc. per minute. The data thereby obtained are set forth in Tabie 11 below. Under comparable conditions, the rhenium-rhodium sulfide catalysts of Example 1 obtained significantly improved conversions to ketone product while providing decreased selectivity loss to carbon dioxide and carbon monoxide by-products. Comparing Run 6-C and Run 5-2, each conducted under similar space velocities and at 300eC, it can be seen that the rhodium-rhenium sulfide catalyst of this invention provided over a 35 percentage point advantage in methyl ethyl ketone selectivity (51.9% in Example 5-2 versus 16.5% in Comparative Example 6-C) while at the same time providing almost a 46 percentage point advantage in decreased total selectivity to carbon dioxide and carbon monoxide (29.1% CO2 + CO in Example 5-2 versus- 75.0% in Comparative Example 6-C). Similarly, the rhodium-rhenium sulfide catalyst of Example 5-1 provided an 18 percentage point increase in methyl ethyl ketone selectivity (50.7% versus 32.78) and over 64 percentage points decrease in total selectivity loss to carbon dioxide and carbon monoxide (CO2 + CO: 24.5 in Example 5-1 versus 88.9% in Comparative Example 6-D), as cpmpared to the rhodium sulfide catalyst of Comparative Example 6, Run D, which runs were conducted under similar conditions of temperature and gas hourly space velocities. TABLE II: Comparison: Rh Sulfide Catalyst Butene O2/N2(1) H2S % Selectivity Run Time Feed Feed Feed GHSV(2) Butene MEK SBA C4SH No. (hrs.) (cc/min) (cc/min) (cc/min) cc/cc/hr Conv.(%) (3) CO2 CO (4) (5) A 0.5 60 730 0 6084 18.0 51.9 36.0 2.8 0.3 1.6 B 1.5 60 730 65 6474 29.0 8.9 16.0 13.1 0.3 46.1 C 0.5 60 730 0 6084 14.3 16.5 63.6 11.4 - 0.2 D 1.5 31 380 0 3138 12.9 32.7 56.2 2.4 - 0.7 E 2.0 60 730 65 6474 43.4 7.6 21.9 25.0 - 31.6 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 7 A 10.2 gram portion of the supported rhenium oxide catalyst prepared as in Example 5 was impregnated with 8 cc. of an aqueous solution containing 0.414 gram of palladium nitrate (Pd(NO3)2.H2O), using the double impregnation, drying and calcining steps described above for Example 5. The mixed Re-Pd oxide catalyst was then mixed with inerts and sulfided using the procedure of Example 3. The mixed palladium sulfide:rhenium sulfide on gama-alumina catalyst was found to contain 1.5 wt.% palladium and 5.0 wt.% rhenium, calculated as the metals, based on the weight of the catalyst support. This oxide catalyst was then mixed with inerts and employed in a series of runs using the procedure of Example 1.- Runs 1 and 3 employed a reaction temperature of 3000C. Run 2 employed a reaction temperature of 250'C. In each case, the gas inlet pressure was about 7 psig and the water vapor feed rate was 224 cc./min. The data thereby obtained are set forth in Table III below. TABLE III: Pd-Re Sulfide Catalyst Butene O2/N2(1) H2S % Selectivity Run Time Feed Feed Feed GHSV(2) Butene MEK SBA C4SH No. (hrs.) (cc/min) (cc/min) (cc/min) cc/cc/hr Conv.(%) (3) CO2 CO (4) (5) 1 2.0 60 730 65 6474 14.3 39.5 4.5 2.2 10.0 35.6 2 3.0 60 730 65 6474 2.4 40.7 0 0 26.5 16.7 3 4.0 60 730 0 6084 7.4 17.8 36.4 22.7 5.9 3.0 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 8 Employing the procedure of Example 1, gammaalumina (12.9 grams) was impregnated with ammonium heptamolybdate by use of an aqueous solution containing 2.19 grams of the ammonium paramolybdate salt, followed by drying and calcining in nitrogen at the temperature conditions described above for Example 1. Thereafter, the solids were impregnated with ammonium perrhenate (NH4ReO4) followed by drying and calcining in air at the temperatures and for the times described in Example 1. The Re-Mo oxide catalyst thereby obtained was found to contain 3.7 wt.% rhenium and 9.5 wt.% molybdenum, calculated as the metals, based on catalyst support. Ten cc. of this catalyst was then employed (with inerts, per Example 1) in Runs 1 and 2 for butene oxidation. A separate rhenium-molybdenum catalyst was prepared by vacuum impregnating 8.9 grams of gamma-alumina with 22 cc. of an aqueous solution of ammonium thio molybdate (containing 1.73 grams of (NH4)2MoR # using the procedure of Example 1, followed by drying of the impregnated solids in helium at 1250C for one hour, 250 C for one hour, and 3500C for 3 hours. This catalyst impregnation procedure was then repeated six times, and the resulting molybdenum sulfide catalyst was vacuum impregnated with Re using the procedure of Example 1 and employing 3.7 cc. of an aqueous solution containing 0.391 gram of 2=20nium perrhenate, followed by drying in air at 1250C for 1 hour, 2500C for 1 hour and 350 C for 1 hour and calcining in air at 5000C for 3 hours. The resulting rhenium-molybdenum catalyst was found to comprise 2.8 wt.% rhenium and 7.5 wt.% molybdenum, calculated as the respective metals, based on the weight of the catalyst support. Ten cc. of the catalyst was then mixed with inerts, sulfided as in Example 3 and employed in Rurs 3 and 4, using the procedure of Example 1. Data are summarized in Table IV. TABLE IV: Re-Mo Oxide Catalysts Gas Feed (cc/min.) GHSV(2) % Selectivities Run Temp Time Press (1) H2O cc/cc/ Butene SBA C4SH No. ( C) (hrs) psig Butene O2:N2 Vapor hr) Conv.(%) MEK CO2 CO (4) (5) 1 308 0.5 7 60 380 224 3984 - 78.5 0 0 6.1 0 2 296 1.5 7 102 730 224 6338 3.4 77.7 0 0 10.5 0 3 302 7.5 9 60 730 224 6084 8.8 81.4 0 2.6 0 0 4 300 1.8 9 60 730 224 3984 7.6 84.4 0 2.1 0 0 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 9 A rhenium-molybdenum sulfide catalyst was prepared using three different methods. Each sulfided catalyst, supported on gamma-alumina, was then employed in a series of runs'for butene oxidation. The first sulfide catalyst was prepared by subjecting the rhenium-molybdenum oxide catalyst which was employed in Runs 1 and 2 of Example 8 to the in situ H2S sulfiding/H2 stripping procedure of Example 3. The resulting sulfided catalyst was found to comprise 2.8 wt.% rhenium and 7.5 wt.% molybdenum, calculated as the metals. This sulfided catalyst was then mixed with inerts and employed in Run 1 of Table V as in Example 1. The second Re-Mo sulfide catalyst was prepared employing the procedure of Example 1 by vacuum impregnating the gamma-alumina support (8.9 grams) with one-sixth of 22 cc. aqueous solution containing 2.284 grams of ammonium tetrathiomolybdate, followed by drying in air at 1250C for I hour and 2500C for 1 hour, and at 3500C for 3 hours. This molybdenum impregnation step was then repeated five times, followed each time by the three-step drying process, and the resulting solids were then vacuum impregnated with 3.7 cc. of an aqueous solution containing 0.391 grams of ammonium perrhenate again employing the identical drying procedure. Finally, after again drying in the three-stage procedure, the solids were calcined in air at a temperature of 5000C for 3 hours and then mixed with inerts and sulfided using the H25 sulfiding/H2 stripping procedure of Example 3. The resulting sulfided catalyst was employed in Run 2 of Table V below. The third Re-Mo sulfide catalyst was prepared by ref fluxing the selected amount of gamma-alumina (12.6 grams) in 50 cc. of methanol containing 2.26 grams of arninonium paramolybdate and 0.68 gram of ammonium perrhenate for 1.5 hours followed by removing most of the methanol heating (65 C, 1 hour) while passing 2 cech the solid/liquid r.--'-ure and drying --n air at 125 C for 1 hour, 2500C for 1 hour, 3500C for 1 hour to remove the methanol and calcining in air at 5000C for 3 hours to obtain the corresponding mixed oxide of rhenium and molybdenum on the gamma-alumina. The oxide catalyst was thereafter mixed with inerts and treated using the H2S sulfiding/H2 stripping procedure of Example 3 to obtain a rhenium-molybdenum sulfide catalyst supported on gammaalumina containing about 3.7 wt.% and 7.5 wt.% rhenium and molybdenum, respectively, calculated as the elements. This sulfide catalyst was then employed in Runs 3, 4 and 5 in Table V below using the method of Example 1. TABLE V: Re-Mo Sulfide Catalysts Gas Feed (cc/min.) GHSV(2) % Selectivities Run Temp Time Press (1) H2O cc/cc/ Butene SBA C4SH No. ( C) (hrs) psig Butene O2:N2 Vapor hr) Conv.(%) MEK CO2 CO (4) (5) 1 300 7.7 7 60 380 224 3984 28.3 70.3 7.6 2.5 4.1 0 2 310 3.4 9.7 102 730 224 6336 6.6 86.4 0 1.3 12.0 0 3 302 0.9 8.9 102 730 224 6336 14.0 68.2 7.0 4.7 6.3 6.0 4 291 7.3 9.1 60 730 224 6084 14.3 74.7 2.0 2.0 11.3 0 5 298 16.2 9.3 60 380 224 3984 9.3 76.7 2.2 1.1 10.8 0 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 10 FOR COMPARISON Employing the procedure of Example 8 above, 37.1 grams of gamma-alumina were vacuum impregnated with ammonium heptamolybdate, followed by drying in N2 at 125 C for 1 hour, 2500C for 1 hour, and 3500C for 1 hour and calcining inN2 at 5000C for 3 hours. The resulting molybdenum-oxide catalyst, supported on gamma-alumina, was found to contain 9.5 wt.% molybdenum, calculated as the metal. This oxide catalyst was then mixed with inerts and employed in Runs A and B of Table VI below using the procedure of Example 1. The catalyst employed in Runs C and D of Table VI comprised the corresponding sulfided catalyst which was prepared by the in situ sulfiding/stripping procedure of Example 3. The data thereby obtained are set forth in Table VI below. In comparing the molybdenum oxide catalysts of Comparative Example 10, Runs A and B, with the Re-Mo oxide catalysts of this invention used in Example 8, it can be seen that the rhenium-catalyst of this invention permitted the formation of the methyl ethyl ketone product in high selectivities with only minimal, if any, selectivity loss to an oxide of.carbon. Thus, the rheniummolybdenum oxide catalyst of Example 8-3 provided 81.4% methyl ethyl ketone selectivity at 8.8* butene conversion : and formed only 2.6% selectivity loss to carbon monoxide with no carbon dioxide being detected. In contrast, Com aratve Example 10-A suffered almost 10 in selectivity loss to total carbon dioxide and carbon monoxide under similar gas flow conditions. Similarly, the molybdenum sulfide catalysts of Compar2tiVe Example 10, Runs C and D, formed only up to about 69% selectivity methyl ethyl ketone with up to about 12e selectivity loss to carbon dioxide and carbon monoxide. In contrast, the rhenium-molybdenum sulfide catalyst o= Example 9 formed as much as 86.4% selectivity to metal ethyl ketone with as little as 1.3% selectivity loss to carbon dioxide and carbon monoxide (Run 2 of Example 9). TABLE VI: Comparison: Mo Catalysts Gas Feed (cc/min.) GHSV(2) % Selectivities Run Temp Time Press. (1) H2O cc/cc/ Butene SBA C4SH No. ( C) (hrs) psig Butene O2:N2 Vapor hr) Conv.(%) MEK CO2 CO (4) (5) Mo-Oxide A 300 2.0 7 60 730 224 6084 9.1 80.6 6.9 2.8 8.1 0 B 305 5.0 7 102 730 224 6338 20.4 71.0 3.8 1.9 4.2 0 Mo-Sulfide C 305 5.2 7 60 730 224 6084 15.1 62.6 10.0 2.0 13.6 0.9 D 298 6.0 7 102 730 224 6336 12.6 68.8 5.8 1.9 9.6 0.9 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 11 A trimetallic oxide catalyst comprising a mixture of oxides of rhodium, rhenium and tungsten, supported on gamma-alumina was prepared by vacuum impregnation of the dried gamma-alumina (38.8 grams) with ammonium tungstate [(WH4)10W12041l, followed by a stepwise impregnation with ammonium perrhenate after which rhodium trinitrate was impregnated. The support was impregnated with the tungsten compound using 16 cc. of an aqueous solution containing 0.72 grams of ammonium tungstate, followed by drying at 2500C in nitrogen. This impregnation and drying procedure was repeated 5 additional times. Then, the final, dried solids were heated at 3500C for 2 hours in air and then calcined in air at 5000C for 3 hours to convert the metal salt to the oxide form. One third of these solids was then vacuum impregnated with 5 cc. of an aqueous solution containing 0.57 gram of ammonium perrhenate, in a single vacuum impregnation, followed by drying in nitrogen and calcining in air according to the drying and calcining procedure used in Example 5. This single-step vacuum impregnation, drying and calcining procedure was then repeated, using S cc. of an aqueous solution containing 0,39'grams of rhodium trinitrate in the vacuum impregnations. The oxide catalyst thereby obtained was found to contain 1.0 wt.% rhodium, 3.1 wit.% rhenium and 7.8 wot.% tungsten, calculated as the respective element. The oxide catalyst thereby obtained was mixed with inerts employed in Runs 1 and 2 of Table VII below. After Run 2, the oxide catalyst was sulfided using the in situ sulfiding/stripping procedure of Example 3, and was employed in Run 3. TABLE VII: Rh-Re-W Catalysts Gas Feed (cc/min.) GHSV(2) % Selectivities Run Temp Time Press. (1) H2O cc/cc/ Butene SBA C4SH No. ( C) (hrs) psig Butene O2:N2 Vapor hr) Conv.(%) MEK CO2 CO (4) (5) Rh-Re-W Oxide 1 303 0.7 7 60 380 224 3984 30.6 74.0 10.9 0.3 5.2 0 2 305 3.2 7 60 730 224 6084 31.8 50.3 0.7 10.3 4.1 0 Rh-Re-W Sulfide 3 294 6.0 7 66 380 224 4020 27.5 72.0 9.9 1.2 4.5 0 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 12 FOR COMPARISON Employing the procedure described above for Example 11, a rhodium-tungsten oxide catalyst, supported on gamma-alumina was prepared by six separate vacuum impregnations of 38. 8 grams of gamma-alumina with the ammonium tungstate salt, followed in each impregnation by a drying and calcining in each step. Thereafter, rhodium trinitrate was vacuum impregnated, again followed by drying and calcining in air to form the desired oxide catalyst. This oxide catalyst was found to comprise 1.0 wt.% rhodium and 7.8 wt.% tungsten, calculated as the elements. The data thereby obtained in a butene-l oxidation using this catalyst (mixed with inerts) as in Example 1, at two different temperature conditions, are set forth below in Runs A and B*of Table VIII. After Run B, the oxide catalyst was sulfided using the in situ sulfiding/stripping procedure of Example 3. The rhodium-tungsten sulfided catalyst, supported on gamma-alumina, was then employed using the procedure of Example 1 in a butene-l oxidation. The data thereby obtained are set forth as Runs C and D in Table VIII below. The above gamma-alumina impregnation procedure was repeated with ammonium tungstate except that no rhodium trinitrate was impregnated. Thus, the gammzalumina (38.8 grams) was subjected to six separate vacuum imrenations with the aqueous solution of ammonium tungstate followed by the drying and calcining after each impregnation using the above-described procedure. The resulting tungsten oxide catalyst was found to comprise 7.8 wt.% tungsten, calculze as the element, based on the weight of the total catalyst support. This tungsten catalyst was then employed, after mixing wit inerts, per the procedure of Example 1 in a butene-1 oxidation, as indi- cated in RunsE and F in Table VIII below. (Ten cc. of =e oxIde catalyst was used.) At the end of Run F, the tungsten oxide catalyst was subjected to the in situ sulfiding/stripping procedure of Example 3 to form a tunsten sulfide catalyst, which was then used in a separate Run G as indicated in Table VIII below. Comparing the trimetallic rhenium-rhodium-tungsten oxide catalysts of Example 11 with the rhodium-tungsten and tungsten oxide catalysts of Comparative Example 12, it can be seen that the rhenium-catalyst of this invention illustrated in Example 11 provide high selectivity to ketone and alcohol product with minimal selectivity loss to the carbon dioxide and carbon monoxide by-products which are undesirable. For example, the rhenium-containing catalyst of Example 1, Run 1, formed the ketone product in a selectivity of i4.0% with only 11.2% total selectivity loss to carbon dioxide and carbon monoxide, as contrasted with Comparative Example 12-A which used similar gas flow rates and which obtained the ketone selectivity of only 56.3% and suffered a total selectivity loss of 17.0% to carbon dioxide and carbon monoxide using a rhodium-tungsten oxide catalyst in the absence of rhenium. In further contrast, the tungsten oxide catalyst of Comparative Example 12-E produced only 68.9% selectivity to ketone and suffered a 20.4% selectivity loss to the carbon dioxide and carbon monoxide by-products. Similarly, the rhenium-rhodium-tungsten sulfide catalyst of Example 11, Run 3, formed a ketone in a selectivity (72.0%) which was significantly higher than was observed with rhodium-tungsten sulfide catalyst (56.4% and 43.1% in Run C and D, respectively) and tungsten sulfide catalyst (28.1% in Run G). Comparable benefits and decreased selectivity loss, carbon dioxide and carbon monoxide with the trimetallic rhenium-containing sulfide catalyst of Example 3 are also seen in this comparison. TABLE VIII: Comparison: Rh-W and W Catalysts Gas Feed (cc/min.) GHSV(2) % Selectivities Run Temp Time Press. (1) H2O cc/cc/ Butene SBA C4SH No. ( C) (hrs) psig Butene O2:N2 Vapor hr) Conv.(%) MEK CO2 CO (4) (5) Rh-W Oxide A 308 7.5 7 60 380 224 3984 32.4 56.3 14.7 2.3 12.6 0 B 312 9.9 7 102 730 224 6338 19.2 46.9 22.7 5.6 7.0 0 Rh-W Sulfide C 316 0.5 7 60 380 224 3984 14.8 56.4 22.5 0 9.5 0 D 310 3.8 7 102 730 224 6338 27.5 43.1 13.5 2.6 12.8 2.6 W Oxide E 301 3.0 7 60 380 224 3984 14.3 68.9 18.8 1.6 0 0 F 293 3.6 7 102 730 224 6338 9.8 67.7 14.4 1.3 0 0 W Sulfide G 310 1.0 7 60 730 224 6084 28.0 28.1 21.4 8.6 0 0 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 13 Thirty cc. of gamma-alumina (12-20 mesh) was heated in air at 5000C for 3 hours using the procedure of Example 1 to provide a dry weight of 26.4 grams. Following the exact impregnation procedure of Example 1, 10.6 cc. of an aqueous solution containing 4.63 grams of ammonium paramolybdate in distilled water was impregnated onto the solids, after which the wet catalyst was dried in air at 1250C for 1 hour, 2500C for 1 hour, and 3500C for 1 hour, followed by calcining in air at 5000C for 3 hours. Upon cooling, the solids were then impregnated with 10.3 cc. of an aqueous solution containing 1.41 grams of ammonium perrhenate, after which the same four-step drying and calcining procedure was used. Finally, these solids were impregnated with a 10.3 cc. aqueous solution containing 0.57. grams employed in nitrate, again followed by the same four-step drying and calcining procedure. The thusproduced solids were found to comprise mixed oxides of palladium, rhenium and molybdenum and to contain 1.08wt.% Pd, 3.7 wt.% Re, and 9.5 wt.% Mo, calculated as the respective elements, on the basis of the weight bf the catalyst support. Ten cc. of this catalyst was then well mixed with 10 - 20 mesh fused ceramic inerts, and sulfided using the procedure of Example 3 and then employed in an olefin oxidation following the procedure of Example 1, using the same gas feed composition and feed rates of Run 1 of Example 11, at a reaction temperature of 3100C and a gas inlet pressure of 9.7 psig. At a butene conversion of 6.5%, the following Selectivities were observed: 58.38 methyl ethyl ketone; 5.3% secondary butyl alcohol; 11.38 CO2; 5.0% CO; and 14.0% secondary butyl mercaptan. EXAMPLE 14 Fifteen cc. of the palladium-rhenium-molybdenum oxide catalyst prepared in Example 13 was further vacuum impregnated using the procedure of Example 1 with a 5.1 cc. aqueous solution containing 0.069 grams of sodium nitrate, followed by the four-step drying and calcining procedure employed in Example 13. The resulting solids were found to additionally contain 0.1 wt.% Na, calculated as the element, based on the weight of the total catalyst support in addition to the 1.08% Pd, 3.7% Re, and 9.5% Mo. This catalyst was then mixed with inerts and sulfided using the procedure set forth above in Example 3, and the resulting sulfided catalyst was then contacted-with a butene gas as in Example 13 except that the reaction temperature was 3040C and the gas inlet pressure was 9.4 psig. At a butene conversion of 10.8%, the following selectivities were observed: 39.8% methyl ethyl ketone, 2.8t secondary butyl alcohol, 13.5% CO2 and 14.8 CO. EXAMPLE 15 Following the procedure of Example 1,26.4 grams of dry gamma-alumina was sequentially impregnated witch Mo (using 10.6 cc. of an aqueous solution containing 4.62 grams of ammonium permolybdate), Re (using 10.3 cc. of an aqueous solution containing 1.42 grams of ammonium perrhenate), and finally by Rh (using 10.3 cc. of an aqueous solution containing 0.37 gram of rhodium trinitrate). After each impregnation, the solids are dried under air at 1250C for 1 hour, 2539C for 1 hour, and 3500C for 1 hour, and then calcined under air at 5000C for 3 hours. The resulting oxide catalyst was found to comprise 0.5 wt.% RS, 3.7 wot.% Re, and 9.5 wt.% Mo, calculated as a respective element, based on the total weight of the support. The oxide catalyst was mixed with inerts and sulfided using the procedure of Example 3, and the resulting sulfided catalyst was employed i a series o; runs using conditions set forth in Table IX. TABLE IX Gas Feed (cc/min.) GHSV(2) % Selectivities Run Time Temp Press. (1) (2) H2O cc/cc/ Butene (4) SBA C4SH No. (hrs) ( C) psig Butene O2:N2 Vapor hr) Conv.(%) MEK CO2 CO (5) (6) 1 0.6 315 9.0 60 380 224 3984 11.8 65.3 22.7 3.4 1.3 4.1 2 2.7 301 9.0 104 730 224 6336 14.0 56.5 20.7 13.0 1.1 1.9 (1) Feed = gas mixture containing 85 vol.% butene-1 and 15 vol.% iso-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. (6) Butyl mercaptan. EXAMPLE 16 The catalyst preparation procedure of Example 15 is repeated except that the catalyst solids, following the last calcining step, were then impregnated with 10.3 cc. of an aqueous solution containing 0.11 gram of sodium nitrate. These impregnated solids, containing 0.1 wt.% Na, 0.5 wt.% Rh, 3.7 wt.% Re and 9.S wt.% Mo (calculated as metals, based on support) were then dried and calcined in air using the procedure of Example 15, and mixed with inerts and sulfided in the reactor employing the procedure of Example 3. Thereafter, the sulfide catalyst was used in a series of runs using the procedure of Example 1. Further data thereby obtained are set forth in Table X. TABLE X Gas Feed (cc/min.) GHSV(2) % Selectivities Run Time Temp Press. (1) (2) H2O cc/cc/ Butene (4) SBA C4SH No. (hrs) ( C) psig Butene O2:N2 Vapor hr) Conv.(%) MEK CO2 CO (5) (6) 1 0.7 285 9.1 60 380 224 3984 11.6 60.2 28.8 0 0.9 4.0 2 1.8 295 9.2 104 730 224 6336 14.5 46.3 22.8 12.0 0.3 4.6 (1) Feed = gas mixture containing 85 vol.% butene-1 and 15 vol.% iso-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. (6) Butyl mercaptan. EXAMPLE 17 The multi-step impregnation procedure of Example 13 above was repeated employing12. grams of the dry gamma-alumina support. The first impregnation employed 5.5 cc. of an aqueous solution containing 2.17 grams of ammonium paramolybdate, followed by use of a 5.4 cc. aqueous solution containing 0.79 grams of ammonium perrhenate, and finally by an impregnation using 5.5 cc. of an aqueous solution containing 0.39 grams of rhodium trinitrate. The four-step drying and calcining procedure of Example 13 was used, and the resulting oxide catalyst was found to contain Rh, Re and Mo in an amount of 1.0 wt.%, 3.7 w% and 9.7 wt.%, calculated as the respective elements based on the catalyst support. These solids were mixed with inerts and tested using. the procedure of Example 1. The data thereby obtained is set forth in Runs 1 and 2 of Table XI. The catalyst employed in Run 2 was next sulfided using the procedure of Example 3 and the resulting sulfided trimetallic rhodium-rhenium-molybdenum catalyst was employed in Run 3 of Table XI. TABLE XI Gas Feed (cc/min.) GHSV(2) % Selectivities Run Time Temp. Press. (1) H2O cc/cc/ Butene (3) SBA No. (hrs) ( C) psig Butene O2:N2 Vapor hr) Conv.(%) MEK CO2 CO (4) C4SH Rh-Re-Mo Oxide 1 5.0 303 7 102 730 224 6338 29.8 68.9 12.9 11.6 1.4 0 2 8.3 304 7 60 380 224 3984 37.2 82.0 11.2 1.9 1.6 0 Rh-Re-Mo Sulfide 3 1.5 305 7 60 380 224 3984 53.0 90.9 6.3 0 0 0 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity. (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. EXAMPLE 18 FOR COMPARISON The procedure of Example 17 was repeated except that no rhenium was employed. The resulting oxide catalyst was found to comprise 1.0 wt.% Rh, and 9.5 wt.% Mo, calculated as the elements, based on the weight of the g2mma- alumina support. Runs A through C of Table XII employs this oxide catalyst. Runs D through F employed the corresponding rhodium-molybdenum sulfide catalyst prepared by sufiding the catalyst after Run C, using the procedure of Example 3. EXAMPLE 19 The catalyst procedure of Example 17-is repeated to provide a trimetallic oxide catalyst containing 1.0 wt.% .soh, 3.7 wit.% Re, and 9.5 wt.% Mo supported on gammaalumina. This catalyst, after mixing with inerts, as in Example 1, is tested as in Example 17 at 3020C employing a gas inlet pressure of about 8.5 psig and a gas feed comprising 60 cc./min. butene-l, 380 cc./min. O2:N2 (10:90 vol:vol mixture) and 224 c-c./min. water vapor, for a total gas hourly space velocity of 3,984 cc/cc/hr., for a period of 9.5 hours. At a 42.9% butene conversion, the following selectivities were observed: methyl ethyl ketone 89.7%, secondary butyl alcohol 2.5%, and carbon dioxide 5.6%. No carbon monoxide by-product was detected. The above catalyst was then sulfided using the procedure of Example 3 and employed in a separate run at 304 C for m period cf 13.0 hours, using the above process conditions. At a 47.6E butene conversion the following seleczivities were observed: methyl ethyl ketone 88.45, secondary butyl alcohol 3.7%, and carbon dioxide 6.08. Again, no carbon monoxide by-product was detected. In addition, no by-product butyl mercaptan was detected. TABLE XII Gas Feed (cc/min.) GHSV(2) % Selectivities Run Time Temp. Press. 1- (1) H2O cc/cc/ Butene (3) SBA No. (hrs) ( C) psig Butene O2/N2 Vapor hr) Conv.(%) MEK CO2 CO (4) Rh-Mo Oxide A 8.9 250 7 102 730 224 6338 7.9 48.7 29.7 7.8 5.9 B 5.9 312 7 102 730 224 6338 28.4 69.5 13.7 6.8 3.6 C 0.6 301 7 60 730 224 6084 29.4 43.8 20.9 18.2 2.5 Rh-Mo Sulfide D 2.4 310 7 60 730 224 6084 46.9 58.6 12.7 6.2 0 E 4.2 300 7 31 380 224 3138 36.3 48.5 31.5 5.3 0 F 6.4 302 7 102 730 224 6338 18.3 48.1 26.2 8.5 0 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity. (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. EXAMPLE 20 The procedure of Example 19 was repeated except that the Rh-Re-Mo on gamma-alumina catalyst thus prepared in oxide form was sulfided using the procedure of Example 3 prior to contacting this oxide solids with a butene-gas. After sulfiding, the catalyst, mixed with inerts, was contacted with a butene-l feed employing the conditions set forth above for Example 19, except that a temperature of 2980C was used and the run was continued for 1 hour. At a butene conversion of 44.5%, the following selectivities were observed: methyl ethyl ketone 86.6%, secondary butyl alcohol 3.2%, carbon dioxide 6.5%, and carbon monoxide 0.8%. In addition, secondary-butyl mercaptan selectivity was 1.2%. EXAMPLE 21 Gamma-alumina (30 cc.;12 -20 mesh) was dried using the procedure of Example 1 to a dry weight of 26.6 grams. A calculated amount of ammonium tetrathiomolybdate (6.85 grams of (NH4)2MoS4) was dissolved in 61 cc. of distilled water and 11 cc. of the solution was employed in a first impregnation using the procedure of Example 1, followed by drying under helium at 1250C for 1 hour, and 2500C for 1 hour. Then the solids were allowed to cool to room temperature. The impregnation and drying procedure was then repeated five times, with each subsequent impregnation employing 10 cc. of the above solution. After the sixth such impregnation and drying step, the dried solids, rather than being allowed to cool to room temperature, were calcined by raising the furnace temperature at a rate of about 100C per minute to 350CC. which was maintained for 3 hours, under helium. Then, after cooling of the solids, one-third of the solids was imPrecnated wit a 3.7 cc. aqueous solution containing 0.39 grams of ammonium perrhenate, and-0.20.grams of room trinitrate. After this simultaneous Re/Rh impregnation, the solids were dried over helium at 1250C for 1 hour. Ten cc. of these solids were then mixed with 20 cc. of fused ceramic inerts (12-20 mesh) which was then loaded into the test reactor and sulfided employing the procedure of Example 3 to ensure complete- sulfiding of the catalyst. A series of runs was then conducted using the catayst, employing the conditions set forth in Table XIII. EXAMPLE 22 Employing the procedure of Example 17, 26.5 grams of dried gamma-alumina 12-20 mesh; 100 m2/gm. 92s sequen- tially impregnated with a 10.7 cc. aqueous solution containing 4.64 grams of ammonium paramolybdate, followed by impregnation twice with 10.7 of an aqueous solution containing 1.42 grams of ammonium perrhenate and then by 10.7 cc. of an aqueous solution containing 1.71 grams of rhodium trinitrate. After each impregnation, the fourstep drying and calcining procedure of Example 17 was repeated under air. The resulting catalyst was found to comprise 2.0 wt.% Rh, 7.4 wt.% Re, and 9.5 wt.% Mo, calculated as the respective metal, based on the total weight of the samma-alumina support. This catalyst t10 cc.) was then mixed with 20 cc. of fused ceramic inerts of 12-20 mesh sulfided using the procedure according to Example 3, and tested followinq the procedure of Example 1, and using the conditions set forth in Table XIV, providing the data set forth in that table. TABLE XIII Gas Feed (cc/min.) GHSV(2) % Selectivities Run Time Temp Press. 1- (1) cc/cc/ Butene (3) SBA C4SH No. (hrs) ( C) psig Butene O2/N2 H2O hr) Conv.(%) MEK CO2 CO (4) (5) 1 4.7 350 9.0 60 380 224 3984 5.6 89.0 0 4.8 0.6 0 2 1.9 300 9.0 60 380 224 3984 7.6 88.3 0 3.8 2.6 0 3 1.3 255 9.0 60 380 224 3984 7.0 89.7 0 1.1 5.7 0 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity. (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. TABLE XIV Gas Feed (cc/min.) GHSV(3) % Selectivities Run Time Temp Press. (1) (2) cc/cc/ Butene (4) SBA C4SH No. (hrs) ( C) psig Butene O2/N2 H2O hr) Conv.(%) MEK CO2 CO (5) (6) 1 1.8 300 9.2 60 380 224 3984 4.3 25.3 48.1 11.5 9.0 0 2 3.0 306 9.3 102 730 224 6336 6.1 23.0 48.5 17.6 2.8 0 3 4.0 296 9.2 60 380 224 3984 10.1 44.9 26.0 8.3 0 3.5 4 6.5 306 9.2 60 380 224 3984 11.3 52.3 25.9 7.1 0 3.9 5* 0.6 302 9.2 60 380 224 3984 7.3 36.1 40.5 2.4 0 11.1 (1) Feed = gas mixture containing 85 vol.% butene-1 and 15 vol.% iso-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. (6) Butyl mercaptan. * A separate catalyst charge, which was formed using the preparation used for the catalyst in Runs 1-4, except that a temperature of 375 C was used in the sulfiding/H2 stripping step of Example 3. EXAMPLE 23 The catalyst preparation procedure of Example 17 was repeated employing 12.95 grams of dry gamma-alumina (12-20 mesh; 100 m2/gm.) in two impregnations; the first using a 5.3 cc. aqueous solution containing 1.16 grams of ammonium paramolybdate;and the second using a 5.3 cc. aqueous solution containing 0.35 gram of ammonium perrhenate and 0.13 grams of rhodium trinitrate. After each vacuum impregnation, the inter-stage, four-stage drying/calcining procedure of Example 17 was repeated, under N2 (after the first impregnation) and air for the subsequent impregnation. The resulting oxide catalyst was found to contain O.S wt.% Rh, 1.85 wt.t Re, and 4.75 wt.%-Mo; calcu lated as the respective elements, based on the weight-of the gamma-alumina support. After mixing this oxide catalyst with inerts as in Example 17, the catalyst was subjected to the in stu sulfiding procedure of Example 3 and then tested as in Example 1, providing the data summarized in Table XV. TABLE XV Gas Feed (cc/min.) GHSV(3) % Selectivities Run Time. Temp Press. (1) (2) cc/cc/ Butene (4) SBA C4SH No. (hrs) ( C) psig Butene O2:N2 H2O hr) Conv.(%) MEK CO2 CO (5) (6) 1 26.7 307 8.8 60 380 224 3984 4.6 38.9 42.9 10.7 3.3 0 2 27.3 309 8.7 30 170 224 2568 4.1 50.0 43.2 0 3.8 0 (1) Feed = gas mixture containing 85 vol.% butene-1 and 15 vol.% iso-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. (6) Butyl mercaptan. EXAMPLE 24 The catalyst preparation procedure of Example 23 was repeated except that 12.9 gm of the dry gamma-alumina was used and the stepwise impregnation employed 6.2 cc. of an aqueous solution containing ammonium paramolybdate (2.25 grams), followed by 5.5 cc. of an aqueous solution containing 0.35 gram of ammonium perrhenate, and then by a 5.0 cc. of an aqueous solution containing 0.18 gram of rhodium trinitrate, again using the inter-stage, fourstep drying/calcining procedure described in Example 17. The resulting oxide catalyst was found.to contain 0.5 wt.% Rh, 1.8 wt.% Re, and 9.5 wt.% Mo, calculated as the elements, based on the weight of the gamma-alumina support. This oxide catalyst was then mixed with inerts as in Example 17, sulfided as in Example 3, and employed in a test reactor with a butene-feed, using the procedure of Example 1. The data obtained are set forth in Run 1 of Table XVI. The catalyst in the reactor was then subjected to a sulfiding, using the procedure of Example 3 and subjected to three additional runs which are summarized in Table XVI. TABLE XVI Gas Feed (cc/min.) GHSV(2) % Selectivities Run Time Temp. Press. 1- (1) cc/cc/ Butene (3) SBA C4SH No. (hrs) ( C) psig Butene O2/N2 H2O hr) Conv.(%) MEK CO2 CO (4) (5) 1 1.0 322 9.0 60 380 224 3984 5.6 77.6 15.9 4.5 0 0 2 1.0 292 8.8 60 380 224 3984 8.8 59.6 23.9 6.5 0 1.4 3 1.3 298 8.8 60 380 224 3984 8.8 60.6 23.9 6.5 0 1.2 4 3.7 392 9.0 60 380 224 3984 13.8 66.6 18.8 6.3 0 1.9 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity. (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 25 The catalyst prepartion procedure of Example 17 was repeated except that the dried support comprised 11.4 grams of dry gamma-alumina (12-20 mesh; 200 m2/gm surface area; 0.50 cc/gm. pore volume; Strem Chemical). The catalyst thus-produced contained the same loading of rhodium, rhenium and molybdenum employed in the catalyst of '1e 17. After mixing 10 cc. of this oxide catalyst with 20 cc. of fused ceramic inerts (12-20 mesh), the catalyst was tested 25 in Example 17 at 3020C and gas inlet pressure of 9.0 psig for 0.5 hour, using a gas feed comprising 60 cc./min. butene-l, 380 cc./min. O°N2 (10:96 vol:vol gas mixture) and 224 cc./min. of water vapor, for a total gas hourly space velocity of 3,984 cc/cc/min. at a 8.0% butene conversion, the following selectivities were ob served methyl ethyl ketone 55.6%, secondary butyl alcohol 11.7%, carbon dioxide 16.9% and carbon monoxide 3.2%. In addition, 0.58 of butyl mercaptan was detected. This catalyst was then subjected to an in situ sulfiding using the procedure of Example 3, and then tested in a separate run at 3000C and a gas inlet pressure of 8.8 psig for 1.5 hours, using the same gas feed composition. At a butene conversion of 11.0%, the following selectivities were observed methyl ethyl ketone 49.7%, carbon dioxide 23.4%, carbon monoxide 4.58 and butyl mercaptan 3.8%. No secondary butyl alcohol was detected. EXAMPLE 26 The catalyst preparation procedure of Example 21 was repeated except that 15 cc. of the dried gamma-alumina solids were subjected to ten successive impregnations, each using 5.8 cc. of an aqueous solution containing 0.33 grams of ammonium tetrathiomolybdate, with each such impregnation being followed by drying at 1250C for 1 hour in a vacuum oven (at u pressure of -30 inches of mercury). After the tenth impregnation, the solids were dried in a Linberg furnace at 2500C under helium for 2 hours, followed by allowing the solids to cool, and a vacuum impregnation using 6.0 cc. of an aqueous solution containing 0.694 grams of ammonium perrhenate and 0.36 gram of.Rh(-N03)3. After drying of these solids in the vacuum oven at 1250C for 1 hour, the solids were dried in the Linberg furnace at 2500C for 2 hours under helium and the solids were then mixed with inerts and sulfided using the procedure of Example 3. A long-term test of these sulfided catalysts, which was found to comprise 1.08 wt.% Rh, 3.7 wt.% Re, and 9.5 wt.% Mo, was then made using the procedure of Example 1. The results were set forth in-Table XVII. TABLE XVII Gas Feed (cc/min.) % Selectivities Run Time Temp. Press. 1- (1) GHSV Butene (3) SBA C4SH No. (hrs) ( C) psig Butene O2/N2 H2O (2) Conv.(%) MEK CO2 CO (4) (5) 1 1.5 296 63 8.5 380 224 3984 27.8 81.6 12.7 0.9 2.5 0.3 2 2.5 310 63 8.5 380 224 3984 28.6 75.9 12.0 2.8 3.9 0.5 3 3.0 301 63 8.5 380 224 3984 30.1 70.4 11.2 2.2 4.1 0.4 4 6.0 298 63 8.5 380 224 3984 27.6 72.5 13.5 2.5 4.3 0.3 5 6.5 296 63 8.5 380 224 3984 27.6 72.5 13.0 2.5 3.2 0.5 6 7.5 300 62 8.5 380 224 3984 27.2 76.5 12.0 2.4 2.4 0.4 7 10.0 308 62 8.5 380 224 3984 27.2 80.0 11.1 1.4 3.4 1.2 8 22.8 299 62 8.5 380 224 3984 31.1 76.6 10.5 1.8 6.6 0 9 23.3 304 62 8.5 380 224 3984 28.0 74.0 11.8 1.9 6.7 0 (1) Fed as 10 vol.% O2 in N2. (2) Total gas hourly space velocity. (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 27 The multi-step impregnation procedure of Example 17 above was repeated except that the support in this experiment comprised 5.37 grams (after the drying step) of silicaalumina (Davison Chemical Company, silica-alumina No. 979: 86.0% silica, 13% alumina; 400 m2/gm.; 1.16 cc./gm. pore volume; 12-20 mesh. In the first impregnation, a 6.2 cc. aqueous solution containing 0.94 gram of ammonium paramolybdate was used, followed by the four-step drying/calcining procedure of Example 17. The second impregnation employed a 6.2 cc. aqueous solution containing 0.29 gram of ammonium perrhenate and the third impregnation used 6.2 cc. of an aqueous solution containing 0.15 gram of ammonium nitrate. The same drying/calcining procedure was also used after each of the last two impregnations. Ten, cc. of the above oxide solids, which were found to contain 1.08 wt.% Rh, 3.7 wt.% Re and 9.5 wt.% Mo, calculated as the respective metals, based on the weight of the total silica-alunina support, was mixed with 20 cc. of 12-20 mesh fused ceramic inerts and charged to the reactor for testing as in Example 1. The data thereby obtained are set forth in Runs 1 and 2 of Table XVIII. At the end of Run 2, the catalyst was subjected to sulfiding employing the procedure of Example 3, except that the passage of the H2S gas was continued for 1 hour and the hydrogen stripping step was carried out for only one-half hour. At the end of this time, the butene-feed was resumed and the catalyst employed in Run 3 of Table XVIII. TABLE XVIII Gas Feed (cc/min.) % Selectivities Run Time Temp. Press. (1) (2) GHSV Butene (4) SBA C4SH No. (hrs) ( C) psig Butene O2/N2 H2O (3) Conv.(%) MEK CO2 CO (5) (6) 1 0.6 296 9.2 60 380 224 3984 7.1 13.2 32.4 29.4 3.4 0.3 2 2.0 295 9.2 102 730 224 6336 8.0 12.2 26.3 42.5 2.1 0.8 3 3.0 304 9.2 60 380 224 3984 4.9 13.6 31.7 38.3 2.0 1.0 (1) Feed = gas mixture containing 85 vol.% butene-1 and 15 vol.% iso-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. (6) Butyl mercaptan. EXAMPLE 28 The procedure of Example 27 was repeated except that the support comprised 5.34 grams (prepared by drying 15.0 cc. of support at 5000C for 3 hours in air) of silica gel (Strem Chemical; 12-20 mesh; 340 m2/gm.; 1.18 cc./gm, pore volume). The sequential impregnation employed the following amounts of the indicated solutions; 6.3 cc. of an aqueous solution containing 0.93 gram of ammonium paramolybdate; 6.3 cc. of an aqueous solution containing 0.29 gram of ammonium perrhenate; and 6.3 cc. of an aqueous solution containing 9.16 gram of rhodium trinitrate. After each impregnation, the four-step drying/calcining procedure of Example 17 was repeated. The resulting oxide catalyst was found to contain l.O wt,% Rh, 3.7 wt,S Re, and 9.5 wt.% Mo, calculated as the metals, based on the weight of the silica gel support. Ten cc. of this oxide catalyst was then well mixed with 20 cc. of 12-20 mesh fused ceramic inerts and charged to the reactor and sulfided as in Example 3 followed by testing using the procedure of Example 1. The reactor was maintained at a temperature of 3100C and a gas inlet pressure of 8.8 psig, for 0.8 hour. The gas feed to the reactor comprised 102 cc./min. of a gas mixture containing 85 vol.% butene-l, 15 vol.% n-butane, 730 cc./min. of an oxygen-containing gas mixture (10 vol.% oxygen in nitrogen) and 224 cc./min. of water vapor, for a total gas hourly space velocity of 6336 cc/cc/hr. At a butene conversion of 5.5%, methyl ethyl ketone was formed only in a selectivity of 0.7% and carbon dioxide selectivity was observed to be 16.7%, with a 63.3% selectivity to carbon monoxide. In view of the low ketone selectivity obtained under the above conditions, silica gel is not a preferred catalyst support for use in the practice of this invention. EXAMPLE 29 Using the procedure as described above for Example l(a), 15 cc:of the gamma-alumina (12-20 mesh) was dried in air at 5000C for 3 hours, to provide a dry weight of 13.4 grams. Ammonium tungstate (1.753 grams, (SH4)1oW1204.5H20) was dissolved in water to make a 27 cc. solution, which was observed to contain some undissolved solids. In a first impregnation, approximately 5.3 cc. of this aqueous solution was impregnated onto the dried solid, after which the impregnated solids were dried in air at 1250C for 1 hour followed by 2500C for 1 hour. This procedure was repeated 3 times, and a total of 0;36 gram of insoluble ammonium tungstate was recovered following the last impregnation, to provide a net of 1.39 grams of ammonium tungstate impregnated, onto the support. The above two-step drying procedure was used after each of the successive impregna- tions, except that after the fifth such mpregnation the catalyst was additionally dried at 3500C for 1 hour, followed by calcining at 500 C for 3 hours, in air. In a subsequent impregnation, 5.4 cc. of an aqueous solution containing 0.58 grams of ammonium perrhenate were impregnated onto the catalyst, followed by drying at 1250C for 1 hour, 2020C for 1 hour, and. 3500C for 1 hour, and calcining at 5000C'for 3 hours, in air. The resulting oxide catalyst was found to contain 3.0 wt.% rhenium and 7.5 wt.% tungsten, calculated as the elements, based on the weight cf the catalyst support. Ten cc. of -the resulting catalyst was then mixed with 20 cc. of fused ceramic inerts (1220 mesh) and tested as in Example 3, at the conditions suiian2rized in Table XIX, Run 1 below. The oxide catalyst used in Run 1 was then sul fizzed using the procedure of Example 3, after which the sulfided catalyst was employed in Run 2; using the conditions described in Table XIX. TABLE XIX Gas Feed (cc/min.) % Selectivities Run Time Temp. Press. (1) (2) GHSV Butene (4) SBA No. (hrs) ( C) psig Butene O2/N2 H2O (3) Conv.(%) MEK CO2 CO (5) Re-W Oxide 1 2.3 313 9.4 60 380 224 3984 5.1 51.0 3.1 4.7 34.5 Re-W Sulfide 2 2.5 299 9.7 60 380 224 3984 5.1 40.5 3.8 7.7 31.0 (1) Feed = Gas mixture containing 85 vol.% butene-1 and 15 vol.% iso-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. EXAMPLE 30 The catalyst preparation and sulfiding procedure of Example 15 was repeated (except that no Rh salt was employed), using 37 cc of gamma-alumina and 12.0 cc of an aqueous solution containing 5.24 grams of ammonium para- molybdate and 12.0 cc of an aqueous solution containing 1.63 grams of ammonium perrhenate, to prepare a sulfide Re-Mo catalyst, supported on gamma-alumina, comprising 3.7 wt.% Re and 9.5 wt.% Mo, calculated as the respective elements. The catalyst was then used in a series of runs over extended time periods. The data thereby obtained is set forth in Table XX below. TABLE XX Gas Feed (cc/min.) % Selectivities Run Time Temp. Press. (1) (1) (2) GHSV Butene (4) SBA No. (hrs) ( C) (psig) Butene O2/N2 N2 H2O (3) Conv.(%) MEK CO2 CO (5) Others 1 10.7 372 8.0 60 60 320 224 3984 2.5 69.7 3.8 0 0.5 26.0 2 11.9 384 9.0 60 30 350 224 3984 2.8 90.2 3.0 0 0.4 6.4 3 14.0 384 9.0 60 30 0 224 1884 2.3 91.1 4.8 0 0.8 2.0 (1) Feed = Gas mixture containing 85 vol.% butene and 15 vol.% iso-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. EXAMPLE 31 The procedure of Example 20 was repeated employing the sulfided Rh-Re-Mo on gamma-alumina catalyst of that example, except that the feed olefin comprised cyclohexene and the conditions of the test were as identified in Table XXI below. A series of runs were conducted in which the reaction temperature was varied, indicating the higher selectivities of cyclohexanone obtained at temperatures of less than about 2200C. TABLE XXI Gas Feed (cc/min.) Cyclo- % Selectivities Run Time Temp. Press. Cyclo- Air GHSV hexene Cyclo- Cyclo No. (hrs) ( C) psig hexene (1) N2 H2O (2) Conv.(%) hexanone CO2 Hexanol 1 1.75 267 18 88 173 0 231 2952 3.0 2-5 > 80 N.D. 2 0.25 216 18 60 83 83 216 2652 0.51 33.3 N.D. 11.8 3 0.50 145 18 54 83 83 220 2640 1.65 12.7 N.D. 63.6 4 0.75 153 18 84 83 83 212 2772 0.64 9.4 N.D. 35.9 5 1.00 150 18 82 83 83 220 2808 0.37 8.1 N.D. 21.6 6 1.25 162 18 70 83 83 187 2538 0.32 6.3 N.D. 18.8 7 1.58 205 75 58 83 83 183 2442 13.6 7.9 41.5 1.3 8 1.83 196 75 77 83 83 332 3450 14.0 8.1 40.3 0.9 9 2.08 210 75 76 83 83 257 2994 25.1 19.0 22.5 0.6 (1) At 10 vol.% O2 (air diluted with N2). (2) Gas hourly space velocity (cc/cc/hr.). (N. D. = Not determined) EXAMPLE 32 The procedure of Example 31 as repeated using the Rh-Re-Mo sulfided catalyst of that example, except that the olef in feed comprised hexene-1, and the conditions employed were as summarized in Table XXII below. TABLE XXII Gas Feed (cc/min.) % Selectivities Run Time Temp. Press. Air n-hexene GHSV n-hexene hexanone unindentified No. (hrs) ( C) psig (1) H2O -1 (2) Conv.(%) CO2 -2 (3) 1 .25 317 18 158 158 64 2280 12.6 34.0 0.6 60.5 2 0.75 304 18 158 149 82 2334 9.1 47.1 0.5 49.8 3 1.00 303 18 158 158 60 2256 9.3 46.3 0.9 50.1 (1) Air contains 20 vol.% oxygen. (2) Gas hourly space velocity (cc/cc/hr.). (3) An unidentified major peak, eluting prior to hexanone-2 on the GC trace, was observed, and is believed to have contained significant amounts of hexanone-3, formed from a large amount of hexene-2 and hexene-3 which result from the rapid thermal equilibrium established between the isomers of hexene in the reactor. EXAMPLE 33 CATALYST PREPARATION (a) Vacuum Impregnation Gamma-alumina (30 cc.; 12-20 mesh; 100 m2/gm surface area; 0.45 cc./gm pore volume; Aifa Products) was dried in air in a Linberg furnace at 500'C for 3 hours to give a dry weight of 26.4 grams. Ammonium paramolybdate f(NH4)6M07O24.4H20)0 (4.63 grams) was dissolved in distilled water to form a 10.6 cc. aqueous solution and transferred into a 60 cc. dropping funnel. The catalyst support was placed in a 125 cc. glass filtering flask equipped with a side arm for pulling a vacuum, and the filtering flask was attached to a dropping funnel using a rubber stopper. After evacuation to a pressure of -15 in Hg, the ammonium paramolybdate solution was added dropwise to the catalyst sup port to achieve complete wetness. The impregnated wet catalyst was placed in a stainless steel gauze boat and dried in air at 1250C for 1 hour, 250'C for 1 hour and 3500C for 1 hour, and finally calcined in air by raising the furnace temperature to 500 C (at a rate of about 10'C/min.), which was maintained for 3 hours. After cooling to room temperature, the solids were then impregnated with 10.3'cc. of an aqueous solution containing 1.41 grams of ammonium perrhenate, after which the same four-step drying and calcining procedure was used. Finally, these solids were impregnated with 2 10.3 cc. aqueous solution containing 0.57 grams of Pd(N03)2, again followed by the same four-step drying and calcining procedure. The thus-produced solids were found to comprise mixed oxides of palladium, rhenium and molybdenum and to contain 1.0 wt,b Pd, 3.7 wt.S Re, and 9.5 wt.% Mo, calculated as the respective elements, based on the weight of the catalyst support. (b) Sulfiding Procedure Ten cc. of the foregoing oxide catalyst and 20 cc. of fused ceramic inerts (12-20 mesh) were well mixed and loaded into a test reactor which comprised a 24-inch (0..38 inch ID) stainless steel tubular reactor equipped with gas inlets and gas outlets at opposing ends of the tubular reactor. The reactor was then heated to a temperature of 325it (which was maintained by means of electric heating tape and a Gardsman temperature control). Temperatures in the reactor were determined by means of a thermocouple positioned in the center of the catalyst bed. A gas mixture of hydrogen sulfide (190 cc./min.; charged as 6 vol.% H2S in N2) and H2 (230 cc./min.) was charged to the reactor at a gas inlet pressure of 9 psig, for 3 hours, to convert the oxide catalyst to the sulfide form. The resulting solids were then contacted under the same flow conditions with H2 (520 cc./min.) to strip out any absorbed, unreacted.H2. The catalyst was then determined to comprise a mixture of rhenium sulfide, palladium sulfide, and molybdenum sulfide, and to contain 1.0% Pd, 3.7% Re and 9.5% Mo, calculated as the respective elements, based on the total weight of the catalyst support. EXAMPLE 3A FOR COMPARISON To determine the performance of the catalyst prepared in Example 33(b) in the presence of an O2-containing feed, a gaseous mixture of the following composition, containing butene-1, oxygen, nitrogen and water vapor was passed to the reactor described in Example 1(b): 380 cc./min. of a 10:90 vol:vol mixture of oxygen:nitrogen; 60 cc./min. of a gas mixture containing 85 vol.% butene-1 and 15 vol.% iso-butane; and 224 cc. per minute of water vapor. The total gas hourly space velocity of the gaseous mixture through this reactor was 3984 cc/cc/hr. A gaseous inlet pressure of 9.7 psig and a temperature of 310-C was employed throughout the reaction (1.2 hrs.). A gaseous effluent was continuously withdrawn from the reactor and was sampled and analyzed by means of an on-line gas chromatograph. After achieving steady conditions, methyl -ehtyl ketone was found to have been formed in a selectivity of about 58,3% at a butene conversion of 6.5%. The following by-product selectivities were observed: 11.3% CO2, 5.0s CO, 5.3% secondary butyl alcohol and 14.0% secondary butyl mercaptan. EXAMPLE 35 In a series of separate runs, the Re-Mo-Pd sulfide catalyst used in Comparative Example 34 was contacted with a butene feed under the conditions indicated in Table:-ymII below. except that no oxygen was passed to the reactor. The data thereby obtained are set forth in Table I. TABLE XXIII Gas Feed (cc/min.) % Selectivities to: Run Time Temp. Press. Butene GHSV Butene MEK SBA C4SH Total Product No. (hrs) ( C) psig (1) H2O N2 (2) Conv.(%) (3) CO2 CO (4) (5) (MEK + SBA) 1 4.0 304 9.2 60 224 380 3984 1.8 93.1 0 0 6.3 0 99.4 2 6.4 297 9.4 31 224 170 2550 2.5 95.1 0 0 4.9 0 100.0 3 10.1 365 9.2 60 224 380 3904 2.0 97.6 0 0 2.3 0 99.9 4 12.0 367 9.5 104 224 730 6336 2.4 97.3 0 0 1.9 0 99.2 5 12.8 371 9.7 60 224 0 1704 2.8 95.0 0 0 4.2 0 99.2 (1) Feed = gas mixture containing 85 vol.% butene-1 and 15 vol.% n-butane. (2) Total gas hourly space velocity. (3) Methyl ethyl ketone. (4) Secondary butyl alcohol. (5) Butyl mercaptan. EXAMPLE 36 Fifteen cc. of the palladium-rhenium-molybdenum oxide catalyst prepared in Example 33 (a) was further vacuum impregnated using the procedure of Example 1 (a) with a 5.1 cc. aqueous solution containing 0.069 gram of sodium nitrate, followed by the four-step drying and calcining procedure employed in Example 33(a), The resulting solids were found to additionally contain 0.1 wt.% Na, calculated as the element, based on the weight of the total catalyst support, in addition to the 1.0% Pd, 3.7% Re, and 9.5% Mo. This catalyst was then mixed with inerts and sulfided using the procedure set forth above in Example 33 (b), and the resulting sulfided catalyst was then employed in a'series of runs following the procedure of Comparative Example,34 under the conditions summarized in XXIV below. TABLE XXIV Gas Feed (cc/min.) % Selectivities to: Run Time Temp. Press. (1) O2/N2 GHSV Butene MEK SBA C4SH Total Product No. (hrs) ( C) psig 1-Butene (2) H2O N2 (3) Conv.(%) (4) CO2 CO (4) (5) (MEK + SBA) 1 0.7 304 9.4 60 380 224 0 3984 10.8 39.8 13.5 14.6 2.8 1.4 42.6 2 3.2 290 9.7 60 0 224 380 3984 1.6 92.2 0 0 7.8 0 100.0 3 6.6 294 9.7 104 0 224 730 6336 2.2 95.4 0 0 4.6 0 100.0 4 12.7 372 7.2 60 0 224 0 1704 5.2 96.8 0 0 2.4 0 99.2 (1) Feed = gas mixture containing 85 vol.% butene-1, 15 vol.% n-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. (6) Butyl mercaptan. EXAMPLE 37 Following the procedure ot Example 33(a), 26.4 grams of dry gamma-alumina was sequentially impregnated with Mo (using 10.6 cc. of an aqueous solution containing 4.62 grams of ammonium paramolybdate), Re (using 10.3 cc. of an aqueous solution containing 1.42 grams of ammonium perrhenate), and finally by Rh (using 10.3 cc. of an aqueous solution containing 0.37 gram of rhodium trinitrate). After each impregnation, the solids are dried under air at 125µC for 1 hour, 25 C for 1 hour, and 350 C for 1 hour, and then calcined under air at 500iC for 3 hours. The resulting oxide catalyst was found to comprise O.S wt.% Rh, 3.7 wt.% Re, and 9.7 wt.% Mo, calculated as a respective element, based on the total weight of the support. The oxide catalyst was mixed with inerts and sulfided using the procedure of Example 33(b), and the resulting sulfided catalyst was employed in a series of runs following the procedure of Comparative Example 3E using conditions set forth in Table XXV. TABLE XXV Gas Feed (cc/min.) % Selectivities Run Time Temp Press. (1) O2/N2 GHSV Butene MEK SBA C2SH No. (hrs) ( C) psig 1-Butene (2) H2O N2 (3) Conv.(%) (4) CO2 CO (5) (6) 1 0.6 315 9.0 60 380 224 0 3984 12.0 65.3 22.7 3.4 1.3 4.1 2 2.7 301 9.5 104 730 224 0 6336 14.0 56.5 20.7 13.0 1.1 1.9 3 4.2 310 9.2 60 0 224 380 3984 2.3 96.9 0 0 1.1 2.0 4 6.2 306 9.4 104 0 224 730 6336 3.5 98.2 0 0 0 1.8 5 6.8 301 9.0 31 0 224 170 2550 3.8 90.2 0 0 1.0 0.9 6 7.8 376 9.4 31 0 224 170 2550 8.6 93.5 0 0 1.1 5.0 7 8.3 375 9.4 60 0 224 380 3984 6.4 98.0 0 0 0 2.0 8 8.8 375 9.4 104 0 224 730 6336 6.5 97.1 0 0 0 2.9 9 12.8 386 9.1 60 0 224 0 1704 12.6 98.4 0 0 0.8 0.8 (1) Feed = gas mixture containing 85 vol. % butene-1, 15 vol.% n-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. (6) Butyl mercaptan. EXAMPLE 3 8 The catalyst preparation procedure of Example 37 is repeated except that the catalyst solids, following the last calcining step, were then impregnated with 10.3 cc. of an aqueous solution containing 0.11 gram of sodium nitrate. These impregnated solids, containing 0.1 wt.% Na, 0.5 wt.% Rh, 3.7 wt.% Re and 9.5 wt.% Mo (calculated as metals, based on support) were then dried and calcined in air using the procedure of Example 37,and mixed with inerts and sulfided in the reactor employing the procedure of Example 33(b). Thereafter, the sulfided catalyst was used in a series of runs using the procedure of Comparative Example 34. The data thereby obtained are set forth in Table XXVI. TABLE XXVI Gas Feed (cc/min.) % Selectivities Run Time Temp Press. (1) O2/N2 GHSV Butene MEK SBA C2SH No. (hrs) ( C) psig 1-Butene (2) H2O N2 (3) Conv.(%) (4) CO2 CO (5) (6) 1 0.7 285 9.1 60 380 224 0 3984 11.9 60.2 28.8 0 0.9 4.0 2 1.8 295 9.2 104 730 224 0 6336 14.5 46.3 22.8 12.0 0.3 4.6 3 2.4 294 9.1 60 0 224 380 3984 2.2 96.3 0 0 0 3.7 4 7.5 300 9.0 31 0 224 170 2550 6.3 95.4 0 0 0.7 3.9 5 9.5 357 9.0 31 0 224 170 2550 11.0 95.7 0 0 1.1 3.2 6 11.8 375 9.1 60 0 224 380 3984 2.9 97.3 0 0 1.0 1.8 (1) Feed = gas mixture containing 85 vol. % butene-1, 15 vol.% n-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. (6) Butyl mercaptan. EXAMPLE 30 The catalyst preparation procedure of Example 33 (a) was repeated employing 12.95 grams of the dry gamma-alumina support, and two impregnations: the first using a 5.3 cc. aqueous solution containing 1.16 grams of ammonium paramolybdate; and the second using a 5.3 cc. aqueous solution containing 0.35 gram of ammonium perrhenate and 0.18 gram of rhodium trinitrate, in that order. After each vacuum impregnation the inter-stage, four-step drying/calcining procedure of Example 33(a) was repeated, under N2 after the first impregnation and under air thereafter. The resulting oxide catalyst was found to contain 05- wt.% Rh, 0.85 wt.% Re, and 4.75 wt.% Mo, calculated as the respective elements, based on the weight of the gamma-alumina support. -After mixing this oxide catalyst with inerts as in Example 33(b), the catalyst was subjected to the in situ sulfiding procedure of Example 33(b) and then tested as in Example providing the data summarized in Table XXVII, TABLE XXVII Gas Feed (cc/min.) % Selectivities Run Time Temp Press. (1) O2/N2 GHSV Butene MEK SBA C2SH No. (hrs) ( C) psig 1-Butene (2) H2O N2 (3) Conv.(%) (4) CO2 CO2 (5) (6) 1 26.7 307 8.8 60 380 224 0 3984 4.5 38.9 42.9 10.7 3.3 0 2 27.3 309 8.7 30 170 224 0 2568 4.1 50.0 43.2 0 3.8 0 3 24.0 303 8.8 60 0 224 380 3984 1.8 92.2 0 0 7.8 0 4 24.6 307 8.8 60 0 224 380 3984 2.0 92.4 0 0 7.6 0 5 30.4 304 9.1 102 0 224 730 6336 1.6 96.1 0 0 3.1 0 (1) Feed = gas mixture containing 85 vol. % butene-1, 15 vol.% n-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. (6) Butyl mercaptan. EXAMPLE 40 Using the procedure as described above for Example 33(a), 15 cc. of the gamma-alumina ( 12-20 mesh) was dried in air at 5000C for 3 hours, to provide a dry weight of 13.4 grams. Ammonium tungstate (1.753 grams, (NH4)10W1204.5H2O) was dissolved in water to make a 27 cc. solution, which was observed to contain some undissolved solids. In a first impregnation, approximately 5.3 cc. of-this aqueous solution was impregnated onto the dried solid, after which the impregnated solids were dried in air at 125 C for 1 hour followed by 250*C for 1 hour. This procedure was repeated 3 times, and a total of 0.36 gram of insoluble ammonium tungstate was recovered following the last impregnation, to provide a net of 1.39 grams of- ammonium tungstate 'impregnated onto the support. The above two-step drying procedure was used after each of the successive impregnatiSons, except that after the fifth such impregnation the catalyst was additionally dried at 3500C for 1 hour, followed by calcining at SOO'C for 3 hours, in air. In a subsequent impregnation, 5.4 cc. of an aqueous solution containing 0.58 gram of ammonium perrhenate were impregnated onto the catalyst, followed by drying at 125'C for 1 hour, 202 C for t hour, and 3500C for 1 hour, and calcining at 500'C for 3 hours, in air. The resulting oxide catalyst was found to contain 3.0 wt.% rhenium and 7.5 wt.% tungsten, calculated as the elements, based on the weight of the catalyst support. Ten cc. of the resulting catalyst was then mixed with 20 cc. of fused ceramic inerts (12-20 mesh) and tested as in Example 35r at the conditions summarized in Table VI,- Run 1 below. The oxide catalyst used in Run 1 was then sulfided using the procedure of Example 33(b), after which the sulfided catalyst was employed in Runs 2-4, using the conditions described in Table XwIII. TABLE XXVIII Gas Feed (cc/min.) % Selectivities Run Time Temp Press. (1) O2/N2 GHSV Butene MEK SBA No. (hrs) ( C) psig 1-Butene (2) H2O N2 (3) Conv.(%) (4) CO2 CO (5) Rh-W Oxide 1 2.3 313 9.4 60 300 224 0 3984 5.0 51.0 3.1 4.7 34.5 Re-W Sulfide 2 2.5 299 9.7 60 380 224 0 3984 2.1 40.5 3.8 7.7 31.0 3 3.5 306 9.5 60 0 224 380 3984 1.5 53.1 0 0 46.9 4 4.0 374 9.7 60 0 224 380 3984 3.1 88.9 0 0 9.2 (1) Feed = gas mixture containing 85 vol. % butene-1, 15 vol.% n-butane. (2) Fed as 10 vol.% O2 in N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. EwA;tIP LE 41 The catalyst preparation and sulfiding procedure of Example 37 was repeated (except that the reactor was loaded with 30 cc. of the oxide catalyst prior to the in situ sulfiding step, and no solid inerts were admixed therewith), to prepare a sulfide catalyst, supported on gamma-alumina, comprising 0.5 wt.% Rh, 3.7 wt.% Re and 9.5 wt.% Mo, calculated as the respective element. The catalyst was then used in a first series of runs, using N2 in the gas feed (Runs 1-4) and then was used in another series of runs (Runs 5-8) in which no N2 was fed to the reactor. The data thereby obtained is set forth in Table XXIX below. These runs indicate the excellent stability and activity properties of the ,catalysts of this invention. TABLE XXIX Gas Feed (cc/min.) % Selectivities Run Time Temp Press. Butene N2 GHSV Butene MEK SBA No. (hrs) ( C) psig (1) (2) H2O (3) Conv.(%) (4) CO2 CO (5) 1 11.5 357 20.6 60 380 224 3984 4.1 97.0 0 0 0.7 2 12.1 370 8.7 60 380 224 3984 4.3 97.0 0 0 0.5 3 12.8 359 8.9 60 380 224 3984 3.8 98.1 0 0 0.5 4 13.3 368 9.0 60 380 224 3984 3.9 96.7 0 0 0.8 5 19.6 367 8.0 60 0 224 1704 4.4 90.8 0 0 0.7 6 20.4 370 8.0 60 0 224 1704 4.3 98.6 0 0 1.1 7 20.9 366 7.9 60 0 224 1704 4.5 96.6 0 0 2.7 8 22.1 367 8.9 60 0 224 1704 4.4 98.4 0 0 1.2 (1) Feed = gas mixture containing 85 vol. % butene-1, 15 vol.% n-butane. (2) Fed as N2. (3) Total gas hourly space velocity. (4) Methyl ethyl ketone. (5) Secondary butyl alcohol. EXA;IPLE 4 2 Following the procedure of Example 33(a), 35 cc. of dried gamma-alumina (Alfa Product) was sequentially impregnated with Mo (using 12.0 cc. of aqueous solution containing 5.2 grams of ammonium permolybdate), Re (using 11.9 cc. of an aqueous solution containing 1.64 grams of ammonium perrhenate) and finally by Rh (using 11.9 cc. of an aqueous solution containing 0.422 gram of rhodium trinitrate). After each impregnation, the solids are dried under air and then calcined, using the procedure of Example .3(a). The resulting oxide catalyst was found to comprise 0.5 wt.% Rh, 3.7 wt.% Re, and 9.7 wt.% Mo, calculated as the respective elements, based on the total weight of the support. The oxide catalyst was -then sulfided using the procedure of Example 33(b), except that the catalyst was not mixed with inerts (instead, 30 cc. of the oxide catalyst was placed in the vessel for sulfiding), and except that the sulfiding step was carried out for a period of 9.0 hours. The resulting sulfided catalysts was employed in a series of runs following the procedure of Comparative Example 34. using conditions set forth in Table XXX. SXA:4PLE 43 The catalyst preparation procedure of Example 4L was repeated employing 45 cc. of the dried gamma-alumina (Alfa Product) which was sequentially impregnated with 15.1 cc. of an aqueous solution containing 6.58 grams of ammonium permolbdate, 15.1 cc. of an aqueous solution containing 2.05 gram of ammonium perrhenate and 15.1 cc. of an aqueous solution containing 0.534 gram rhodium trinitrate. The drying and calcining procedure of Example 42 was used after each impregnation. Thereafter, the dried catalyst was subjected to, an additional impregnation, sequentially, with 13.2 cc. of an aqueous solution containing 1.77 grams of ammonium perrhenate followed by 12.5 cc. of an aqueous solution containing 1.46 grams of rhodium trinitrate. Again,. the drying and calcining procedure of Example 42 was formed after each impregnation. The resulting oxide catalyst was found to comprise 2.1 wit.% Rh, 7.4 wt.% Re and 9.5 wit.% Mo. Thirty cc. of this catalyst was then sulfided using the procedure of Example 42 and employed in a series of runs following the procedure of Comparative Example 3e using the conditions set forth in Table XXX. TABLE XXX Gas Feed (cc/min.) % Selectivities Run Time Temp Press. Butene GHSV Butene No. (hrs) ( C) psig (1) H2O N2 (2) Conv.(%) MEK CO2 CO SBA Others 43A 3.0 375 9.3 60 224 380 1328 5.1 95.5 0 0 0.7 3.8 43B 8.0 375 9.0 60 224 60 688 5.1 96.7 0 0 0.7 2.6 43C 14.0 375 9.0 60 224 60 688 3.2 97.1 0 0 0.5 2.3 44A 3.0 300 9.6 60 224 60 688 3.7 98.3 0 0 1.1 0.7 44B 6.1 375 9.6 60 224 60 688 6.5 95.9 0 0 0.8 3.3 44C 9.8 375 9.6 30 224 60 668 8.4 95.1 0 0 0.7 4.2 44D 13.5 375 9.3 30 224 0 508 7.6 98.4 0 0 0.5 1.1 44E 18.9 375 9.9 30 224 0 508 6.9 96.6 0 0 0.6 2.8 (1) Feed = gas mixture containing 85 vol. % butene-1, 15 vol.% iso-butane. (2) Gas hourly space velocity (cc feed/cc catalyst/hour). EXAMPLE 44 Following the catalyst preparation procedure of Example 42, 35 cc. of dried gamma-alumina (UCI-L-1278) was sequentially impregnated with 14.0 cc. of an aqueous solution containing 3.93 grams of ammonium permolybdate, 13.5 cc. of an aqueous solution containing 1.214 grams of ammonium perrhenate, 13.5 cc. of an aqueous solution containing 1.17 grams of ammonium perrhenate and finally by 13.5 cc. of an aqueous solution containing 1.262 grams of rhodium trinitrate. The resulting oxide catalyst, after the repetitive air drying and calcining after each impregnation, was found to comprise 2.0 wt.% Rh, 7.4 wt.% Re and 9.5 wit,96 Mo. This oxide catalyst was then sulfided using the conditions of Example 42 (30 cc. of catalyst; no inerts, 9 hours) and the trimetallic sulfide catalyst was then employed in a series of runs using the conditions set forth in Table XXXI and following the procedure of Comparative Example 34. EXAMPLE 45 The catalyst. preparation procedure of Example 42 was repeated employing 35 cc. of dried gamma-alumina (Alfa Product) and sequential impregnation, followed by intermediate air drying and calcining, using impregnation with 12.0 cc. of an aqueous solution containing 5.25 grams of ammonium permolybdate, 12.0 cc. of an aqueous solution containing 1.61 grams of ammonium perrhenate and 12.0 cc. of an aqueous solution containing 0.837 gram of ammonium trinitrate. The resulting oxide catalyst was found to comprise 1.0 wt.% Rh, 3.7 wit.8 Re, and 9.5 wit.% Mo. This' oxide catalyst was then sulfided using the procedure of Example .42 (30 cc. catalyst, no inerts, 9 hours), and the sulfided trimetallic catalyst was then employed in a series of runs using the conditions set forth below in Table XXXI following the procedure of Comparative Example 34. TABLE XXXI Gas Feed (cc/min.) % Selectivities Run Time Temp Press. Butene GHSV Butene No. (hrs) ( C) psig (1) H2O (2) Conv.(%) MEK CO2 CO SBA Others 44A 21.5 375 280 122 229 702 9.4 96.0 0 0 1.6 2.4 44B 24.5 375 280 122 482 1208 10.8 94.6 0 0 2.0 3.5 45A 5.8 375 286 92 482 1148 13.4 92.2 0 0 1.9 6.0 45B 9.3 375 286 92 482 1148 12.1 95.1 0 0 1.7 3.3 45C 13.5 375 9 93 482 1150 1.7 95.9 0 0 1.4 2.7 45D 18.5 375 800 121 482 1206 12.9 94.7 0 0 2.0 3.3 45E 21.5 375 800 121 482 1206 10.2 95.7 0 0 2.2 2.1 (1) 99+% butene-1. No N2 was used in the feed to the reactor in these runs. (2) Gas hourly space velocity (cc feed/cc catalyst/hour at STP). EXAMPLE 46 The procedure of Example 41is repeated in two separate runs employing the Rh-Re-Mo sulfide catalyst except that the gas feed to the reactor comprised 60 cc./min. cis-butene-2, 380 cc./min. N2 and 224 cc./min. water vapor, at a pressure of 8.0 psig at the selected temperatures and for the selected period of times, providing the following deserved results: Run 1: 3720C, 4.1 hrs. -- 3.5% butene-2 conversion, 95.9% MEK selectivity, 1.1% SBA selectivity. Run 2: 376iC, 5.2 hrs. -- 3.8% butene-2 conversion, 96.6% MEK selectivity, 1.4% SBA selectivity. No C02 or CO by-products were detected. EXAMPLE 47 The catalyst vacuum impregnation procedure of Example 33(a) was repeated, except that no Pd salt was employed and the following calculated aqueous solutions of ammonium paramolybdate and ammonium perrhenate were used to sequentially impregnate 37.0 cc. of the gamma-alumina; 12.0 cc. of an aqueous solution contains 5.24 gms. of ammonium paramolybdate; 12.0 cc. of an aqueous solution containing 1.63 grams of ammonium perrhenate. The resulting Re-Mo oxide catalyst was then sulfided using the procedure of Example 33(b) and employed in a series of runs for MEK formation from butene-1 as summarized in Table XXXII below. The catalyst comprised 3.7 wt.% Re and 9.7 wt.% Mo, calculated as the elements. No CO2 or CO was detected in any run. TABLE XXXII Gas Feed (cc/min.) % Selectivities Run Time Temp Press. Butene GHSV Butene No. (hrs) ( C) psig (1) H2O N2 (2) Conv.(%) MEK CO2 CO SBA Others 1 0.6 371 8.7 60 224 380 3984 2.5 92.5 0 0 0 9.5 2 2.1 374 9.3 60 224 380 3984 2.4 96.7 0 0 0.5 2.8 3 2.7 365 9.3 60 224 380 3984 3.0 98.2 0 0 0.2 1.5 4 7.8 314 8.0 60 224 380 3984 2.3 99.0 0 0 1.0 5 10.0 369 8.0 60 224 380 3984 2.3 98.6 0 0 0.5 0.9 (1) 99+% butene-1. (2) Gas hourly space velocity (cc feed/cc catalyst/hour). EXAMPLE 48 The Re-Mo sulfide catalyst of Example 47 was employed in a series of experiments to illustrate the adverse affect of butadiene in a butene-1 feed to the process of this invention. In a first run the catalyst is contacted with a butene-l feed comprising essentially pure butene-1 (99+8 butene-1) in the absence of any butadiene and high selectivities to MEK and a high selectivity to MEK was observed, as summarized for run No. 1 in Table XXXIII below. Thereafter, butadiene was substituted for butene-1 (butadiene feed rate = 60 cc/min.) for a total time of 1.2 hours at a temperature of about 3750C and a pressure of about 9.0 psig. After 0.7 hours, about 10 % of the butadiene was converted to product and methyl vinyl ketone was formed in a selectivity of about 23%. After about 1.2 hours, the butadiene conversion dropped to about 3% during the interval of 0.7 to 1.2 hours, and methyl vinyl ketone selectivity was found to be 26%. the thus-treated catalyst was then contacted in a second run (Run No. 2) with a fresh butene-l feed. After one hour, only trace amounts of methyl ethyl ketone were found using the conditions summarized in Table XXXII. To illustrate the catalyst rejuvenation procedure of this invention, the feed to the reactor was changed to comprise 380 cc/hr. of a 10:90 vol:vol oxygen/nitrogen mixture at a temperature of 375C, which was passed over the catalyst at 1.0 hour. Thereafter, the resulting Re-Mo oxide catalyst was sulfided with a gas mixture comprising 190 cc./min. of hydrogen sulfide (6 vol.% in nitrogen), and 220 cc./min. hydrogen at temperature of 375'C for 1 hour, followed by purging of the sulfided catalyst to remove excess H2S with 500 cc./hr. of hydrogen at 3750C for 1/2 hour. Following this rejuvenation procedure the catalyst was again exposed to a fresh butene-1 feed in Runs No. 3, 4 and 5, which is summarized in Table XXXIII. In this run,the rejuvenated catalyst was found to be again capable of forming high selectivities of the desired methyl ethyl ketone from the butene-1. TABLE XXXIII Gas Feed (cc/min.) % Selectivities Run Time Temp Press. Butene GHSV Butene No. (hrs) ( C) psig (1) H2O N2 (2) Conv.(%) MEK CO2 CO SBA Others 1 2.7 383 9.0 60 224 380 3984 2.3 98.9 0 0 1.1 2 1.0 375 9.0 60 224 380 3984 < 0.1 trace - - - 3 0.7 382 8.9 60 224 380 3984 3.0 93.3 0 0 0.6 6.1 4 1.8 379 8.9 60 224 380 3984 1.8 95.9 0 0 0.6 3.5 5 2.3 384 8.6 60 224 380 3984 1.8 96.6 0 0 0.5 2.8 (1) 99+% butene-1. (2) Gas hourly space velocity (cc feed/cc catalyst/hour). EXAMPLE 49 To illustrate the formation of acetone from propylene, the Rh-Re-Mo sulfide catalyst prepared as in Example 46 was tested at the conditions summarized in Table XXXIV and high selectivities to acetone were observed. TABLE XXXIV Gas Feed (cc/min.) Selectivities Time Press. Temp. Propyl- GHSV Propylene IPA (hrs) psig ( C) ene N2 H2O (1) Conv.(%) Acetone CO2 CO (2) Others 2.2 9.3 369 60 300 224 1328 7.4 99.5 0 0 Trace 0.5 5.0 9.3 369 60 300 224 1328 7.1 99.4 0 0 Trace 0.6 7.2 8.6 371 60 300 224 1328 9.7 91.7 0 0 7.6 0.7 9.5 8.6 371 60 300 224 1328 11.7 99.7 0 0 Trace 0.3 10.0 8.7 375 60 380 224 1328 8.2 98.7 0 0 1.2 0.1 11.0 6.1 371 60 0 224 568 12.3 85.8 0 0 Trace 14.2 12.8 6.9 372 60 0 224 568 12.7 91.0 0 0 2.5 6.5 13.3 6.9 369 60 0 224 568 15.3 96.1 0 0 3.5 0.4 (1) Gas hourly space velocity (cc feed/cc catalyst/hour). (2) IPA = isopropyl alcohol. EXAMPLE 50 To illustrate the selective conversion of cyclohexene to cyclohexanone, a series of runs are performed in which a gaseous mixture containing cyclohexene, nitrogen and water vapor is contacted with a Re-Rh-Mo sulfided catalyst prepared as in Example 46, and employing the conditions summarized below in Table '. < XXV. The data thereby obtained are also set forth in Table XXXV. TABLE XXXV Feed Rate Selectivity (%) (cc/min.) Cyclo Time Press. Temp. Cyclo- GHSV hexene (min) (psig) ( ) N2 H2O hexene (1) Conv.(%) CO2 Cyclohexanone 15 18 297 167 236 41 2664 2.1 -- 1.9 30 18 303 167 286 38 2946 1.9 -- 24.1 60 18 302 167 236 37 2640 1.9 -- 15.5 90 18 302 167 224 45 2616 2.0 -- 17.1 (1) Gas hourly space velocity (cc/cc/hr) In each of the foregoing examples, illustrative of the process of this invention, butane by-product was observed to be formed from the butene feeds in selectivities of less than about O.5 mol.%, based on the butene fed to the reactor. Thus, the improved process of this invention allows the formation of the desired ketone in the substantial absence of olefin hydrogenation by-products, that is, the hydrogenation by-products will be generally formed in a selectivity of less than about 1 mol.%, based on the olefin fed. Preferably, monoolefin feeds to the process of this invention are substantially free (e.g., contain less than 1 wt.%) of diolefins or acetylenic hydrocarbons to obtain the highest catalyst activity to form the ketones corresponding to the monoolefin feeds. It will be obvious that various changes and modifications may be made without departing from the invention and it is intended, therefore, that all matter contained in the foregoing description shall be interpreted as illustrative only and not limitative of the invention.

Claims: CLAIMS: 1. A process for preparing ketones in high selectivity which comprises contacting the corresponding olefin in the gaseous phase with water vapor in a reaction zone in the presence of at least one catalyst comprising rhenium or a compound or complex thereof. 2. The process according to claim 1 wherein said catalyst consists essentially of rhenium or a compound or complex thereof and-optionally at least one promoter selected from the group consisting of Group VIB metals and Group VIII noble metals and compounds and complexes thereof. 3. A process for preparing a ketone in high selectivity which comprises contacting the corresponding olefin in the gaseous phase with water vapor in the presence of a catalyst comprising a mixture of (1) an oxide or sulfide of Re, (2) an oxide or sulfide of Cr, Mo, or W, and (3) an oxide or sulfide of Ru, Rh, Pd, Os, Ir, or Pt. 4. The process according to any of claims 1 to 3, wherein said olefin comprises a linear alkene of from 4 to 10 carbon atoms or a cycloalkene of from 4 to 10 carbon atoms. 5. The process according to any of claims 1 to 4, wherein the catalyst is supported on gamma-alumina. 6. The process according to any of claims 1 to 5, wherein said olefin and water vapor are contacted in said reaction zone in the additional presence of molecular oxygen, and the catalyst comprises a compound or complex of rhenium. 7. A process for preparing ketones in high selectivity which comprises passing a secondary aliphatic alcohol having from 3 to 10 carbon atoms in the gaseous phase with water vapor as feeds to a reaction zone con taining a catalyst selected from the group consisting of a compound or complex of rhenium to form the ketone corres ponding to said alcohol. 8. The process according to claim 7 wherein said rhenium catalyst additionally comprises at least one promoter selected from the group consisting of metals of Group VIB and Group VIII noble metals and compounds and complexes thereof. 9. A catalyst useful in the conversion of olefins to ketones which comprises a supported compound or complex of rhenium promoted with at least one compound or complex of a Grout VIII noble metal or Group VIB metal. 10. A 'catalyst useful in the conversion of ole- fins to ketones which comprises a supported catalyst prepared by the steps of: (a) impregnating a thermally decomposable molybdenum compound on a catalyst support, and drying and calcining said impregnated catalyst; (b) impregnating the solids obtained in step (a) with a thermally decomposable rhenium com pound or complex and drying and calcining the thus-produced solids impregnated with molybdenum and rhenium.

Inventors: SAVINI, CHARLES, YEH, CHUEN YUAN
Applicants: EXXON RESEARCH AND ENGINEERING COMPANY
Application year: 1983
Main classification: C07C45
IPC codes: C07C45, B01J23